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JPRS ID: 10355 TRANSLATION PESTIIDE CHEMISTRY AND PRODUCTION PROCESSES BY N.N. MEL'NIKOV

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APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL US,E ONLY JPRS L/ 10355 1 March 1982 ~ Translation ~ ~ PESTICIDE CHEMISTRY A(VD PRODUCTION PROCESSES ~ By . N.N. Mel'nikov _ F~~$ FOREIGN BROi4DCAST INFORMATION SERVICE - FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 NOTE JPRS publications contain information prima-rily from foreign newspapers, periodicals and books, but also from news agency transmissions and broadcasts. Materials from �oreign-Ianguage sources are translated; those from English-language sources are transcribed or reprinte~, with the original phrasing and other characteristics retained. - ,I~eadlines, editorial reports, and material enclosed in brackets are supplied by JPRS. Processing indicators such as [Text1, or [Excerpt] in the first line of each item, or following the _ last line of a brief, indicate how the original information was processed. Where no processing indicator is given, the infor- mation was sumniarized or extracted. Unfamiliar names rendered phonetically or transliterated are enclosed in parentheses. Words or names preceded by a ques- tion mark and enclosed in parentheses were not clear in the original but have been supplied as appropriate in context. Orher unattributed parenthetical not.~s with in the body of an item originate with the source. Time:, within items are as _ given by source. 7'he contents of this publication in no way represent the poli- cies, views or at.titudes of the U.S. Gavernment. ~ COPYRIGHT LAWS AND REGULATIONS GOVERNING OWNERSHIP OF MATERLALS REPRODUCED HEREIN REQUIRE THAT DISSEMINATION OF THIS PUBLICATION BE RESTRICTwD FOR OFFICIAL USE OI~TLY. APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE ONLY JPRS L/10355 ~ � 1 March 1982 PESTICIDE CHEMISTRY AND PRODUCTION PROCESSES Moscow KHIMIYA I TEKHNOLOGIYA PESTITSTDOV in Russian 1974 pp 1-28, 32-47, 60-74, 177-187, 244-247, 257-259, 267-289, 402-410, 471-590, 665-683 ~ � � [Excerpts froni book "Pesticide Chemistry and Production Processes" by N.N. Mel'nikov, Izdatel'stvo "Khimiya'", 768 pagesJ CONTENTS ~ Page Annotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Z Foreword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~ 7 Introductior~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Chapter 1. Forms of Pesticide Use . . . . . . . . . . . . . . . . . . . . . 24 Powders (Dusts) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ' 25. Wettable Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 - Emulsion Concentrates . . . . . . . . . . . . . . . . . . . . . . . . 30 = Aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 - Other Forms o~ Yt~ticide Use . . . . . . . . . . . . . . . . . . . . . . 34 = Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 Chapter 2. Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . 36 Petroleum Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 Chapter 4. Halide Derivatives of Alicyclic Hydrocarbons 41 - General Description of Pesticide Properties . . . . . . . . . . . . . . . 41 Some Rep~esenta::ives . . . . . . . . . . . . . . . . . . , . . . . . . . . 41 _ Hexachlorocyclohexane (HCH)~and Its Analogues . . . . . . . . . . . . 41 _ Polychloroterpenes . . . . . . . . . . . . . . . . . . . . . . . . 52 Chapter 10. Aliphatic Carboxylic Acids and Theiy Derivatives 56 _ Chapter Z2. Aromatic Carboxylic Acids and The:ir Derivatives 67 Benzoic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . 67 Arylalkane Carboxylic Acids and Their Derivatives . . . . . . . . . . . . 69 Chapter 13. Aryloxyalkane Carboxylic Acids and Their De~ivatives 72 General Description of Pesticide Properties . . . . . . . . . . . . . . . 72 ~ Aryloxyacetic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . 7b Aryloxypropionic Acids . . . . . . . . . . . . . . . . . . . . . . . . . 91 - a - [I - USSR - D FOUO] FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAI. USF. ~NLY Chapter 18. Mercaptans, Suliides and Their Derivatives Perchloromethylmercaptan and Its ~erivatives . . . . . . � . , . . � . ~ 94 Bibliography . . . . . . . . . . . . . . . . . . . . . . . ~ . . . . . � 102 , . . . . . . . _ Chapter 25. Organic Phosphorus Compounds . . . . . . . . . . . . . . . . . 104 Chapter 29. .F~eterocyclic Compounds With Three and M~cre :Ie~erocyclic Atoms Per Ring . . . . . . . . . . . . . . . 240 . . Derivatives of Six-Membered Heterocycles . . . . . . . . . . . . . . ' 240 s-Triazine Derivatives. . . . . . . . . . . . . . . . . . . o . . . � 240 Derivatives of Other Heterocycles . . . . . . . . . . . . . . . . . . 25~ . J ~ � a ~ -b- FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 ' ANNOTATION This book is a scientific monograph describing the chemistry of all classes of com- ~ounds used as pesticides, and the production processes for some products. Toxicity data for mammals and fish are presented for most products. ~ The book is interided for a broad range of chemists and process.engineers as well as workers in agriculture, agrochemists, biologists and physicians. zt may be used as a training aid by students at chemical and agr?cultural WZ's. . ~ CCNTENTS ' PAGE Foreword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Chapter 1. Forms of Pesticide Use . . . . . . . . . . . . . . . . . . . . . . 25 Powders (Dusts) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 Granulatesi Preparations . . . . . . . . . . . . . . . . . . . . . . . . . 29 Microcapsulated Freparations . . . . . . . . . . . . . . . . . . . . . . . 29 Pesticide Solutions in Water and Organa.c SoZvents . . . . . . . . . . . . . . 30 ~ Wettable Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 Emulsion Concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 A~rosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 ~ Other Forms of Pesticide Use ~ . . . . . . . . . . . . . . . . . . . . . . . . . 40 _ Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 , Chapter 2. Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . ~2 ~etroleum Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 Coal Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4? Bibiliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 _ Chapter 3. Halide Derivatives of Aliphatic Hydrr~carbons . . . . . . . . . . . 50 General Description of Pesticide Properties . . . . . . . . . . . . . . . . 50 ~Some Representatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 ~ - Sibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 1 FOR .OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY Chapter 4. Halide Derivatives of Alicyclic Hydrocarbons . . . . . . . . . . . 60 ~ General DesGription of Pesticide Propertie~ . . . . . . . . . . . . . . . . . ~60 Some Representatives . . . . . . . . . . . . . . . . . . . . . . . . . : . . . 60 HexachlorocyclohPxane (HQi) and Its Analogues . . . . . . . . . . . . . . . . 60 Polychloroterpenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70 Polychlorocyclodienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 Chapter 5. Halide.Derivatives of Aromatic Hyd~rocarbons . . . . . . . . . . . 96 General Description of Pesticide Properties . . . . . . . . . . . . . . . . . 96 Some Representatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97 DDT and Its Analogs . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107 Chapter 6. tditro Compounds . . . . . . . . . . . . . . . . . . . . . . . . 109 Aliphatic Nitro Conpounds , , , , , , , , , , , , , , , , , , , , , , , , , , 109 Aromatic t:itro Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . 112 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . 114 Chapter 7. Amines and Salts of Quaternary Ait�nonium Bases 116 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128 Chapter 8. Alcohol, Phenols and Ethers . . . . . . . . . . . . . . . . . . . 130 Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130 Fhenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136 Nitrophenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140 Phenol Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148 Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161 Chapter 9. Aldehydes, Ketones and Quinones . . . . . . . . . . . . . . . . 165 Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165 Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 i Quinones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171 Bi.bliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175 Chapter 10. Aliphatic Carboxylic Acids and Their Derivatives 177 Aliphatic Carboxylates . . . . . . . . . . . . . . . . . ~ . . . . . . . . . . 187 Aliphatic Carboxylic Acid Amides and Nitriles . . . . . . . . . . . . . . . . 189 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2(?3 Chapter 11. Alicyclic Carboxylic Acids and Their Derivatives 209 G~clopropane Carboxylic Acid Derivatives . . . . . . . . . . . . . . . . . . . 209 Gibberelins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222 - Other Alicyclic Acids and�Their Darivatives . . . . . . . . . . . . . . . . . 226 Bi.bliography . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . 228 . 2 . ~ FaR OFFICIAL USE ONLY . APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 ;hapter 12. Aromatic Carboxylic Acids and Their Derivatives . . . . . . . . . 232 General Description of Pesticide Properties . . . . . . . . . . . . . . . . . 232 B~nzoic Acid Derivatives . . . . . . . . . . . . . . . . . . . . ~ . . : . . . 236 Oxybenzoic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . 24~ Di.basic Acids and-Their Derivatives . . . . . . . . . . . . . . . . . . . . . 250 ~lrylalkane Carboxylic Acids and Their Derivatives . . . . . . . . . . . . . . 253 ~ibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261 ^hapter 13. Aryloxyalkane Carboxylic Acids and Their Derivatives 267 :~neral Description of Pesticide Properties . . . . . . . . . . . . . . . . . 267 ~ryloxyacetic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . , . . 271 - Aryloxypropionic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . 287 Y- (Aryloxy)-Butyric Acid . . . . . . . . . . . . . . . . . . . . . . . . . 289 r^orms of Use of Aryloxyalkane Carboxylic Acids . . . . . . . . . . . . . . . 291 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292 Chapter 14. Carbanic Acid Derxvatives . . . . . . . . . . . . . . . . . . . 295 - Gener~l Description of Pesticide Properties . . . . . . . . . . . . . . . . . 295 Carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296 , Thio- and Dithiocarbonic Acids . . . . . . . . . . . . . . . . . . . . . . . . 296 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301 Chapter 15. Carbamic Acid Derivatives . . . . . . . . . . . . . . . . . . 303 ~ General Description of Pestici~e Properties . . . . . . . . . . . . . . . . . 303 Aryl N-Alkylcarbamates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307 N-Methylcarbamoyloximes . . . . . . . . . . . . . . . . . . . . . . . . . . . 324 Alkyl N-Arylcarbamat~s . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~327 ~ Bi.bliography . . . . . . . . . . . . . . . . . . . . . . . . . . . e . . 335 ~ Chapter 16. Thio- and Dithiocarbamic Acid Derivatives . . . . . . . . . . . 342 - Genera.l Description of Pesticide Properties . . . . . . . . . . . . . . . . . 342 ~ - Thiocarbamates . . . . . . s . . . . . . . . . . . . . . . . . . . . . . . . . 345 ~ " Salts of Substituted Dithioaarbamic Aci.ds . . . . . . . . . . . . . . . . . . 350. Salts of N,N~-Ethylene-Bis-(Dithiocarbamic) Acid . . . . . . . . . . . . . 354 Dithiocarbamates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362. ~ ~ibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363 ~hapter 17. Urea and ~Thiourea Derivatives . . . . . . . . . . . . . . . . . . 367 ::;eneral Description of Pesticide Properties . . . . . . . . . . . . . . . . 30% � ~ ~v-Alkyl- and N-Cycloalkylurea . . . . . . . . . . . . . . . . . . . . . . . . s71 - rT-A�ryl-N',N'-Dialkylurea . . . . . . . . . . . . . . . . . . . . . . . . . . . 375 - I'hicurea and Its Derivatives . ~ . . . . . . . . . . . . . . . . . . . . . . . . 387 - �.:~uaniciine Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390 ~ ibli.ography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391 _ 3 - FOR OFF'ICIAL USE UNLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OFFICIAL USE ONLY Chapter 18. Mercaptans, Sulfides and Their Derivatives . . . . . . . . . . . . 396 General Description of PeSticide Properties . . . . . . . . . . . . . . . 396 Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . � 397 5ulfones . . . . . . . . . . . . . . . . . . . . . . . . . 399 Perchloromethylmercaptan.and�Its�Derivatives . . . . . . . . . . . . . . . . 402 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409 Chapter 19. Thioc~~anates and Isothiocyanates . . . . . . . . . . . . . . . . . 411 General Description of Pesticide Properties . . . . . . . . . . . . . . 411 Aliphatic Thiocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415 - Aramatic Thiocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418 Isothiocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420 _ Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420 - Chapter 20. Sulfuric and Sulfurous Acid Derivatives ' . . . . . . . . . . . . . 422 Sulfuric Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . ~22 Sulfuraus Acid Derivatives . . . . . . . . . . . . . . . . . . . 424 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429 Chapter 21. Sulfonic Acids and Their Derivatives . . . . . . . . . . . . . . . 430 General Description of Pesticide Properties . . . . . . . . . . . . . . . . . . 430 Sulfonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431 Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432 Sulfonic Acid Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435 ~ Other Sulfonic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . 437 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438 Chapter 22. Hydrazi.ne Derivatives and Azo Compounds . . . . . . . . . . . . 440 Bib~iography . . . . . . . . . . . . . . . . . . . . . . . , . . . . . : . . 445 Chapter 23. Organic Mercury Compounds . . . . . . . . . . . . . . . . . . . . 446 General Description of Pesticide Properties . . . . . . . . . . . . . . . . . 446 - ~Li.xed Aliphatic Organomercuric Compounds . . . . . . . . . . . . . . . . . . . 448 Mixed Aromatic Organomercuric Compounds . . . . . . . . . . . . . . . . . . 457 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460 Cnapter 24. Orqanic Tin, Silicon, German_.um and Lead Comp;,~nds 461 Tin Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461 5ilicon, Germanium and Lead Derivatives . . . . . . . . . . . . . . . . . . . 468 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468 Chapter 25. O:ganic Phosphorus Compounds . . . . . . . . . . . . . . . . . . . y71 = General Description of Pesricide Properties. . . . . . . . . . . . . . . . . . . 471 Paosphorous Acid Derivatives . . : . . . . . . . . . . . . . . . . . . . . . . 476 Phosphoric Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 479 '~^hiophosphoric Aaid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 495 4 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 Dithi.aphosphoric Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . 536 Uyrophosphoric Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 562 ~ Phosphonic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 566 Phosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579 - Chapter 26. Arsenic, Antimony, Bismuth, Iron and Boron Compounds 591 F.rsenic Compounds:,.� . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591 Inorganic Arser.ic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . 591 ~ ' Organic Arsenic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . 593 ` CeFI~~-CH-CIIz-C-CI1 > I ~ OH 0 ~ ci~,n~Qa~ N cia? CeN~~-Cit=Cii-C~CH C�Fi~~-C1i=Cll-C~CM~fir = Cr ~ J? CeFT~~-CH=CfI-C-C-CHz-CHz01i ' CFfzNs C~H�-CTi=CH-C-C-CH;-COOH C~Ff~~-C1~i=CH-C=C-CI~Iz-COOCH~ t s? CeHi~-CFf=CFI-CI1-CF(-CF~z-COOCfI~ t~~ > CeHi~-CI~=Cf 1-CF1=CI I-CFiz-COOH ~ Honeybee attractant released together with secretions from the uterus is an unsatura- ,ted keto acid (1,2,3). It has been determined to be trans-9-ketodecen-2-oic acid, and it may be obta'ined from cycloheptanone (2,8,9): ' Ci~Is I O ~ _F~~o I ~ CH, ~ CH-} ~ yOF I ~a CNz(CC~OCsI l,)q ctr,-co-~cr~,~g-cHO ~ Cfi,-CO-(CFTz)s-CFt=CH-CaOIt and from glutaric aldehyde (2,~10,11) : _ OHC-(CFIz)~-CHO (Ce~f61aP=CN-COOCH~ . CI1=C-CHzRt; AI o~~c_~cf~:),-c~a-cri-coocH, nQO: nzso, cH=c-cti,-c�-~cii:),-ct~=cti�-cooci~, bF~ cw,-co-cti=c.ir-tr.it~),-C(f-=CFI-COOCIi, ~ N igf,0. C}i,-CO-(CH,),-~:f 1-('f 1-COOCN, Cll,�-CO-(~;l{f}4~-CH-=CH-CUOtI The second method is rather simple, and it may be used to make sizeable quantities of the preparation. 7.'he greatest difficulties lie in isolating the pure trans-isomer. Among the natural substituted unsaturated acids, we should mention an insect juve- r~ile hormone--the methyl ester of trans,~rcz'n~3-3,11-dimethyl-7-ethyl-10,11-epoxytri- decadien-2,6-oic acid (I) (17-15): ~ 57 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY u c~ i,-cE i,-~ ~FI-C( (~-CH,-C=CI {-CFIz-CFIz-C.-c:i t-r.oa~cr r, ~:r~, ~sr-r, cri, i - ~ presence of which in the necessary quantities promotes normal deve:lopment of insectsj in excess quantities it disturbs metamorphosis and subsequently caiises the death of the insect. Hormone preparations of this sort have been proposed 1~,o control plant pests (12-19). ~ A relatively simple way for synthesizing juvenile hornione and similar compounds has been developed (15); however, only very pure compounds, ones which 3o not contain _ isomeric impurities, have high activity, and their purification preaents significant difficulties. ' It has been established that the hormonal activity of substances such as juvenile hormone may be amplified by the addition of synthetic synergists (17). The properties of juvenile hormone are possessed by some derivatives of farnesilic , (3,7,11-trimethyldodecatrien-2,6-10-oic) acid (II) (16,18,19): (Cl l~)zC=CH-Cf iz-Ciiz-C=CH -CH~-CHs-C=C1(-COOTi ~ f Cli~ n Esters of 7,11-dichloro-3,7,11-trimethyldodecen-2-oic acid have high activity in particular (18,19). 7,11-Dichloro-3,7,11-trimethyldodecen-2-oic acid (melting point 92-93�C) (III) forms in sizeable quantities when farnesilic acid solutions in methanol are saturated with gaseous hydrogen chloride: (CFI~)zCC l- (CI (z),-CCI-(C( lz),-C--Ct I-COUti CN~ CH, nt Its methyl es~er apparently possess the greatzst activity. The farnesilic acid re- quired for its synthesis may be obtained by oxidation of farnesol (3,7,11-trimethyl- dodecatrien-2-6,10-01-1, which enjoys a certain amount of use in perfume industry. 'it~o preparations have been released as experimental pesticides (19a): entakon (TsR- 515)--the isopropylate of 11-methoxy-3,7,11-trimethyldodecadien-2-4-oic acid (LD50 10,000 mg/kg), and entokon (TsR-512)--the ethylate of 3,7,11-trimethyldodecadien-2,4- -oic acid (LDSp 34,000 mg/kg). 2-Methylene butyrolactone is a factor in the natural resistance of poppies and some other plants to Fusarium oxyspoz~ium (20): = f~=~- I=CH, H~~ O C~0 � 58 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFF[CIAL USE ONLY The pesticidal activity of acids qrows dramatically when hydrogen atoms in the alkyl radical are substituted by halogens. Thus compounds as simple as acetic monohalide possess significant pesticidal activity, and some of them are used in agriculture and public health. ~ ~he pesticide activity of carboxylates is higher as rule than the activity of free acids and their salts. Amides of various aliphatic acids and their halide deriva- tives are the mo~t active. Amides exhibit moderate insecticidal and acaricidal activity, but they are rather strong fungicides and herbicides. More than 20 ali- phatic acid amide~~have achieved practical use in the control of plant weeds and for other purposes. Acid nitriles and thio derivatives as well as derivatives of dibasic aliphatic acids also possess pesticidal properties. The toxicity of fluoroaZkylcarboxylic acids to homeothermic animals depends on the number of CH2 groups separating fluorine from the carbon atom of the carboxyl group. ~'he toxicity of some fluoroalkylcarboxylates (in propylene glycol) to animals is - given below: LD50 mg/kg FCFizC00CFi, . . . . . . . . . . . 15 F(CHz)~COOCzFIe . . . . . . . . . 200 F(CH,),COOCzH6 . . . . . . . . . 160 F C}~s1sC00C,lls . . . . . . . . . 4 F~CHe),COOCz[1, . . . . . . . . . 9 ~ F(CI~z)9COOCzHs . . . . . . . . . 10 F(C~1~),oC00CzHs . . . . . . . . . I00 F(CH,)~~COOCzIIs . . . . . . . . . 20 Compounds with an odd number of CH2 groups are more toxic. This is explained by the fact that compounds with an even number of CH2 groups are oxidized to form fluoroformic acid, and subsequently carbonic acid, while acids with an uneven number of CH2 groups prvduce extremely toxic fluoroacetic acid: FCHz-CHz-CHi-COOH FCFiz-CH=Cfi-COOH _~p=-~ y o FCH~-COOH The toxicity of fluoroacetic acid is associated with a number of inetabolic processes, the most important one of which is formation of fluorocitric acid (21). Salts and some amides of fluoroacetic acid are used as extremely toxic zoocides. Fluoroacetic acid amides may be used as systemic insecticides to control sucking plant pests (22-32) and as herbicides (33). iluoroacetic acid is obtained by reacting monochloroacetates with potassi~n fluoride at 200-220�C under pressure: - +Hr� +ti,~ cic~?,-coocti, _K~~ ec~~,-cooc:~~, _ ~~i.~~~ r�cti,-cooFi , 59 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE ONLY and by causing a reaction between ca~bon monoxide, formaldehyde and hydrogen chloride under pressure: HF CO CH,O FCHz-COOt I Fluoroacetic acid may also be obtained by oxidation of 2-fluoroethanol and a number of other compounds (3A,35). ' . Amides and analides of fluoroacetic acid can be produced in sizeable quantities by _ reacting fluoroacetyl. chloride, fluoroacetan hydride or fluoroacetic acid w~ith the appropriate amines (26,28,32,36,37)s RNH= FCFI~COOI t _N~o FC1~~CONHR or by reacting the appropriate ami.des of monochloro- or. monobromoacetic acids with - potassium fluoride (29,32): XCH,(:ONHR ~ ~CFI,CONHR _ Sodium and barium fluoroacetates-=white crystalline substances that are freely soluble in water--have enjoyed practical use in rodent control. These salts are used as aqueous solutions or, in dietary bait. Their LDSp is 0.22-4 mg/kg. Due to the very high toxicity of thes~ preparations, only specially trained people are allcwe3 to work with them. The amide and anilide of fluoroacetic acid (melting points 108�C and 75-76�C respectively) have also been proposed as zoocides. They are less toxic to verte- brates and safer to use. The toxicity of fluoroacetamide to homeothermic animals (LDSp) is 4-5 mg/kg, wnile the toxicity of fluoroacetanilide is 10-12 mg/kg. N-Methyl-N-'(naphthyl-1)-fluoroacetamide(NQ1FA), obtained by any of the methods de- scribed above (32), has enjoyed some use as a systemic insecticide. It is a white crystalline substance with a melting point of 87-88�C. It is poorly soluble in water and freely soluble in organic solvents. It may be used to control plant pests as a wettable powder or an emulsion concentrate. Its LDSp is 25 mg/kg in rats and 158 mg/kg in mice. : A vezy large number of various fluoroacetanilides and fluoroacetamides have been studied (22-32,36,38), but they have not as yet enjoyed practical application. Fluornacetates and halide phenolates have insecticidal properties (39), while poly- fluoropropionic acid analides possess fungicidal and herbicidal properties (40). . Sodium 2,2,3,3-tetrafluoropropionate--a white, extremely hygroscopic substance with , a melting point of 152�C--has recently enjoyed application as a herbicide ~o control annual and perennial monocotyledonous weeds. It is practically insoluble in hydro= phobic organic solvents. Sts solubility in water at 20�C is about 3,000 gm/liter , 60 . FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPR~VED F~R RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OFFQCIAL USE ONLY _ (41-44). Its LDSp in rats is about 10 gm/kg. Tts AC50 in fish is about 100 mg/liter. It is extremely stable when stored, and it is highly resistant to various external factors. It is used for ~eed control in the form of an aqueous solution containing 900 gm/1it~r active ingredient, in the form of granules with 6 percent active ingredient (Orga-3045 and Orqa-3045-granulyat) and in the form of a granulated preparation combined with diuron (6 and 3�~percent), simazine (6 and 2 percent) and amitrole 44. The prepara- tion's consumption norm is 3-6 kg/ha (active ingredient). The most convenient way to obtain 2,2,3,3-tetrafluoropropionic acid is to react per- fluoroethylene with sodium cyanide in the presence of water in acetonitrile or di- methylformamide, followed by hydrolysis of the formed nitrile by sulfuric acid (45, 46) : +IIgO +~IIqO; +H~SO~ - CzF~ NaCN _Nn~~~> CIiFz-CI',-CN _NH,F~s~~ ' CHFi-CF, COUII The first reaction proceeds at low pressure and a temperature up to 80�C, while the second proceeds at 70-80�C. This acid may also be obtained by oxidation of fluoro- olefins (34) . The pesticidal properties of chloroalkane carboxylic acids have been studied to the greatest detail in recent years. Derivatives of chloroalkane carboxylic acids have achieved the greatest significance as herbicides. In particular, herbididal proper- ties are possessed by mono- di- and trichloroacetic acids, di-, tri-, tetra- and tetrachloropropionic acids, mono-, di- and trichlorobutyric and isobutyric a~ids and many others. The biological activity of halogenated acids is significantly influenced by the position of the halogen in relation to the carbonyl qroup. a-Haloqenated acids possess the greatest activity. Bromo- and iodo- acids have been studied less, but active funqicides and herbicides have been found amonq them (47,48). Monochloroacetic acid: This acid has a melting point of 63�C, it is freely soluble in water and in many organic solvents, and it causes burns on plants. Monochloroacetic acid is now obtained by chlorination of acetic acid in the presence of catalysts (iodine, sulfur, phosphorus chlorides and their combinations): CFl,COOt[ CI~ _Fi~i GICH,COOEI as well as by hydration of trichloroethylene followed by hydrolysis of the resulting alcohol: CIiC1=CClz fIfSO, CICFIz-CCI,-f)SO:,II } -IIzSn~ Flizp CICH,-CCI,OH CICH,-COr.,i CiCtt,-~oc~Ft 61 FOR OFF[CIA~. USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY The first method is used in various modifications in the industry of many countries. Acetic acid is chlorinated at high temperature in the presence of catalysts. Recently sulfur or phosphorus has been used most often as the catalyst, in an amount equivalent to 3 percent of the mass of acetic acid to be chlorinated (49). Chlorination of acetic acid produces a small quantity of dichloro- and trichloroacetic acids as by- - products. By chlorination in harsher conditions this mixture is transformed into tri~hloroacetic acid and is then used to produce herbicidal preparations (50). Acetic acid may be chlorinated in the presence of acetic anhydride (0.07 percent of the mass of monochloroacetic acid obtained) (51). A basic flowchart �or production of monochloroacetic acid using this method is shown in Figure 8(51). ~ y~cycHaA (1) yutnoma ~ HCINa notaOit~CNUt . ~2~ ~ ~ ~ z (3)~ ~ xnop ~4 ~ Ha4~.r,oopupo- S- _ 8~~~ ~ 6 NoNosnop- ~ .~IA'C!lfH/IA ~ ! ~r~tnCm� . Figure 8. Basic Flowchart for Producticn of Monachloroacztic Acid by a Continuous Method: 1--gaging tanks; 2,3--chlorinators; 4--crystallizer; 5--centrifuge; 6--mother liqua~ coZlector; 7--heat exchangers Key: l. Acetic acid 4. Final chlorination 2. Absorption 5. Monochloroacetic acid 3. Chlorine Pure monochloroacetic acid is usually isolated by crystallization from the reaction mixture (or from the distilled reaction mixture); upon cooling, the bulk of the monochloroacetic acid contained in this mixture precipitates out, and the mixture of high-chlorine products and unreacted acetic acid remains in liquid form, and is separated by centrifuqation. ~ Monochloroacetic acid is used in agriculture in the form of its soditun salt, obtained by the acid's neutralization by soda or by sodium hydroxide at low temperature, since at high temperature sodium monochloroacetate transforms readily into glycolic acid. Sodium monochloroacetate is used as a herbicide and a defoliant at a consumption norm o= 5-20 kg/ha. 62 FOR OFFICIAL USE ONI.Y APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE ONLY Monochloroacetic acid and its sodium salt are used to produce important herbicides such as 2,4-D, 2M=4C, 2,4,5-T and others. Use of monochloroacetic acid esters and amides as herbicides and fungicides has also been proposed. Trichloroacetic acids Melting point 57.3�C, boiling point 195�C at 760 mm ~g� Trichloroacetic acid is obtained by direct catalytic chlorination of acetic, mono- chloroacetic and dichloroacetic acids and their mixtures, or by oxidation of the chloral~form of nitric acid: CfT,COOF( C?? CCI~COOF{ CCI,CHO The latter method is somewhat simpler, and it produces a good yield of trichloro- acetic acid. Salts of this acid can be obtained by neutralizing it with the appro- priate basis at the lowest possi.ble temperature, since higher temperature would cause the acid's decompvsition: CCI,COO(~ CHCI~ CO? ~ Trichloroacetic acid is used in agriculture to control monocotyledonous weeds. It is used almost exclusively in the form of salts of alkali metals or amines. Alkali meta.l trichloroacetates are used inainly to control monocotyledonous weeds in sugar beets, alfalfa, sugar cane and other crops, in which case the consumption norms of the preparation are relatively high (12-60 kg/lia). The preparations are applied prior to sprouting or prior to planting, since crops can be injured when the consumption norms are so high. The preparations are practically nontoxic to homeothermic animals. The LDSp of sodium trichloroacetate is 3,300-5,000 mg/kg. Tne glycolic ester of trichloroacetic acid (qlita;c) has enjoyed some use as a herbicide (19a). a,a-Dichloropropionic acid: Boiling point 193-197�C at 760 mm Hg. LDSp 6,000-8,000 _ mg/kg. a,a-Dichloropropionic acid is obtained by chlorination of propionic acid at high temperature (the reaction proceeds better in light) in the presence of catalysts: +xi, CFf~-CFI,-COOH _211C1 * Ci-T~-~CCI,-COOH The technical-grade preparation contains an insignificant quantity of a,s -dichloro- and ~x-cnloropropionic acids. 63 - FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL. USE ONLY a,a-Dichloropropionic acid is used to control monocotyledonous weeds in the form of a water-soluble sodium salt. Sodium a,a-dichloropropionate (dalapon): Melting point 174-176�C (some decomposi- tion occurs). It is produced in the form of an 87-95~percent preparation. To obtain the sodium salt, concentrated acid is processed with 40 percent sadium hydroxide solution in a chilled environment; the crystallized salt is filtered out and dried, and the mother liquor is used as a solvent to obtain new portions of salt. A sufficiently pure salt is obtained in this way with minimum losses. When the pre- paration is neutralized in diluted solutions followed by evaporative concentration, a significant proportion of the preparation decomposes, and a highly contaminated product results. ~ Dalapon is capable of moving through the plant vascular system, owing to which it is highly active against many monocotyledonous plants in relation to which other herbicides exhibit low activity. The consumption norm is 12-40 kg/ha. Alkali metal dichloropropionates react with water to form herbicidally inactive pyruvic acid; therefore storage of their aqueous solutions for a long period of time is not recommended.~ Because the simplest halogenated alkane carboxylic acids are used extensively in agriculture, the metabolism of chloroacetic acids and of dichloropropionic acid in soil, plants, animals and microorganisms has been studied in rather great detail (61). Decomposition of these compounds in soil may be represented by the following general fozmulas: CII,CI-COOIi ~ CH70f1-COOH HOOC-COOII -I ICI -f Izc) CHCIz-COOH - 2F~~ ' OfIC-COOH � IfOOC-COOH +zti,o - CC1,-CO~II - _3F~~~ ' f f00C-COOH +N~O CH,-CCIz-COOI~ _2iiC1. Cli,-CO-COOH Oxalic acid formed upon hydrolysis and oxidation of haloacetic acids transforms, upon further oxidation, into carbonic acid, while pyruvic acid obtained from dalapon may be included in Krebs' cycle to form amino acids and proteins. 2,4,5-Trichlorophenoxyethyl dichloropropionate (erbon): Melting point 49-50�C; boiling point 161-164�C at 4 mm Kg; LDSp 700-1,100 mg/kg. Used as a general herbi- - cide at a consumption norm of 14-20 kg/ha. In addition to dalapon, the sodium salt of a,u,,3-trichloropropionic acid is ~ised in agriculture. At a consumption norm of 4-12 kg/ha this salt produces satisfactory results in the control of monocotyledonous annual weeds. 64 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY Trichloropropionic acid (melting point 65-66�) is obtained by chlorination of _ ~:~rylonitrile followed by saponification of trichloropropionitrile in 50 percent sulfuric acid: +2i~o: CH==CHCN +~C~~ CICHz-CCI~-CN +F- ~ CICH~-CGs-C001{ - -HC( -NH~HSO{ The sodium salt of trichloropropionic acid is obtained in conditions similar to those of obtaining dalapon. The sodium salt of dichloroisobutyric acid has been suggested as a plant sterilizer ~ (it elicits male sterility). Melting point 170-175�C (some decomposition occurs). The boiling point for the free acid is 130-134�C at 35 mm Hg� Its LD50 in rats is ai~out 8,000 mgJkg. It is synthesized as follows: +CI= +N n011 Ci~t2= C-~COUCff, CICI~Iz--CCI -CUOCII~ _G,H oH C[ t~ . ~Cli~ - CICII,-CCI-~CUUNa - I CI-{, Dicnloroisobutyrates have been proposed for use as herbicides (52). ~!'he sodium salt of a,a-dichlorobutyric acid (DBA) is a white crystalline substance. It is freely soluble in water and almost insoluble in hydrophobic organic solvents. It is used in the form of an aqueous solution. It may be obtained by chlorination of hutyric acid followed by neutralization with sodium hydroxide. Its LD50 is more than 2,000 mg/kg. It is used as a general herbicide at a consLUnption norm of 10-30 kg/ha. 2,3,4,5,5-Pentachloropentadienic acid: Melting point 124-125�C. It is obtained when potassium hydroxide reacts with hexachlorocyclopentanone: O ~ cl S /~I ^~.zKOii ~ r.~,C--cC~-cC~=CC~-cc~oK -icci; -it,o - (:I~ CI CI =:n~:cl,:nloropentadienic aci.3 has been proposed as a dessicant and herbicide, but it st:i'_1 ir. the research s:.age. _ I'~r~.e sodium salt of c~Ns~3 -chloroacrylic acid (PREP-defoliant) has a melting point of 1~;1�C, and its solubility in water is 40 percent. It is moderately toxic to animals, ~ ::nd its LDSu in rats is 320 mg/kg. Its toxicity to the goldfish is 5,000 mg/liter _ . t ~ e~osure time of 48 hours. 65 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 . FOR OFF'ICIAL USE ONLY At consumption norms from 2 to 5 kg/ha it quite satisfactorily removes leaves from cotton plants. Derivatives of dichloro- and trichloroacrylic acids and their homologues have also .been proposed as herbicides and fungicides (53-58).. Defoliant and dessicant prnpeY- _ ties are possessed by 2,3,5,5,5-pentachlora-4-ketopenten-2-oic acid, which is a satisfactory cotton dessicant at a cons ~nption norm of 2-8 kg/ha (59), and it ca~ises leaf drep within 6-14 days. Mucochloric acid is an important intennediate product in the synthesis of a number of pyridazone derivatives with herbicidal action. This acid may be obtained by chlorination of furfural in a hydrochloric acid medium: ~ ~ +~it,~; +sr,i, CFfU ai~T UIiC-CC1=CC1-C0~)1f O and by oxidative chlorination of butynediol: +1CIs: +~IpO ~roctr,-c-c-cFrzor~ OFiC-CC1--CC1-COOf1 Depending on the conditions of the process, the yield of mucochloric acid is 50-90 percent of theoretical (60). Because of the high aggressiveness of the reaction medium, great difficulties are encountered in selecting the chlorination equipment and in waste treatment. Mucochloric acid is rather highly poisonous,, and when it settles on exposed skin it causes severe irritation. Blisters recallinq those produced by thermal burns appear. Mucochloric acid and some of its simplest derivatives have fungicidal action, but owing to their high phytotoxicity their use in this direction is im- possi.ble at the moment. 66 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 CHAPTER 12 AR(JMATIC CARBOXYLIC ACIDS AND THEIR DERIVATIVES - Benzoic Acid Derivatives N,N-diethyl-m-toluamide (DETA)--colorless liquid; boilin~ point 111�C at 1 rmn Hg; ~ d~~ 1.0095, �rc~~ 1.5206. Practically insoluble in water, freely soluble in most organic solvents, in ethyl and isopropyl alcohols, in propylene glycol and cotton- - seed oil, in halogen derivatives of aliphatic and aromatic hydrocarbons and in aro- matic hydrocarbons. Its LDS~p in rats is 2,000 mg/kg. The technical-grade preparation contains not less than 95 percent total isomers of N,N-diethyltoluamide, in which case the concentration of N,N-diethyl-m-toluamide must be not less than 70 percent. When applied to the skin, DETA repels blood-sucking insects for 8-10 hours, in contrast to dimethylphthalate, which provides absolute protection from mosquito bites to the skin for only i.5-2 hours. Diethyl-m-toluamide is obtained by reacting m-toluyl chloride with diethylamide in the presence of caustic alkalis or excess amine, or by reacting m-toluylic acid with diethylamine at high temperature in the presence of catalysts: CFI, Cil~ / } ~Cq11R1~N11 / ~ COCI CON(C,NR), The apparent simplicity of the second method is enticing, but conversion does not exceed 70 percent, and in just 10-20 hours the ca.talyst loses its activity and con- -:ersion declines to 30 percent. - flowcnart for production of DETA using the first method is shown in Figure 9 (?.7-30). 67 FOR OFFIC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 FOR OFFICIAL USE ONLY ( 3 ) Qu~m~cnaMaH ( 4 u anop~maN 6 ) ) (1) Z ~ Bo a C,xcame~i~ Bo6dyx n-TOnyr~no- 6aa Kucnoma ~ (2) 4 - TicoNUn- Pacm~op ~rnop~d NnOH - ' ~ ~ . JZ~ - ~ ~ S . /3 14 15 9 ~ , r E ~ ,Q 37A !0 (8) ; (9) (10) . _ ~y + ~ y Figure 9. Basic Flowchart for Production of the Diethylamide of m-Toluylic Acid (DETA): 1--thionyl chloride storage tank; 2--receiver; 3--dichloroethane gaging tank; 4--reactor for m-toluyl chloride synthesis; 5--reactor for DETA synthesis; 6,7,8--gaging tanks for diethylamine, water and aqueous alkali solufion; 9--neutral- izer; 10--reaction mixture distillation vat; 11--heat exchanger; 12--spray trap; 13,14--dichloroethane-water and dichloroethane _ fraction collectors; 25--finished product collector Key: l, m-Toluy..lic acid 6. Compressed air , 2. Th.ionyl chloride 7. Solution 3. Diethylamine 8. Dichloroethane + water 4. Dichloroethane 9. Dichloroethane ~ 5. Water 10. DETA A good yield of m-toluylic acid is obtained by oxidation of m-xylol by atmospheric oxygen at high temperature and slight pressure in the presence of catalysts, usually cobalt salts and organic acids. This reaction also produces a certain quantity of isophthalic acid. T1-i~ mixture is separated by fractional precipitation out of aqueous alkali salt solutions by mineral acids, or by extraction of m-toluylic acid by organic solvents, in which isophthalic acid is poorly soluble. Strong repellent properties are also inherent to hexamethylene benzamide, which is synthesized by reacting benzoyl chloride with hexamethylenamine in the presence of alkali: + r~i i - cqrr:,r:oc:i -i- rrv~ ~ ~o~.r,cc-rv _ - i iz~? 68 ~'OR OFFICIAL USE uNLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007142/09: CIA-RDP82-40854R040500040001-1 _ FOR OFFICIAL USE ONLY This preparation is used in the USSR under the name of benzimin. It is an ingredient of "Tayqa" repellent creaTa. Benzimin does not cause irritation of the skin, its toxicity to man is low, and it remains active for a long period of time. This preparation was first proposed by A. N. Kost, and it is now regularly used to prot~ct man and animals from blood-sucking insects. " The ethyl ester of N-benzoyl-N-(3,4-dichlorophenyl)-alanine (sufiks, VL-17731) (131) is a white crystalline substance with a melting point of 70-71�C. It is practically insoluble in water and freely soluble in organic solvents: 45 percent in carbon, tetrachloride at 20�C, 70 percent in acetone, 20 percent in methanol and about 10 percent in ethanol (weight by volume). Its LD50 in rats is 1,550 mg/kg, _ it is 715 mq/kg in mice, and it is about 1,000 mg/kg in domesticated birds. It is moderately toxic~to fish. ' It may be abtained by benzoylation of the ethyl ester of N-(3,4-dichlorophenyl)- alanine by benzoyl chloride in the presence of hydrogen chloride acceptors: N H-CH-COOC,Fis " I CH~ NaOH \ ~ -F C6fisCOCI _Na~~~- ~l -H'� CI C6EI6C0-N-CI~-COOCzFi6 I / CH, ~ � ~ CI ~ CI :'he preparation is a selective herbicide used to control wild oats in wheat fields. It produces satisfactory results at consumption norms up to 1 kg/ha, and it is safe to wheat. Barley is more sensitive to the preparation. It is used in the crop's tillering phase. The preparation is marketed as a 40 percent wettable powder and as solutions in mineral oils. The ratio of preparation to mineral oil is 1 to 12-14 kg. The total liquid volume (including water for spraying under var:ious conditions) is.from 66 to - 500 liters/ha. Arylalkane Carboxylic Acids and'Their Derivatives c~-Naphthylacetic acid is a white crystalline substance with a melting point of ~ i31-132�C. Its solubility in 100 ml water at 25�C is 41-42 mg, and it is practically nontoxic to mammals. The acid amide melts at 183'=C. 69 FOR OFFICIAL USE 4NLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL U~E ONLY - The most important methods of obtaining a-naphthylacetic acid are as follows: 1. Condensation of monochloroacetic acid with excess naphthaline at 200-220�C in the presence of a catalyst: CI-Iz-CUUN ~ I \ , -I- GCI~Iz-COOH C\./\ \ ~ -nr,~ ~ I ~ . This reaction proceeds for 15-20 hours. The a-naphthylacetic acid yield is about 70 percent. A certain quantity of naphthylenediacetic acid is formed as a byproduct. It is easily.separated owing to its better solubility in water. It may also be separated by distillation of inethylates in a vacuum. This method is used for in- dustrial production of a-naphthylacetic acid (see Figure 10). HC[ 9oaQ 6 B (6) (1)MoNOxnop - � = y~cycNa~ ~r~cnOma 3 S ~ ( 2 ~1aq~man~H ( 3 yYamanu3a~op ~ N~om NaOH 5' ~3 Hd Cr~Utky t~ y pacg~acoBky - ! 12 (7) Z ~ Pacmeop NaCi (5) Figure 10. Basic Flowchart for Production of a-Naphthylacetic Acid: 1--reactor; 2--reactor-extractor; 3--extract settling tank; 4--Nutsch filter; 5--extract qaging tank; 6,7,8--gaging tanks for NaOH, HC1 and water; 9--neutralizer; 10--salt solution collector; 11--resin collector; 12--c4-naphthylacetic acid - precipitation apparatus; 13--vacuum filter Key: 1. Monochloroacetic acid 5. Solution 2. Naphthaline 6. Water 3. Catalyst 7. To drying and packaging 4. Nitrogen _ 2. Hydrolysis of naphthylacetonitrile. The latter is synthesized by reacting chloromethylnaphthaline with hydrocyanic acid salts: 70 - . FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OFFICIAL USE ONLY ' i,H~CI / \ CI~~O; IICI / KCN ' ~ I ~ ~C ~ ~ CHzCN CH=-COOH ' / ~ / ~ \ I / \ ~ / . Z'his method is more complex, but it produces a good yield of pure preparation. 3. Synthesis out of a-naphthylmethylketone using Willgerodt's reaction produces a-naphthylacetic acid with a high degree of purity: COCI1, cn,coct: / \ AtCI~ i \ INH~)~5~~ I I \ / \ / . CHzCONH? CHz-COOFI . ~ \ I ~ ~ \ I ~ The intermediate product in this reaction is a-naphthylacetamide, which may be used without further processing as a plant growth regulator, The a-naphthylmethylketone required for this synthesis is produced by the Fridel-Crafts reaction f.rom naphthylene and acetylchloride in dichloroethane at 34�C. The yield is 94 percent. When the re- _ action conditions are kept optimum, the technical-grade separation contains not more than 3 percent 2-isomer impurities (234). - Esterification of a-naphthylacetic acid by methanol in the presence of sulfuric acid forms a q~iantitative yield of inethyl-a-naphthylacetate (boiling point 122-122.5�C at 1 mm Hg). A quantitative yield of the ester is achieved oaly when the reaction is performed at room temperature; its yielc] decreases dramatically when hzated. _ This ester is used as a 3.5 percent dust in clay (preparatian M-1) to retard sprouting in long-term storage; the consumption norra is 100 gm per ton of potatoes. _ a-Naphthylacetic acid and its amide are also used to thin out apple blossoms and to ' - delay blossoming with the purpose of protecting the blossoms from freezing, and in some other cases. The metabolism of a-naphthylacetic acid, its amide and its methyl ester has been studied. It has been established that the acid decomposes into oxymethylnaphthaline, u-naphthoic acid and phthalic acid. a-Naphthylacetic acid undergoes analogous de- composition when its aqueous solutions are illuminated by sunlight or ultraviolet liqht (235). 71 FOR OFFICIAL USE ONLY ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007102/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY CHAPTER 13 ARYLOXYALKANE CARBOXYLIC ACIDS AND TETEIR DERIVATIVES _ General Description of Pesticide Properties - The aryloxyalkane carboxylic acids and their derivatives that have been studied _ possess weak insecticidal properties, but many compounds of this group are herbi- _ cides, fungicides and plant growth regulators. Aryloxyalkane carboxylic acids have greatest significance as herbicides and plant growth regulators. In terms of the - scale of their production and use, aryloxyalkane carboxylic acids have the lead among preparations of other classes; production of this important group of herbicides is exhibiting a tendency for growth. The physiological activity of many aryloxyalkane carboxylic acids has been studied, and the general dependencies between variations in.activity and structure have been established, thouqh the mechanism of their action upon plants is not yet sufficiently clear (1,102). The physiological activity of phenoxyacetic acid increases when halogen atoms are introduced into its molecuie. Fluorine and chlorine have the greatest influence, while that of bromine and iodine is less signi.ficant; moreover the activity of the compound is al~o affected by the position of the halogen. 4-Halophenoxyacetic acids exhibit the highest activity. Isotneric dichlorophenoxyacetic acids fall into the following order in relation to their physiological activity: 2,4- > 2,5- > 3,4- > 3,6- > 2,0- The herbicidal activity of 2,5-dichloro- and 3,4-dichlorophenoxyacetic acids is so great that they have been proposed for agricultural use together with 2,4-dichloro- phenoxyacetic acid. One favorable property of 3,4-dichlorophenoxyacetic acifl is its greater selectivity of action in comparison with the preparation 2,4-D: Zt is less harmful to cotton, alfalfa, potatoes and suqar beets, but it is highly toxic to sunflower and many dicotyledonous weeds. Among isomeric trichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid possesses the greatest activity; it is clase to 2,4-D in the strength of its herbicidal action. Isomeric trichlorophenoxyacetic acids fall into the following order in terms of their activity: 2~�1~5- > 2,3;1� > 3,~1,5� > 2~3~5� > 1~4,6. ~ I~g~g. . ~2 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007142/09: CIA-RDP82-40854R040500040001-1 FOR OFF[CIAL USE ONLY Among tetrachlorophenoxyacetic acids, anly 2,3,4,5-tetrachlorophenoxyacetic acid displays noticeable physioloqical activity in relation to plants, while 2,3,4,6- and 2,3,5,6-tetrachlorophenoxyacetic acic~s are inactive. Pentachlorophenoxyacetic acid is inactive as a plant qrowth regulator, but it is a systemic fungicide (2). 2,4,6-Trichloro- and 2,4,6-tribromophenoxyacetic acids are inactive as herbicides, and according to some data tt,ey are even antagonists to preparation 2,4-D, but 2,4-dichloro-6-fluoro- and 2,4-dibromo-6-fluorophenoxyacetic acids are similar to this preparation in their activity. 2,4,6-trifluorophenoxyacetic acid, many mixed polyhalofluorophenoxyacetic acids and their derivatives exhibit relatively high herbicidal activity. Introduction of an aliphatic hydrocarbon radical into the benzene ring of the phenoxy- acetic acid molecule raises the compound's activity insignificantly. In this case the activity of 2-alkyl-, 4-alkyl, 2-halogen-4-alkyl- and 4-halogen-2-alkylphenoxy- acetic acids decreases as the alkyl radical increases. A similar pattern is observed when an aromatic radical is introduced into the phenoxyacetic acid molecule. When the benzene ring of alkyl- and arylphenoxyacetic acids is halogenated, their activity rises. 4-Haloqen-2-alkylphenoxyacetic acids are somewhat more active than 2-halogen-4-alkyl- phenoxyacetic acids. Isomeric halomethylphenoxyacetic acids differ especially strongly in their activity. When a second haloqen atom is introduced into the alkylphenoxy- acetic acid molecule, the compound's activity declines in most cases. The same is observed with the addition of a third halogen atom. An exception is 2,4-dichloro- -5-methylphenoxyacetic acid, which exhibits rather strong herbicidal action. This acid is a structural analogue of 2,4,5-trichlorophenoxyacetic acid. Introduction of a fluoromethyl group into the phenoxyacetic acid molecule does not affect its activity as a plant growth stimulator, but it sharply reduces the com- pound's herbicidal ~ctivity. Thus for example, 4-chloro-2-chloromethylphenoxyacetic acid is of no practical interest as a herbicide, while 4-chloro-2-methylphenoxy- - acstic acid (preparation ~M-4C) is broadly employed in agriculture to control di- cotyledonous weeds (3,4). Chloromethylphenoxyalkane carboxylic acids exhibit the properties of systemic fungicides (5,6). A similar pattern is observed when a thiocyanomethyl group is introduced (7), but such derivatives are somewhat more pY!ytotoxic. - Acetylphenoxyacetic aci~s are inactive, apparently due to presence of a carbonyl group in their molecule and the consequent possibility of forming additional hydrogen bonds. The activity of phenylenediacetic acids and carboxyphenoxyacetic acids is probably low for the same reason. Among aryloxyacetic acids containing an alkoxy group in their aromatic ring, compounds - with the alkoxy qroup in position 3 are most active, while 2-isomers are the least ~ictive. By increasing the number of carbon atoms in the alkoxy residue, we can raise activity, but only to a certain limit (C3), after which it falls abruptly. This is possi.bly connected with the substance's lower rate of diffusion in plant cells. Halogenated alkoxyphenoxyacetic acids are less active than acids not containing halogen. Thus 2-chloro-4-methoxyphenoxyacetic acid is close in its ability to stimulate root formation in bean plant cuttings to that of y-(indolyl-3)-butyric acid. 73 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED F~R RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFF'IC[AL USE ONLY _ 4,5-Dichloro-2-methoxyphenoxyacetic acid and its derivatives exhibit noticeable fungicidal activit.y (8). A mixture of aryloxyacetic acids obtained from phenols with a boiling point of 180-200�C, obtained from dry wood distillation, has been proposed for weed control,. This mixture contains up to 40 percent chloroguaiacoloacetic acids (a mixture of iso~rs) and about 25 percent 2,4-dichloro- and 4-chloro-2-methylphenoxyacetic acids. Nitro-, amino-, acylamino-, alkylamino- and sulfo- derivafives of phenoxyacetic acids have low physiological activity. Even 2-nitro-4-chlorophenoxyacetic acid and - its analogues exhibit low activity. However, sulfamidophenoxyacetic acids exhibit fungicidal properties (9,10). Introduction of halogen into the methylene group of 2,4-dichlorophenoxyacetic acid reduces the compounds's physiological ac.*.ivity. Thus 2,4-dichlorophenoxyfluoroacetic _ acid is less active than 2,4-dichlorophenoxyacetic acid, in which case the (+)-form of 2,4-dichlorophenoxychloroacetic acid is a stronger growth stimulator in relation to pea epicotyl cuttings than the (-)-form and the racemic mixture, and it is more active as a herbicide. The activity of 2,4-dichlorophenoxydifluoroacetic acid is lower than that of monofluoro- derivatives. _ Substitution of hydrogen in the methylene group by a hydrocarbon radical decreases the compound's activity as a rule; in this case the more carbon atoms there are in the hydrocarbon radical, the more activity declines. The (+)-forms of stereoisomeric compounds are more active than racemates, while the (-)-forms exhibit low activity, or they are antagonists to plant gr.owth stimulators. Axyloxyacefiylchlorides and aryloxyacetic acid anhydrides do not differ from the acid forms in their activity, since upon hydrolysis they transform into the corresponding acids. Hydroxamic acids are herbicides and rather strong fungicides (11,I2). Esters formed from hydroxamic acids have strong herbicidal action (12-16). The activity of amides, anilides and other similar derivatives is similar in most cases to the activity of _ the correspondinq acids. A ve ry large number of N-substituted amides of aryloxyalkane carboxylic acids (17-33)of both the aliphatic (19,21,24-26,29,31-34) and aromatic (20,22,23,25,30,35,36) series containing the most diverse substituents in the hydrocarbon ring at the nitrogen atom--thiocyanate (19), amino (21), alkylthio (24,28), carbonyl (22,32), trifluoro- methyl (20,23,30), thiophosphoryl (33) and other groups--have now been synthesized - and studied. Aryloxyacetylamino acids exhibit high activity that depends not only on the structure of the aryloxyacetic acid but also on the confiquration of the initial amino acid. This may be connected with the capability of various plant enzymes for breaking aryloxyacetylamino acids down into the corresponding aryloxyacetic acids. Aryloxyacetylates are stronger herbicides than the free acids and their salts. This is usually explained by the higher rate of their penetration through the leaf cuticle. However, this cannot satisfactorily explain the fact that a significantly 74 FOR OFFICIAL L'5E ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 I 1~7C[AL U5'E UNLY lower dose of the ester is required to achieve the same effect as the salt (a two- to three-fold difference) (37). The herbicidal activity of the esters of high molecular weight alcohols is.lower than that of esters of low molecular weight alcohols, which is connected in all probability with their lower solubility in lipoids and waxes and their lower rate of diffusion in plants. The activity of the salts of aryloxyacetic acids formed from various organic bases is 1.2-1.7 times greater than the activity of the salts of these acids made with alkali metals. It may be possible that the herbicidal action of amine salts in- creases owing to change in the surface tension of their aqueous solutions. Other factors responsible for the higher activity of these salts have not yet been established. In certain cases aryloxyacetic acids dissolved in organic solvents exhibit higher herbicidal activity than do their salts and even their esters. When hydroxyl oxygen in the carboxyl group of aryloxyacetic acids is substituted by sulfur, significant changes do nok~ occur in the compound's physiological activity, whxle substitution of the ester oxygen by sulfur or by other diatomic groups re- duces the compound's activity. - A large number of aryloxyalkanethiocarboxylates have been synthesized. Some of them may be of interest as herbicides and dessicants (38-41). Esters made with substituted benzyl alc~hoZs (42), with heterocyclic oxygen-containing (43,46), phosphorus-con- taining (44) and nitrogen-containing compounds (45,46) and with dithiophosphoric .acid derivatives (47) also exhibit herbicidal properties. Arylthio- and arylsulfonyl- alkane carboxylic acids and their derivatives exhibit fungicidal and bactericidal action (48). Naphtnoxyacetic acids are significantly inferior to phenoxyacetic acids in their activity. Of the naphthaxyacetic acids, S-naphthoxyacetic acid is the most active. Introduction of halogens and other substituents into the naphthaline ring reduces the compound's activity. However, the esters and amides of these acids as well as the appropriate derivatives of ~c- and R- pilenoxypropionic acids (34,35,49,50) are of certain practical interest because they are effective against a number of weeds resistant to other preparations made from this group of compounds. Fluorenyloxy- and acenaphthenyloxyacetic acids and analogous derivatives of other polycyclic hydrocarbons are weak herbicides, 3nd they offer no practical interest. Aryloxyalkane carboxylic acids [Ar0(CH2)nC00Fi] with an odd number of.methylene groups has herbicidal activi.ty in relation to many dicotyledono~xs plants, while acids con- taining an even number of inethylene groups do not display herbicidal action. The explanation for this is that most plants (except the lequnes) subject aryloxyalkane carboxylic acids to S-oxidation, as a result of which tne former group of compounds is transformed into the appropriate aryloxyacetic acids while the latter group is transformed into inactive phenols: ArU(CI~I,),COQl1 - ~ p1 ArOCH,COOH -2COy: -2UqU - ArU(Clli)lCO01( - ArOC0U1-{ r Ar0(I -2C01; -~11,0 -.(;Q~ 75 ~OR O~F'K7AI. UB~ ONI.Y APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-40850R000500040001-1 F~OR OF~AL USE ONLY In leguminous plants, B-oxidation of Y- (aryloxy) -butyric acids to the corresponding aryloxyacetic acids does not occur, and therefore y-(aryloxy)-butyric acids can be used successfully to control dicotyledonous weeds in fields of leguminous crops. As the number of inethylene groups in acids with an odd number of inethylene groups in- creases, their herbicidal activity decreases. Nitriles of aryloxyalkane carboxylic acir~s display the same form of activity that acids do (51,52). Thus the nitriles of fluoro- and fluorochlorophenoxyalkane carboxylic acids are strong herbicides (51), and the nitrile of pentachlorophenoxy- acetic acid (melting point 158-160�C) is a strong furiqicide (52). Aryloxyacetic Acids Aryloxyacetic acids and their various derivatives are used as herbicides to control dicotyledonous weeds in cereal grain plantations and brush and tree seedlinqs on meadows, to destroy :uidesirable trees when cleaning terrain for construction of hydro- electric power plants and so on. Compounds in widespread use include 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro- -2-methylphenoxyacetic acid (2M-4C), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and their derivatives. 3,4-Dichlorophenoxyacetic acid, ?.,4-dichloro-5-methylphenoxy- acetic acid, 4-chlorophenoxyacetic acid and other compounds are presently undergoing industrial experimentation. 2-Naphthoxyacetic acid is a plant growth requlator. It is used in some countries in small amounts to obtain seedless tomatoes. All aryloxyacetic acids are weak acids. Their dissociation constants are within 5.2�10'~*-25�10-4. . - Aryloxyacetic acids are similar in chemical properties to other carboxylic acids. They typically form acid chlorides and anhydrides, amides, esters and many other derivatives. When aryloxyacetylchlorides react with silver phosphate, the aromatic ring undergoes alkylation: t 2~a~p0~ , 6ArOCH~COCI ~aQ~i, t 3AraCH,C00CFi,0Ar -r,oa; -aco ~OH 3Ar ~CHzCOOCHzOAr Silver salts oY aryloxyacetic acids react with bromine in approximately similar fashion: + Br, 2ArOCH:COOA~ _zAQer;~o? ArOCHzC00CH=OAr 76 " I~OR ORRK7AL UB6 ONI.Y APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 F~OR OFF~AL tlSE ONLY ~ When alwainum chloride reacts with aryloxyacetylchlorides, ring foxmation occurs and the corresponding coiunaranone derivatives are obtained: � , OCEi=COCI a~~~~ / O ~ I -Y \ I ~ . _ I~ O When aryloxyacetic acids are mixed with aldehydes Perkin's reaction occurs, with the corresponding derivatives of cinnamic acid forming: - ArOC11~COOK Ar'CHO _~i~o ArO-C-COOK ~HAr' When aryloxyacetic acids are mixed with concentrated nitric acid, mono- or dinitro- aryloxyacetic acids form depending on the nitration conditions and the structure of the initial acid. . When aryloxyacetic acids are subjected to halogenation, the corresponding haloc,en ~ derivatives are formed, some of whic;~ are obtained rather pure and in good amounts. This reaction is often used for industrial synthesis of 2,4-D, 2M-4C and 4-fluoro- ~ phenoxyacetic acid. Chlorination and bromination proceed the most easily, while iodination is significantly more difficult. Some aryloxyacetic acids are not iodinated by free iodine. Hydrolysis of the simple ester bond proceeds relatively easily when aryloxyacetic acids are heated together with acid halides. The reaction proceeds quickly with hydrogen iodide and significantly more slawly with hydrogen chloride. The more acid tr.e phenol obtained upon hydrolysis, the faster this reaction proceeds. Esters are obtained in~good amounts when aryloxyacetic acids interact with alcohols in the presence of catalytic quantities of sulfuric acid or other similar compounds. The reaction between aryloxyacetic acid salts and dimethylsulfate (53) or between the acids themselves and tetramethylamnwnium hydroxide (55) is used to synthesize methyl ethers of these acids, which are use~: in chromatographic analysis. Several general methods of obtaining aryloxyacetic acids are known. 1. Oxidation of aryloxyethanols by various oxidants or oxygen in the presence of catalysts: - Ar0-CH~-Ci~IzOH Ar0-CIIz-COOH -i i,o 77 F~OR OI~FiC1AL U~ OM.Y ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007142/09: CIA-RDP82-40854R040500040001-1 ~10R AF~~i. USE ONLY This reaction produces a very small yield of aryloxyacetic acid. When oxidation occurs in the presence of platinum catalysts, the yield is higher but the productivity of the catalyst is low. 2. Oxidation of unsaturated phenol esters, for example arylallyl esters, 1-aryloXy- -2-chlorobutene-2 and others: Ar0-CFlz-CN=CH? - +SO Ar0-CH,-COOH -co:: -~i,o 3. Synthesis of aryloxyacetic acids by way of arylchloromethyl ethers, obtained by chlorination of the corresponding anisoles in the presence of phosphorus penta- chloride: + i ~so ArOCFI ArOCH CI +NaC~ ArOCFi CN ' -~ic~ 7 -NeC1 ~ _N11~ ArOCH,C00H This is the way 2,4-dichlorophenoxyacetic acid is syr~thesized from anisoles with a 60 percent yield. 4. One of the most widespread methods of obtaininq aryloxyacetic acids is to react alkali metal phenolates with the salts of monochloroacetic acid: +CICII~COONa +HCI ArONa _Nact ' ArOCtI_COONa ArOCiIzC00H -NaCI _ This reaction may be performed both in aqueous solution and in organic solvents using excess phenolate, or in the presence of table salt with the purpose of reducing hy- drolysis o~ sodium monochloroacetate, and so on. When carried out without pressure, the optimum temperature for the process is 105-107�C. 5. Aryloxyacetic acids may also be obtained by way of the esters or amides of haloacetic acids: } ,(Cf IgC00R + NsOtf ArONa _N~x } ArOCNzCOOR _ROH + 1 iCl - ArOCE1~COONa _-N~ ArOCH~COOH +cicH,covt+, ~i,o; ?i~so, ArON;~ _N,~~ ArOCFI~CONFI, _N~i HSa~~?- ArOCFItC00lf _ The latter method is only of preparatory significance in the synthesis of aryloxy- - acetic acids in the laboratory. 6. Aryloxyacetic acids may be obtained by reacting phenolates with cnlorocyanacetates, - but this method is only of theoretical significance: 78 . F~OR aRRK1AI. US~ OM.Y APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2447/02/09: CIA-RDP82-44850R444544444441-1 F~OR OF1F'fCtAL USE ~NI.Y CN +CI~fICOOCztty NaON; IIzO ArONa ArOCt-ICOOC,H6 -NaCI { -NIl~; -CZtlSOH CiY + 2HG ArOCII(COONa)z ArOCH,COUH _ ~ -NoCI; -COi 2, 4-Dichlorophenoxyacetic acid (2, 4-D) is a white crystalline substance with a melting point of 141�C and a boiling point of 160�C at 0.4 itIIn Hg. The pure acid is practically odorless. Not m~re than 0.3 percent dichlorophenol is pennitted in technical-grade preparation. Its solubility in water at 20�C is 540 mg/liter; - solubility in 100 gm solvent is, at 25�C, 130 qm for ethanol, 243 gm for ester, 0.67 gm for toluol and 0.1 gm for n-heptane. It is readily soluble in benzene, carbon tetrachloride, acetone and tetra- and pentachloroethanes. The dissociation constant is 2:i ~ 10-4 . 2,4-Dichlorophenoxyacetic acid is stable when stored as solutions in various solvents, ' and when stored in ..:rystalline state;.it may decompose to a slight extent when ex- posed to ultraviolet light. It forms stable salts with inorganic and organic bases. The properties of some salts of 2,4-dichlorophenoxyacetic acid are shown below: Solubility in 100 gm Water, - Melting gm (at Indicated Salt Point, �C Temperature, �C) Ammonium - 1. 2( 31. 5) Sodium (monohydrate) 216-218 27.5 (0) 33.5 (20) 50.6 (30) 74. 6 (45) Potassium - 7 (20) Calcium - 0.025 (20) Magnesium - ~.17 (20) Methylamine 157-159 450 (20) n-Butylamine 9~-94.5 1.8 (30.5) Allylamine 106-107 1.2 (31.5) Benzylamine 138-319 1.6 (31.5) - Monoethanolamine 145-147 >50~ (20) Dimethylamine 85-87 Good (20) Diethylamine 129-131 >50~ (ZO} Di-n-butylamine 107-109 1.2 (31.5) _ Diallylamine - 710 (32) Diethanolamine 9=~-94.5 480 (30) Tricthylamine - 340 (20) - Triethanolamine - 440 (32) Morpholine 136-138 220 (30) Piperidine 131-132 230 (31) 79 ~'aR OF'FiC7AL US~ ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2447/02/09: CIA-RDP82-00850R000500444441-1 ~ FOR OE'[7C[AL USE ONLY - The salts of bivalent metals are poorly soluble in water, which is why a precipitate = may form when 2,4-dichlorophenoxyacetic acid is dissolved in hard water. To avoid this, complexones (Trilon B) are added to technical-grade 2,4-D preparations. With lengthy boiling of 2,4-dichlorophenoxyacetic acid together with hydrobromic or hydrochloric acids, it may decompose: OCHzCOOH OH = / Cl Fiz~, IiC! CI , ~ \J HOCHlCOOFt \ ~ ~ i Chlorination with gaseous chlorine forms 2,4,6-trichlorophenoxyacetic acid, but at 200-205�C breakdown products have been discovered: 2,4-dichlorophenol, bis-(7.,4,- -dichlorophenoxy)-methane and others. Chlorination of the ethyl ester of 2,4-dichlorophenoxyacetic acid at 195-210�C without a catalyst produces 2,4-dichlorophenoxychloro- and 2,4-dichlorophenoxydichloroacetate, _ dich.loroacetate and 2,4-dichlorophenylchloromethylate. . The principal product of this acid's nitration by nitric acid or a nitrating mixture is 2,4-dichloro-4-nitrophenoxyacetic acid with a slight amount of 2,4-r3ichloro-6-nitro- phenoxyacetic acid impurity: OCHzC00!! OCFi,C00H OCH. COOfI ~ ~ CI t~NO, I Ct O:N~ / CI + Y~ OzN CI ' . ~ CI A large number of amides having high herbicidal activity have been obtained by re- acting 2,4-dichlorophenoxyacetylchloride with amino acids: , OCIizCOCI OCFizCONHRCUGH / I f17NItCOOfI; KOtf / C~ \ -KCI: -tiz0 ~ CI ~ Some species of microor anisms oxidize 2 4-dichloro heno g ~ p xyacetic acid into 4-chloro- pyrocatechin (by way of the oxy derivative and 2,4-dichlorophenol). 2,4-Dichloro- _ phenoxyacetic acid has antiseptic properties; this is aspecially true of its phenol esters. 80 ~OR . 'ICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 ILY 2,4-D is moderately toxic to mammals. When introduced orally into experimental animals, the LDSp is 375-1,000 mg/kg; the maximum safe dose in monkeys is 214 mg/kg. ; It is presumed that the lethal dose of 2,4-D in� man is about 15 gm, The norm set in the USA for 2,4-D traces in foodstuffs is 5 mg/kg. A large number of inethods of obtaining 2,4-D are known, but only two have practical significance to industrial production. . 1. Condensation of the salts of monochloroacetic acid with 2,4-dichlorophenolates ; of alkali metals or ammonium, in water or in a water-free medium (55-59); ONa OCIizCOOFI J Cl i. CICH~COONa / CI -NaCI C1 C~ To decrease hydrolysis of monochloroacetic acid, the reaction may be performed with excess 2;4-dichlorophenolate, which is removed after oxidation of th~ reaction medium by distillation with live steam. The yield from 2 moles of sodium 2,4-di- _ chlorophenolate and 1 mole of sodium monochloroacetate attains 94 percent of theoret- ical, while without excess phenolate the yield under similar conditions does not exceed 83 percent.. 2,4-Dichlorophenol distilled away with steam may be later re- turned to the process. Adding sodium chloride has been sugyested as a way to suppress hydrolysis in the reacticn mixture. - It should be noted that the purest possible 2,4-dichlorophenol would best be used to - produce 2,4-D; this would mean lower waste of expensive monochloroacetate in the formation of byproducts. Additionally, the 2,4-D obtained from pure 2,4-dichlorophenol is higher in quality. The technical-grade preparation almo~t always contains a small quantity of 2,4-di- chloropr~enol, and owing to this it has an unpleasant odor. 2,4-Dichlorophenol is obtained by direct chlorination of phenol by chlorine, followed by purification of the chlorination products by rectification. Perfozming chlorina- tion at a temperature somewhat .tibove the melting point of phenol is usually recommended. Chlorination at higher temperatures produces a large quantity of 2,6-dichlorophenol as a byproduct. Very pure (98 percen~) 2,4-dichlorophenol may be obtained by chlori- nation of phenol in liquid sulfur anhydride at a temperatu_e not exceeding the boiling point of sulfur anhydride, which hinders formation of the 2,6-isomer and practically - excludes the possibility of obtaining 2,4,6-trichlorophenol. Sufficiently pure 2,4-dichlorophenol is also obtained when phenol is chlorinated in nitromethane (the phenol concentration should be about 25 percent, the temperature is 40�C) (61-63). 2,4-Dichlorophenol may be purified by extraction of the 2,6-isomer with alkali (60), since the latter's acidity is higher. - 81 - FOR OF'FICIAL USL ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 ~ o~c~ac usE oNLY 2,4-Dichlorophenol may also be obtained by alkaline hydrolysis of a mixture of iso- meric forms of trichlorobenzene (from nontoxic isomers of hexachlorocyclohexane), but the resulting product is a mixture of isomeric dichlorophenols, in which the concentration of the needed isomer does not exceed 25 percent. 2,4- and 2,5-isomers of dichlorophenol may be separated by sulfation with sulfuric acid at 50-100�C: The 2,5-isomer is separated in the form of sulfonic acid, since it is sulfated more easily than the 2,4-isomer (64). Separation may also be . achieved by precipitation of the binary compound of 2,5-dichlorophenol and urea out of their solutions in organic solvents (65). The basic flowchart for production of 2,4-dichlorophenoxyacetic acid by this method (1) is shown in~Figure 11. ~ 1 ~,+;vNoxncpuKCycNa.q ~ 4 ) Kucnom� 1,4 -,Q~zn~p~aeNa.v.+Buoa SO�/u~ N~OI I ~ S ~Z) 4-~(urnvo e- ~ir~ y - ti�o.o ~ J 3 Boda ~ 4-/j u a,vop. (3) Boda t 6 (2) tici -8 ~ ~.9 /0 Z, 4 ;Q (5) Figure 11. Basic Flowchart for Production of Preparation 2,4-D: 1--reactor for synthesis of the sodium salt of 2,4-D; 2--intermediate storage; 3--apparatus for removal of excess 2,4-dichlorophenol; 4--2,4-dichlorophenol dis- tillation uni.t; 5--heat exchanger; 6--settling tank; 7--collecting tank for 2,4-D sodium salt solution; 8--2,4-D isolating apparatus; 9--centrifuge; 10--dessi- Key: cator - 1. Monochloroacetic acid 4. 2,4-Dichlorophenol + water 2. 2,4-Dichlorophenol 5. 2,4-D 3. Water 2. Chlorination of phenoxyacetic acid or its esters. Chlorine, sodium hypochlorite, a mixture of sodium chlorate and hydrochloric acid, sulfuryl chloride and chloramines can be used as chlorinating agents. Phenoxyacetic acid is chlorinated with chlorine both in an aqueous medium and in organic solvents and in melt (66,67): UC[I~CUUI( ()CH~CnOH / I + /~~CI -'t~ I~ ~ I - I C~ 82 FOR OFFiC1AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 The product obtained by this method does not contain 2,4-dichlorophenol. The im- ourities it contains include 4- and 2-chlorophenoxyacetic acids, 2,4,6-trichloro- phenoxyacetic acid and 2,4,6-trichlorophenol. The 2,4-D yield, when calculated in relation to total chloropheno:cyacetic acids, is more than 90 percent, but this method produces a product of lower quality than that obtained from purified 2;4- dichlorophenol. Phenoxyacetic acid necessary for production of 2,4-D by the chlorination method is _ formed by reacting sodium phenylate with sodium monochloroacetate at high tempera- ture, the yield being 80-90 percent: CslisUNa CICII COONa +~~c~ ~ -NaCI C6tIsOCN~COONa _N --Y CdHSOC1I,COOH The metabolism of 2,4-dichlorophenoxyacetic acid in various environmental objects has been studied (68-80). It has been established that the first stage of inetabolism in plants is hydroxylation (71,79,80), which proceeds to fonn 2,3- and 2,5-dichloro- - -4-oxyphenoxyacetic acids. Under the influence of soil microorganisms, not only does the ring undergo hydroxylation, but also the ester bond breaks down and the aromatic system is destroyed (70,71,74). It should be noted that when 2,4-D is applied re- peatedly to soil, its decomposition accelerates. Decomposition of 2,4-dichloro- phenoxyacetic acid may be represented in general form as follows: i CII,COOtI OCHzC00F! / G CI , + CI oi r of~ ~ ofi oc~{,cooFi oi~~ I Of I , CI OF~ CI~ I `CI ~ ~ ~ - ci _ j ~ . o ~ t~ooc ~ cooii coo~i ~ ,CJ ~ cfi-coo~i ~ ~ 0 ci ~ Acetates and dicarbox1lic acids ~ Cli-('OOfI - 83 FOR OFFICIAI. USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE ONLY Esters of 2,4-dichlorophenoxyacetic acid: The effectiveness of esters derived from 2,4-dichlorophenoxyacetic acid against various weeds is significantly higher than the effectiveness of its salts and of its various other derivatives. Destruction of _ an equal amount of dicotyledonous weeds by esters requires consumption norms that are two to three times lower than the consumption nonns for the sodium salt (as corrected for the acid). In a number of cases esters act upon weeds against which salts are not very effective. 2,4-Dichlorophenoxyacetates are enjoying increasingly broader use in agriculture. They noea represent more than 50 percent of the tatal production of all other deriva- tives of this acid. Lower alkyl esters of 2,4-dichlorophenoxyacetic acid (ethyl, isopropyl, butyl and so on) have relatively high volatility, and their vapors may injure crops sensitive to this acid located on plots neighboring those being processed. As molecular weight increases, the volatility of the esters decreases. Thus the vapor pressure of iso- octyl ester is almost 17 times lower than the vapor pressure of butyl ester. However, high molecular weight esters such as, for example, cetyl ester, are less effective, apparently due to their poor solubility in plant juices and thEir slow movement through the plant vascular system. The properties of some esters of 2,4-dichlorophenoxyacetic acid (C12C6HgOCH2C00R) are shown below: Melting Boiling Point, �C (at R Point, �C Indicated Pressure, mm Hg) Cf1, . . . . . . . . . . . . . . . . 43 I19 (I,0) C~f-(S . . . . . . . . . . . . . . . 15,2-15,4 149-150 (I,0) (GI,);CH . . . . . . . . . . . . . 24 183 (18,0) CN,(CIlz)~CH: . . . . . . . . . . 9 146-147 (I,0) (Cli,),CfICHz . . . . . . . . . . . 17 133-134 (I,0) CH,(Cli.)~CH; . . . . . . . . . . 15 160 (2,0) (CFI~)~CliC1I,Cfl, . . . . . . . . . - 136-138 (I,0) Cl1,(Cf(J)~Cf(((:,lis)Cil, . . . . . . 12 173-174 (0,5) CFI,(CI~,)6C11: . . . . . . . . . . . - 173-174 (1,0) CII,(CFI.),CH, . . . . . . . . . . . 43 - CII~C(:1=(:II(:II, . . . . . . . . . 33-34 186-188 (I,0) 2,d�ClzCefl~UCHtCfi~ . . . . . . . 88 Does not su}~limate ~~Ctl~ . . . . . . . . . . . - 197- 198 (2,0) / O Of the large number of esters of this acid that have been studied, the ethyl, isopropyl, butyl, amyl, heptyl, octyl and isooctyl, chlorocrotyl, polypropylene and polyethylene glycol, and other esters have enjoyed practical use. 2,4-Dichlorophe*!~xyacetates are produced industrially by esterification of the acid by appropriate alcohols, or by chlorination of phenoxyacetates. Esterifica- tion is usually perforrned in the presence of acid catalysts, in which case water is distilled dway in the form of an azeotropic mixture with an organic solvent. 84 FOR OFF[ClAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFF'ICIAL USE ONLY The basic flowchart for production of 2,4-dichlorophenosyacetates by esterification of the acid by alcohol followed by azeotropic distillation of water is shown in _ Figure 12. ~ ~ 1) 2, 4-,q l'n~pm ~ Bada ~ z ) C~~pm e - (-3~aman~aa- BvJa y mop ~ 3 ! C~up 2 l . ~6 acno Z 3Myn6ta- ~ (7 0~ ~ s s S 7 Ha ' pac~nacoBKy(8) Figsre 12. Basic Flowchart for Production of Esters of 2,4-Dichlorophenoxy- acetic Acid: 1--ester synthesis reactor; 2,3--filters; 4--~ster collector; 5--apparatus for acquisition of ester emulsion con- centrate; 6--intermediate storage; 7--finished product collectc..~; 8--heat exchanger; 9--water removal apparatus; Key: . 1. 2,4-D 5. Water - 2. Alcohol 6. Oil 3. Catalyst 7. Emulsifier 4. Alcohol + water 8. To packaging 2,4-Dichlorophenoxyacetates may be obtained by chlorination of phenoxyacetates in the presence of catalysts. The esters obtained in this way contain 96-97 percent of the required isomer (60). The 3-chlorocrotyl ester of 2,4-dichlorophenoxyacetic acid (crotyline) is obtained by reacting dichlorobutene with the sodium salt of this acid: OC! 1zC0UNa OCH~COOCI-irC11=CCICII~ ~ +cicu,50.0 Diethanolamine 157-159 >50.0 ~ The principal m^thod used to synthesize 2,4,5-trichlorophenoxyacetic acid is to heat concentrated aqueous solutions of 2,4,5-trichlorophenylates anci monochloroacetates of alkali metals at pH 10-12 and a temperature of 103-107�C. CI C1 CI-~ ~ ONa CICFIzC00Na CI-" "-OCH~COONa -NaCI ` ~CI ` . ~CI This process may be performed in butanol, but this method is less convenient since greater difficulties are encountered in removing, from the 2,4,5-trichlorophenoxy- acetic acid, trichlorophenol that had no~ reacted with monochloroa.cetate. _ When sodium hydroxide reacts with 2,4,5-trichlorophenol small quantities of tetra- chlorodibenzodioxine form as a byproduct. Not only does this compound exhibit teratogenic action, but it also severely irritates the skin. This was a cause of occupational illnesses among workers (87). Formation of tetrachloradibenzodioxine proceeds as follows: CI� / I 011 tNa01{ ~=1 / I I~ ~ CI 2 ~i~~/\ r CI ~ CI -1NaCt; -~~,o /\\k~ i'~ CI ~ CI 90 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFIC[AL USE ONLY Impurities are removed from 2,4,5-trichlorophenoxyacetic acid by crystallizing its , ~alts (89). - 2,4,5-Trichlorophenoxyacetates are obtained by esterification of the acid by the appropriate alcohols and distillation of water in the form of an azeotropic mixture with organic solvents (90,92). The melting and boiling points of some esters of this acid are shown below: ' Melting Point, Boiling Point, �C (at Ester �C Indicated Pressure, mm Hg) Ethyl 66-67.5 - Isopropyl 46 - , n-Butyl 29 - Amyl 15 - n-Hexyl 26 - n-Octyl - 187-189 (0.3) n-Nonil 43 - 2-Methoxyethyl - 145-150 (1.0) 2-Methoxypropyl - 148-152 (1.0) Phenyl 116-117 - Pentachlorophenyl 269-270 - 2,4,5-Trichlorophenoxyacetates are used as herbicides against undesirable woody plants when clearing pastures,and against trees on land to be flooded in connection with construction of hydroelectric power plants. T'ne sodium salt of 2, 4, 5-trifluorophenoxyacetic acid is used as a plant growth st:.mu- lator (to obtain parthenocarpic tomatoes). In addition to the arylox~acetic acids described above, a large number of other compounds of this class have been synthesized and studied, and are now attracting a certain amount of practical attention as well. The melting points of some of these compounds are shown below: Acid Melting Point, �C 4-Chlorophenoxyacetic acid 159-160 4-Fluoraphenoxyacetic acid 117 2,5-Dichlorophenoxyacetic acid 157 3,4-Dichlorophenoxyacetic acid 156 2,3,4-Trichlorophenoxyacetic acid 141 2,4-Dichloro-5-methylphenoxyacetic 143 acid 2-Naphthoxyacetic acid 155-156 tiryloxypropionic Acids - As was indicated above, B-aryloxypropionic acids do not possess pesticidal proper- ties, and in this connection there is no interest in using them in agriculture. a-Aryloxypropionic acids are active herbicides and plant growth regulators. 91 FOR O~FICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007102/09: CIA-RDP82-00850R000500040001-1 F'OR OFFIC[AL USE ONLY cc-(4-Chloro-2-methylphenoxy)-propionic acid (2M-4CP) is a white crystalline substance with a melting point of 94-95�C. Its solubility in 100 ml water at 20�C is 0.06 gm. The solubilities of salts in water at 20� are: 32 percer~t (corrected for acid) for tne potassium salt and 58 gm in 100 ml for the diethanolamine salt; solubilities in 100 ml water at 0�C are: 26 gm for the sodium salt, Q.45 gm for the calcium salt and 4.5 gm for the magnesium salt. The free acid and its salts are stable when stored. The active form of the acid is the (+)-form. Its Ln50 in mice is 650 mg/kg. 2M-4CP is used against weeds in the form of salts of alkali metals or amine salts (ethanolamines, diethylamine) at consuu~ption norms of 2-2.5 kg/ha. It is one of the new herbicides used against bedstraw and common chickweed on grain fields. a-(4-Chloro-2-methylphenoxy)-propionic acid is synthesized by condensation of the salts of a-chloropropionic acid and 4-chloro-2-methylphenol (93-95): Cf I, CFI, C~ ~ ~ -ONa CICfICUONa _N~C CI- ~ ~ -O-CIICOONa I ~ CI t~ CH~ _ and by chlorination of 2-methylphenoxypropionic acid by chlorine (96,97). The process would best be performed in water-free hydrophobic orqanic solvents, similar to that used to make preparation 2M-4C. The acid can be extracted from organic solvents with an aqueous solution of alkali or a ~ower amine. In the latter case we obtain a commercial product having the form of an aqueou.s solution of amine salts with a minimum phenol concentration (98). a-(2,4-Dichlorophe:~oxy)-propionic acid (2,4-DP, dikhlorprop) is a whit~ crystalline substance with a melting point of 117-118�C. Its solubility in 100 ml water at 20�C ~.s 0.35 gm. The solubility of the sodium salt is 66 percent, that of the potassium salt is 90 gm in 100 gm water, and the solubility of the diethanolamine salt is 74 gm in 100 gm water. Its LDSp in rats is 800 mg/kg. a-(2,4-Dichlorophenoxy)-propionic acid is obtained by chlorination of phenoxypro- pionic acid or by reacting 2,4-dichlorophenol with monochloropropionic acid. It is used in the form of salt~ or esters of various alcohols. It is close in biological activity to preparation 2M-4CP, differing somewhat from the latter only in its range of action on weecis. a-(2,4,5-Trichlorophenoxy)-propionic acid (2,4,5-TP) is a white crystalline sub- stance with a melting point of 179-181�C. Its solt~bility in 100 ml water at 25�C - is 0.014 gm, and its salts aith alkali metals and amines exhibit much better solu- bility. Zts LDSp is ~SO mg'kg. y 92 FOR OFFIC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 The herbicidal activity of 2,4,5-TP is close to that of 2,4,5-T, but it is safer to cotton, which permits its use against woody vegetation and brush in cotton growing r~gions. When pears are sprayed in fall, the yield in the following year increases somewhat. = a-(2,4,5-Trichlorophenoxy)-propionic acid is obtained by reacting sodium 2,4,5-tri- - chlorophenylate with sodium a-monochloropropionate in an aqucous medium. - Other u-(aryloxy)-propionic acids have been synthesized and studied as well: . a-(3-chloro-2-methylphenoxy)-propionic (melting point 131-132�C), a-(4-chloro-2,3- -dimethylphenoxy)-propionic (melting point 136.5-137.5�C) etc. Some of them have � been found to be rather active selective herbicides, but they have not as yet en- ' joyed practical use in agriculture. In addition to derivatives of phenoxyacetic and phenoxypropionic acids, derivatives _ of 3-naphthoxyacetic and a-naphthoxypropionic acids have recently found some uses. Salts of a-naphthoxyacetic acid are used to obtain parthenocarpic tomatoes, while its methylester is used as a hsrbicide. The me,thylester of S-naphthoxyacetic acid is a white crystalline substance with a " melting point of 75�C. It is practically insoluble in water, an& it is soluble in ~ most organic solvents. Its LDSp to rats is 2,800 mg/kg. It is obtained by esterification of the acid with met~anol, similarly as in obtaining 2,4-dichlorophenoxyacetates. It is produced in the form of a wettable powder. When used at consumption norms on the order of 3 kg/ha, it exhibits good results against field camomile and (romashka nepakhuchaya) (unscented daisy?~. 1-(2',4'-Dichlorophenoxyacetyl)-2,5-dimethylpyrazole (tomakon) is a white crystal- linE substance with a melting point of 136�C. Its LDSp in mice is about 1,100 mg/kg. It is used as a tomato growth regulator in the form of a 0.15 percent aqueous dis- persion. _ Also described as an experimental herbicide is the diet2-.ylamide of a-naphthoxypro- pionic acid (LDSp 5,000 mg/kg), reco~nended against weeds such as quick-grass and some others (50). 93 - FOR O~FICLA,L USE Ol~iL3f APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OF FICIAI. U:iC UNLY CHAPTER 18 MERCAPTANS, SULFIDES AND THEIR DERIVATIVES - Perchloromethylmercaptan and Its Derivatives Owing to its high toxicity to man and animals and its stzong corrosive action, per- chloromethylmercaptan is not used in agriculture. It is the principal raw material for synthesis of various trichloromethylthioimides and trichloromethylthioamides possessing fungicidal properties. Perchloromethylmercaptan is a red oily liquid with a boiling point of 148�C at 760 mm Hg (partial decomposition occurs) and 73�C at 50 tmn Hg; d~~ 1.6947. It is so toxic to mammals that it was proposed as a toxic agent in World War I, but for practical purposes it was almost never used for this purpose. . _ Metals and other reducing agents transform perchloromethylmercaptan into tniophosgene: CCI~SCI CSCI, Oxidants o:cidize it to trichloromethane s u].fochloride: CCI~~C! 20 CCI,SOzCI Alkali hydrolize perchloror~thylmercaptan to form salt mixtures, slowly when cold _ and quickly when heated. Perchloromethylmercaptan reacts relatively easily with unsaturated compounds to pro- duce trichloromethylchloroalkyl sulfides: ' i~ci~i=cii, cci,sci iicF~ci-cti=-s-cci, itctt=ciiscc;~, -i~c, As,a rule these sulfides are strong fungicides, and they kill many species of phyto- _ pathogenic microorganisms, but the majority of them are also dangerous to agricul- - tural p~ants, since they cause severe burns on leaves. Perchlorometnylmercaptan may be used as a donor of a trichloromethylmercaptan group to the molecules of organic compounds, for example: ~ 94 FOR O~'FICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 co ~ \ itt+c~ ~rvtc + cisca, Rr~c [v-scci, co ~o = Perchloromethylmercaptan is obtained by the following basic methods. l. Chlorination of carbon disulfide in the presence of iodine: . ~ 2CS, 5C1, 2CCI,SC1 SzC!, ~ The byproduct of this reaction is sulfur chloride, the separation of which presents certain difficulties: The simplest laboratory method of purifying perchloromethyl- mercaptan is to distill it with live steam. In this case sulfur chloride is broken down cornpletely by water, but the perch~.~,romethylmercaptan yield decreases to 10-15 percent owing to its hydrolysis by water. However, this method of purifying per- chloromethylmercaptan is difficult in industrial condit~ons owing to the high corrosiveness of the medium. The second (industrial) method of removing sulfur chloride from perchloromethylmercaptan is to rECtify it in a vacuum, but in this case ~l:e purified preparation contains up to 3 percent sulfur chloride, and repeat _ rectification means significant losses of the product. , Puri�ying perchloromethylmerca~.Lan by p~ocessing it with sulfuric acid at a tempera- ture not higher than 10�C has been proposed. In this case the sulfur chloride trans- forms into water-soluble tetrathionic acid: StCI, 2h1,S0~ N~S,Os 2HC1 the calcium salt of which is used to control true powdery mildews. The shortcoming of this purification method is the possibility of side reactions - when the temperature is higher and when the time of contact o` perchloromethylmer- , ~antan wi_th aqueous sulfuric acid solution is longer. At temperatures above 35�C perchloromethylmercaptan is reduced by sulfuric: acid to thiophosgene (melting point 78�C), which is highly voltdile and more toxic thar, perchloromethylmercaptan: CCI~SCI H,SO, N,O ~ CSCI, 2HC1 H,Sa~ Separation of sulfur chloride from perchloromethylmercaptan may be performed in a continuous process (24), as shown in Figure 14. 2. Chlorination of carbon disulfide in the presence of a small quantity of water at low temperature (25,26): - CS~ SCIz -F~ 4fI,U CCI,SCI IItSO, -I- 611C1 This process can also be performed in the presence of diluted mineral acids (27). - Chlorination would best be performed at the lowest possible temperature (not above ~ 95 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 FOR OFFICIAL USE ONLY 4 SCI, C~p y zntpva ~ s - ~ 6~ . ftp~y7~ep0a ~ ~2 ~,t.~rp t � CCI~ /lepsnopMeman-(4 ~ aep,ranmaN � CCI~ npoay.,in ~a 7 . - . ( 31npoMe,B,.y a ~acm~nnsqr~a � Figure 14. Basic Flowchart for Continuous Production of Perchloromethyl- mercaptan: 1--carbon disulfide ch~.orination reactor; 2-- _ chlorination product distillation ~olumn; 3--carbon disulfide distillation column; 4--condenser; 5--carbon disulfide separating unit; 6--perchloromethylmercaptan, carbon tetra- chloride and sulfur chloride distillation column; 7--carbon tetrachloride residue distillation unit Key: 1. Carbon disulfide 3. Product to be washed and dis`cilled 2. Chlorine . 4. Perchloromethylmercaptan + CC14 10�C) wnile agitating well in glass or (igurit) apparatus. In this case the pr4- � ductivity of the apparatus is 30-35 kg/hr perchloromethylmercaptan in a 100 Ziter reac.tion volume; the yield is up to 85~percent, and purity is 95 percent (27). 3. Chlorination of inethylmercaptan and dimethyldisulfide: (CH,S), -F 7C1~ --~2CCI~SC1 6FIC1 This method produces a good yiel.d of sufficiently high quality perchloromethylmer- captan. ~n addition to sulfur chloride, technical-grade perchloromethylmercaptar. also con- tains some carbon tetrachloride formed due to fur'r~?er chlorination of ~erchloro- methylmercaptan by chlorine. Perchloromethylmercaptan may be used to obtain chlorofluromethylsulfinyl chlorides-- intermediate products in the synthesis of a number of fungicides t28-32): , CCI~SCI IIF -i~ CFCI~SCI (;CI~SCI 2F1F ~ CF,CISCI uC~ ` 96 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 A very large r.umber of derivatives of trihalomethylsulfenic acid have now been described in the literature, but the su~fenylamides of various carboxylic and sul- fonic acids are the main ones to have achi~eved practical application, though there are indications that heterocyclic sulfenamides do have high fungicidal activity (33). N-Trichloromethylmercapto-1,2,3,6-tetrahydrophthalimide (captan) is a white almdst odorless crystalline substance with a melting point of 172�C. The technical-grade product is yellow or gray, and it has the typical odor of perchloromethylmercaptan ~ and thiophosgene, with a melting point of 164�C. It is practicaZly insoluble in water, and it is.~oorly soluble in most organic solvents. Its LDSp in rats is 9,000 mg/kg. No abnormal deviations were noted in the course of a year and more ~ when the preparation was introduced into animal feed. It may cause slight irrxta- tion when coming in regular contact with the skin. Captan undergoes hydrolysis when wet: ~O CU � I ~ + 2u,o ~ ~ /N-SCCI, y ~ /NH -CUz; -JIICI; -S Ca C~ This reaction proceeds especially quickly in the presence of alkali and at high temperature. In this connection captan is incompatible with all other alkaline preparations. Captan is obtained by reacting tetrahydrophthalimide with perchloromethylmercaptan in an aqueous alkaline medium, while agitating well at the lowest gossa.ble tempera- ture, to avoid hydrolysis of both captan and perchloromethylmercaptan: ~ ~,n CO I } NaOH C~ /r~~~ + cci,sci _N~ ~ jrr-scc~, cu -"'o co When the conditions of the process are complied with strictly, the captan yield reaches 90 percent. Tetraaydropnthalimide is obtaine~ from ammonium and tetrahydrophthalic anhydride at temgeratures above 200�C: CO CO C~ /O Nfi, - 11 0 ~ ~NH ~ ' CU CU Tetrahyarophthalic anhydride is formed with a practical quantitative yield upo:~ con- densation of divinyl with maleic anhydride, at 100-160�C. This process :nay be per- formed very easily under industrial conditions as a continuous process: ~p CO ~ ~ jo + c~r~cii-cEi=c~-~, C~ /o co 97 FOR OFFIC[AL USE ONY.Y APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/49: CIA-RDP82-00850R040500040001-1 - FOR UFHICIAL USE ONLY The ~lowchart for captan production is shown in Figure 15 (3~). f1aneuNOBaiu ~ 1 ~vHtudpua (2) A~om 1 8 ( 3}~MMUaa ( 4 uB~tNUn 2 /7e�z~.nop- nemun ( 5 ) ' ne Kanman N~OH' 6 3 4 5' 7 npodyrrm Na ( 6 ) q~unempac~uro Figure 15. Basic I'lowchart for Captan Acquisition: 1--maleic anhydride = hopper; 2--reactor for synthesis of tetrahydrophthalimide; 3--crystallizer; 4--tetrahydrophthalimide mill; 5,6--meterinq tanks for per~hloromethylmercaptan and alkali; 7--reactor for captan synthesis; 8--heat exchanger; 9--condensate collector Key: 1. Maleic anhydride 4. Divinyl ~ 2. Nitr~g~n 5. Perchloromethylmercaptan 3. Ammonium 6. Product to be filtered Captan is produced in the form of 50 percent wettable powder and 75 percent prepara- , tic~c~ as a seed disinfectant; it is used for plant protection at a.concentration of 0.3-4.5 percent. Captan is used as a broad-profile protective fungicide to control varir~us diseases of agricultural plants, including as a disinfectant of the seeds of a number of - crops. When qrapes are processed with captan, the latter r.as an unfavorable effect - on alcohol fermentation during wine production, since it inhibits development of yeast fungi. N-Trichloromethylmercaptophthalimide (ftalan, phaltan) is a white crystall~ne sub- stance with a melting point of 177�C. It is insoluble in water, and it is poorly _ soluble in ordinary organic solvents. Ftalan is mildly toxic to mammaZs, and its LDSp in rats is more than 10,000 mg/kg. It is slowly hydrolyzed by water, especially in an alkaline ~redium. In this connec- tion tne preparation must be carefully dried during its production, and dr.y fillers - 98 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R400540040001-1 _ FOR OFFiCiAL USE ONLY must be used. Presence of 1 percent water ir the preparation may hydrolyze about 10 percent of the ftalan: CO CO ~ \ +2ii,o 1 r~ ~ ~y ~ /N-SCCI, -3iici: -s: -co I /NH CO CO . ~ Hydrolysis liberates a large quantity of hydrogen chloride and therefore, as is equally true with captan, ftalan cannot be packaged in paper containers, since the latter break down very quickly. It is produced in the form of 50 percent wettable powder, and the concentration of the active ingredients of the applied product is 0.2-0.3 percent. Ftalan is obtained similarly as with captan, by reacting~perchloromethyl.mercaptan with phthalimide in the presence of sodium hydroxide in an aqueous medium. When sufficiently pure perchloromethylmercaptan is used, the ftalan yield is about 90 percent of theoretical. The main impurity in the technical-grade product is the initial phthalimide that did not react or ~hat fc:_zned as a result of hydrolysis; a slight quantity of sulfur is present as well. Phthalimide and its analogues are foxmed with a practical quantitative yield when pnthalic anhydride is heated in the presence of urea tv 130-140�C (35). N-(1',1',2',2'-Tetrachloroethylmercapto)-1,2,3,6-tetrahydrophthalimide (captafol, difolatan, foltsid) is a white crystalline substance with a melting point of 162�C; . it is practically insoluble in water and poorly soluble in most ordinary organic solvents, though it is somewhat more soluble than captan. Its LD50 in rats is more than 6,000 mg/kg. The preparation is more resistant to hydrolysis than captan and �talan, and it is hydrolyzed slowly by water and faster by caustic alkali: CO CO~ \ \ +~N~~ N-SCCIi-CFIC1~ ? I~ JI\ /NH CfiCIzC00Fi CO CO ~ _ ~Dif~Iatan is obtained by reacting tetrahyd�rophthalimide with tetrachloroethylsulfinyl chloride in the presence of sodium hydroxide: CO CO C\/\ +Nnott~ ~N-SCCI Cf(CI ~ ~NH CHCI,-CCI,SCI _Naa ~ ~ ' ' CO CO 99 - FOR OFFIC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL U~E ONLY Tetrachloroethylsulfinyl chloride is synthesized out of sulfur chloride and trichloro- ethylene, followed by chlorination of the resulting bis-(tetrachloroethyl)-di~ulfide - ( 36) : + c~, CHCI=CC1, S,CI, (CHCI,-CCI,),S, - ` 2CHCI,CCI,SCI It is less difficult to obtain this product than perchloromethyLnercaptan, and there . are qrounds for suggestinq that N-(1~,1',2',2'-~etrachloroethyl)-1,2,3,6-tetrahydro- phthalimide is a serious competitor of captan. Difolatan is produced in the forn? of a 50 percent wettable powder, and it is used � similarly as captan and italan. mhe main crops for which this preparation is recommended are potatoes and grapes. A large number of other similar compounds have be=n synthesized as well, but they , have not yet found applications in agricuYture. - N-Trichloromethylsulfamides of aliphatic sulfonic a~ids are close in fungicidal activity to captan, while the corresponding ami.des of aromatic sulfonic acids are significantly less active. Introduction of a trichloromethylmercapto group does not always raise the activity of sulfonic acid amides. Thus N-(trichloromethyl-mErcapto -t7-(4-cY:lorophenyl)-metnanesulfa~iciz is a stronq fungicide while N-(trichZoromethyl- mercapto)-N-(4-thiocyanatophenyl}-methanesulfa.mide is not very active. N-(Trichloromethylmercapto)-N-(4-chlorophenyl)-methanesulfamide (mesul'fan, an analoque of captan No 6) is a white crystalline st:bstance with a melting point of 113-114�C. It is in~,l.ubla in water and moderately soluble in organic solvents. Its LD50 in rats and mice is more than 5,000 mg/kg (37). I~ _recalls captan in its chemical properties: It is unstable in an alkaline n~edium and it is hydrolyzed by water: CH~SOj-N-C~H,Cf 2FIi0 _3~~c~; -s; -co~i CFI,SO,-NH-C61t,C1 ~CCI, Mesul'fan is produced at a qood yield by reactinq perchloromethylmercaptan with 4-chlorophenylmethanesulfamides in the prese~ce of sodium hydroxide: NHSO,CH, +Neoii N-SO,Cfi, i~ CCI~SCI -H~ 'I ~CCI~ CI ~ Cl ~ Mesul'fan is produced in the form of 50 percent wettable powder; it is less active _ than captan. , , 100 FOR OFFIC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-00850R000500040001-1 FOR OFF'ICIAL USE ONLY N-TricY,":.oromethylsulfamide homologues of inethanesulfonic acid are somewhat less active, with the exception of ethanesulfonic acid deriva~ives, which are equivalent to the corresponding derivatives of inethanesulfonic aci~. Introduction of chlorine into the methyl radical of inethanesulfonic acid d4es not raise the compound's activity. Research i~as also been condv::ted on a large number of aliphatic and aromatic tri- chloromethylthiosulfonates. Many of them have strong funqicidai action, but all compounds of this type are phytoto~cic, owing to which they are not used in agricul- ture. Trichloromethylthiasulfonates are obtained �~ith a good yield by reacting the sodium salts of sulfinic acids with perchloromethylmeccaptan: ' RSOzNa CCI~SCI _Ne~i~ RSOtSCCI, The fungicidal activity of compounds containing a trichloromethylmercapto group is ~ connected, in the opinion of many researchers, with the hig:~ reactivity of this group. Interacting with different sulfhydryl groups in the fungal cell, it disturbs vitally important biochen~;:al processes in microorganisms. Research has been ~onducted on, in addition to derivatives of sulfonic acids, the . _ N-alkylmercapto derivatives of sulfuric acid amides, of which the preparation eparen (dikhlorfluanid) has enjoyed practical application (28-32). N-N-dimethyl-N~-dichlorofluoromethylmercapto-N'-phenylsulfamide (eparen, dikhlorflu= anid) is a crystalline substance with a meiting point of 105.5-105.6�C. Its vapor pressure is 1�10'6 nun Hg at 20�C and 4�10-5 mm Hg at 45�C. It is practically in- soluble in water. Its solubility (gm per 100 mi sol~ent) is 1.5 in methanol and 7.0 in xylol. Its LDSp in rats is 500-1,000 mg/kg with different methods of ad- ministration. In its chemical properti~:s it recalls the corresponding derivatives of perchloro- methylmercaptan, but it is somewhat more stable. Eparen may be obtained as follows: + cr�cizsc~ (CII~)tN-SOzCI ~aH6Nti, H (f~H~)tN-SOt-NFICaHb -H~~ (CI[,)zN-SO,-NC~H~ SCFCI~ . The acid chloride of sulfuric acid dimethylamide may be obtained by re~cting dimethylau;ine with sulfuryl chloride or by reacting dimethylchloramine. with sulfur dioxide: t S01CIz + SOz (Cti~)~NH _i~~~ ? (CH~)zN-S01C1 (CH,),NCI 101 ' FOR OFFICIAL USE ONILY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 - FOR OFFICiAL USE ONLY Eparen is produced in the form of 50 percent wettable powder to be used as a 0.075- 0.1 percent aqueous suspension and as a 7.5 per~ent dusting powder. Eparen has a good effect against apple scab, gray mold on strawberries an3 stone !~ruit crops, = and other plant diseases. _ N,N'-Dimethyl-N~-dichlorofluoromethylmercapto-N'-p-tolylsulfamide (eparen M) has a melting point of 95-95�C, and its vapor pressure at 20�C is 10'S mm Hg. Its solu- bility in water at 20�C is 4 gm/Iiter. It is freely soluble in most organic solvents (41,42). Its LD50 in rats is 1,000 mg/kg. The N,N-dialkyl-N'-tetrachlorofluoroethylmercapto-N'-phenylamides of sulfuric acid ` (38) and of organic sulfonic acids (39) also have fungicidal properties. . BIBLIOGRAPHY . 1. U.S� Patent 3491156 (1970); RZHKHIM, 5N698, 1971. 2. Japanese Patent 22318 (1969) ; RZHIQIIt4, 16r1696, 1970. 3. U.S. Patent 3449388 (1969); RZHIC~IIM, 19N603, 1970. 4. Japanese Patent 8873 (1970); RZHKHIM, 1.SN717, 1971. . 5. USSR Patent 30472Z (1971); OTKRYTIYA. IZOBk. PRAM. OBRAZTSY. TOVARN. ZNAKI, No 17, 1971. 6. U.S. Patent 3529025 (1970); RZHF~TiIM, 4N622, 1971. 7. U.S. F:3tent 3501502 (1970); 1~^HKHIM, 13N621, 1971. _ 8. USSR Patent 291389 (1971); OTKRYTIYA. IZOBR. PROM. OBRAZTSY. TOVARN. ZNAKI, _ No 3, 1971. 9. U.S. Patent 3444222 (1969); RZHKHIM, Z5N703, 1970. 10. U.S. Patent 3522293 (1970); RZHKHIM, 1ON590, 1971. = 11. U.S. Patent 350671i3 (1970); RZfiKHIM, SN696, 1971. 12. U.S. F:~tent 3444239 (1969); RZHKHIM, 15N704, 1970. 13. Japenese Patent 14320 (1970); RZHKHIM, 1ON587, 1971. ~ 14. U.S. Patent 343822 (1969); RZHI~iIM, 19N600, 1970. 15. U.S. Patent 3463330 (1969); RZHKHIM, 18N656, 1970. 16. Japenese Patent 8874 (1970); RZHKHIM, 15N716, 1971. 17. Swiss Patent 485398 (196:'); RZHKHIM, 22N672, 1970. 102 - FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 - FOR OFFICIAL USE ONLY 18. USSR Patent 293315 (1971); OTKRYTIYA. IZOBR. PROM. OBRA2TSY. TOVARN. ZNAKI, . No 5, 1971. 19. Japanese Patent 10773 (1970); RZHIQiIM, 12N1019, 1970. 2Q. Kaspers, H., and Grewe, F., "Seventh International Congress of Plant Protecti4n. ~ Summaries of Papers," Paris, 1970, p 203. 21. FRG Patent 1227891 (1969); CHEM. Z., Vol 138, 43-2752, 1967. 22. Prilezhayeva, Ye. N., Lukin, V. V. ec al., DAN SSSR, Vol 194, 1970, p 727. 23. Huisman, H.~O:, Uhlenbrock, J. H., and Meltzer, J., REC. TRAV. CHIM., Vol 77, 1958,- -p 103. - 24. U.S. Patent 2575290 (1951). - 25. CSSR Patent 130980 (1970); RZHKHIM, 20N93, 1970. 25. CSSR Patent 134692 (1971); RZHIQIIM, 15N125, 1971. 27. CSSR Patent 133435 (1970); RZHKHIM, 7N697, 1971. 28. FRG Patent 1235301 (1967); QiEM. Z., Vol 138, 43-2753, 1Q67. 29. Australian Patent 227677 (.1966); 227678 (1966); CHEM. Z., Vol 137, 37-3191, 1966. 30. Muller, H. E., PF'LANZENSCHUTZ-NACHR. BAYER, Vol 21, 1968, p 257. 31. Kuh1e,~E., and Klauke, "Sixth Interziational Congress of Plant Protection," _ Vienna, Verlaq der Wiener Medizinischen Akademic Abstracta, 1967, p 342. 32. Goeldner, H., PFLANZENSCHUTZ-NACHR. BAYER, Vol 21, 1968, p 261. 33. USSR Patent 225108 (1967). 34. U.S. Patent 2653155 (1953). . 35. Australian Patent 286271 (1970); RZHKHIM, 15N207, 1971. 36. U.S. Patent 3454631 (1969); RZHKHIM, 16N712, 1970. ~ 37. Mel'nikov, N. N., Sokolova, Ye. M. et al., KHIM. PROM., No 10, 1961, p 692. . 38. USSR Patent 284735 (1970); OTKRYTIYA. IZOBR. PROM. OBRAZTSY. TOVARN. ZNAKI, - No 32, 1970. 39. USSR Patent 257375 (1968). 40. Trepka, R. D. et al., J. AGR. FOOD CHEM., Vol 18, 1970, p 1176. 41. Kolbe, W., PFLANZENSCHUTZ-NACHR. BAYER, Vol 25, 1972, p 123. 42. Wackers, R., and van den Berge, C., PFLANZENSCHUTZ-NACHR. BAYER, Vol 25, 1972, p 163. 103 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 - FOR OFFICIAL USE ONLY q ~ CHAPTER 25 ORGANIC PHOSPHORUS CONiPOUNDS General Description of Pesticide Properties One of the most important classes of modern pesticides is the orgat~ic compounds of phosphorus, more than 100 of which are used in aqriculture. Among the organic phos- phorus compounds, substances have been found with different pesticidal properties, to include insec~icides, acaricides, nematocides, herbicides, defoliants and fungicides. Organic phosphorus compounds are used especially broadly to control plant pests and the ecto- and, in part, endoparasites of domesticated animals. The scale of application of organic phosphorus compounds as pesticides is close to - the scale of use of organic chlorine compounds in agriculture. World production of the most important p~eparations in this class, intended for con- tro~. of weeds and plant pests and diseases, has now exceeded 150,000 tons per year, and the number of preparations now in use is nearing 150. Such swift growth in the production and application of orqanophosphorus pesticides is connected with a number of their positive properties, the most important ones of which are: 1. High insecticidal and acaricidal activity and broad spectrum of action against plant pests. - 2. The possibility of having compounds with the most diverse persistence, the decomposition of which in :iifferent living orqanisms proceeds with ' formation of compounds that are practically nontoxic to.man and animals. 3. Relatively fast metabolism in the vertebrate body and absence~of a capability for deposition in the body, as well as relatively low product ~ toxicity or its complete absence. - 4. Systemic or deep action of a number of preparations. 5. Low consumption of preparations per unit of worked surface and fast action against plant pests and animal parasites. ~ 6. Fast decomposition in soil and moderate toxicity to fish. One negative property of many organophosphorus compounds is their relatively acute toxicity to vertebrates, which requires compliance with the appropriate precautionary m:asure~s when using them. A large number of organophosphorus compounds that are mod~rately ct mildly toxic to mamcnals have also been synthesized in recent years. Such compounds are fully safe to use in agriculture. 104 ~ . FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R004500040001-1 Research on the mechanism of action of organophosphorus compounds up~n mammals and insects showed that in the animal body, they phosphorylate vitally important esterases, ~ inhibiting their normal functions. It is believed that the action of these compounds 'is based mainly on inhibition of cholinesterase, the physiological f~nctions of which 8�re very important in the animal body. Cholinesterase hydrolyzes acetylcholine: + c~,E-ti + (CIi~),NCHlCH,OCOCH, (CH~)~NCH~CH~OH CF(~COOII � The mechanism by which cholinesterase is inhibited by organophosphorus compounds may ' be diagrammed as follows (1-4,549): O p - - ChE-H RO~(OR')i RO-P(OR')~ _'ROH } F~I-Ch E' ~ O P(OR'), ChEP(OR')i ChE` At first, esterase apparently forms a complex with the organophosphorus compound. This complex then breaks down to produce an esterase phosphorylation product and the corresponding oxy compound. Phosphorylated ~sterase may be gradually hydrolyzed by water, which reStores its esterase activity. The rate of deph~sphorylation is . so low for some substances that it does not have practical significance. Thus for example, dephosphorylation of cholinesterase inhibited by tetraethylpyrophospYiate p~oceeds very slowly in water, and in 28 days only ~0 percent of the initial activity is restored: ChEP(~R')~ -F H,0 ~ Chlsti HOP(OR')z II II 0 0 The activity of organophosphorus compounds depends strongly on the structure of the ester groups in the molecule of the phosphoric acid ester; nor is the structure _ of each of the radicals im material. Thus for example, 0,0-diisopropyl-O-4-nitro- phenylthiophosphate is almost 100 times less active against bee cholinesterase than 0,0-diethyl-0-4-nitrophenylthiophosphate. Foz maximum effect, the organophosphorus molecule must have a"lock and key" fit with the active centers of the esterase (5). It is entirely obvious that the activity of the same compound would differ in rela- tion to cholinesterase from different species of animals and insects. Thi~ is _ connected with the difference in the structure of choli.nesterase from different organisms (1,�~) and with differences in the metabolic pathways of organophosphorus compounds in the insect and animal body (2). Thus for example, carbofos undergoes 105 FQR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00854R000500040001-1 FOR OFFICIAi. USE ONLY the usual transformations in the housefly body, while in the rat body it transforms into mildly toxic malathionic acid: - S (CII;,U)_~P~ S C I I COO I-i I ~ cEr,coofi while pyrophosphoric acid octamethyltetramide transforms in the animal body into a product that is more toxic than the initial compound. - To correctly understand the reasons why specific organophosphorus compounds are toxic to particular species of animals, we need to know not only the general mechanism of their a:tion but also their metabolism within the given animal species. - Very often the activity of a compound in relation to ch~linesterase is associated with the organophosphorus compound's rate of hydrolysis, which is not always valid: Activity also depends on the steric features of molecular structure. - In addition to hydrolysis a.zd the structural features of organophosphorus molecules, the rate of dealkylation of phosphoric acid esters also has a great influence on their toxicity (6). Phosphate deallcylation is apparently the principal reaction in the _ animal body competinq with phosphorylation of cholinesterase. That methylphosphates are less toxic to mam~nals than homologous esters can be explained by dealkylation of phosphoric esters. In this case esters are decomposed by dealkylation before they - reach their place of action, as was first asserted by the author back in 1~61. This point of view has now achieved substantial confirmation (7). Various phosphorus compounds are used as pesticides, to include derivatives of phosphorous and thiophosphorous acids, thio- and dithiophosphoric acids, and phos- phonic and thiophosphonic acids. In contrast to the situation w~ith most other classes of compounds, the nomenclature of organophosphorus compounds has not been adequately worked out yet, and different countries use their own naming systems. In most cases orqanophosphorus compounds are interpreted as derivatives ~f the appropriate acids and hydrogen phosphide-- phosphine. - Derivatives of phospharous acid have "ite" endings while derivatives of phosphoric acid have "ate" endings. For example the diethyl ester of phosphorous acid (I) is called diethylphosphite, while the diethyl ester of phosphoric acid (II) is called diethylphosphate: - /O (CaIi60)jPtlO (C~f160)~P~ ~OH i u 106 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 = FOR OFF(CiAL USE ONCY When a sulfur atom is present in the molecule, the compound is named ~s follows: Dnpending on the position of the sulfur atom, the diethyl ester of thiophosphor.ous acid is called O,0-diethylthiophosphite (III) or O,S-diethylthiophosphite (IV): C,H60~ /O ~CsHeO)zPHS P C,H6S~ ~�H - i~i iv The derivatives of thiophosphoric acids are named analogously, as can be seen from the following examples: ,S ~ ~~t~.~bp~~p/ O,0-Diethylthiophosphate - ~OH Czfl~O~ /O p G,S-Diethylthiophosphate C~H6S~ ~OH _ C,H60~ /S P O,S-Diethyldithiophosphate C,HSS~ ~OFi O (CzFI`S)7P~OH S,S-Diethyldithiophosphate Amides of the acids of phosphorus are named according to the same system. Thus com- pound V, would be named 0,0-diethyl-N-methylamidophosphate, while compound VI would be named O-ethyl-N-methyl-N~-propyldiamidothiophosphate: O CF{,NH S ~~~H`~~zP% \P% . � ~N11CH, C~N,NH~ ~OC,H6 v vi ' The names of complete amides of phosphorous acid are sometimes derived from hydrogen phosphide as well. In this case compound VII may be called hexamethyltri~minophos- phine: . ((CH,),N),p , vlt _ 107 ~ - FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 _ FOR OFFICIAL U~E ONGY Acids of phosphorus having a C-P bond are named as follows: ~~i RPFI~ Alkylphosphonous R,PHO p Dialkylphosphinous RP~~H~' Alkylphosphonic /O R'P\~H Dialkylpiiosphinic The nomenclature of the derivatives of these acids may be explained by the following examples: ~ ' ~~F~6~~ 0-Ethyl-0-phenylmethylphosphonite PCI Cgf~b~/ CzEf60~PCH 0-Ethy~.-S-phenylmethylthiophosphonite a C61 ~bs � ~~F~'~\ 0-Ethyl-N-methylamidcmethylphosphonite PCIi~ CH~NII~ - C~H6O\ ~O _ p 0-Ethyl-S-propylmethylthiophosphonate C~H,S~ ~CH, _ Cz(160~ /S P 0-Ethyl-ri-ethylamidomethylthiophosphonate Cz~(6NH~ ~Cti, O (C=Hs)~P~ 0-Ethyldiethylphosphinate ~OC2Ha _ CFI~\ - P S-Ethylethylmethylthiophosphinate - CzH6/ ~g~zH6 The names of alkyl- and arylphosphinous acid chlorides may be derived from phosphine; for example CH3PC12 (VIII) is called methyldichlorophosphine. Compounds with the general fazmula IX below are called phosphines while compounds with the general formula X are called phosphinoxides: R~ R~ ' R'-P R'-P~O RN/ ~x x '08 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 . . The salts of tetrasubstituted phosphonium (XI) R'\~-R,., X- . R"~ xt - are named similarly as the correspondinq ammoni~un derivatives. Phosphorous Acid Derivatives � ~ Research on the pesticidal properties of a large ntur~er of phosphorous acid deriva- ~ives established that many compounds in this series have weak insecticidal and acaricidal activity, but some derivatives of phosphorous an,d thiophosphorous acids have high herbicidal activity. ~he herbicidal activity of esters cf phosphorous acid increases as the number of carbon atoms in the aliphatic ester radicals grows. Complete esters formed from phosphorous aaid and haloaryloxyetrianols display the greatest activity; one such compound used in agriculture is falone. Tributyltrithiophosphi~e has enjoyed rather broad use under the names merfos and foleks as a defoliant of cotton and some other crops (9). The compound is also activ~ ~ when combined with the most diverse compounds including tertiary amines.(10): Other " active defoliants are dibutyldithiochlorophosphite (11) and triarylphosphites (12). ; G~iclic pyrocatechol chlorophosphites (13) and diallylphosphite (14) exhibit.fungi- ~idal action. Cyclic phasphi.te (XII) has been proposed as an insect steril3.zer (15). Phosphites are broadly employed as intermediate products i.n the synthesis of a large number of pesticides. CFI~O~ ' ~POCFIzCN=X CI i,0' xn = Ci, Br~ F. ~1 The most important methods of obtaining dialkylphosphites are as follows.(.16). . 1. Interaction of phosphorus trichloride and alcohols: - PCI, 3ROFI, (RO)~PHO + RCI 2FtCl 2. Partial hydrolysis of trialkylp.hosphites or dialkychlorophosphites: - (RO),P -I- FIzO (RO)~PHO RQIi - ~ 109 ~ . FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY 3. Dialkylphosphites can also be obtained by oxidation of white phosphorus in the appropriate alcchol (17). The yield of diethylphosphite in this case is about 43 percent. - Of these methods, the first has the greatest practical significance. I: is used extensively in industry. The reaction is usually ~,erformed in an inert organic solvent at low temperature (16). A convenient solvent fo~ acquisition of ~i.methyl- chlorophosphite would be mett~ylchloride, which acts here as a coolant as well, _ since the reactian is usually performed at its boiling point (-24�C). This method can also be used to obtain dialk.yphosphites with mixed radicals (19) and alkylaryl- - phosphites (20,21,j, using a mixture of two alcohols and methanol in a reaction with PC1~3 : ~ RO~ I'C.I, -i- CI~I~UIi ROtf R'Of( R~O/PHO C}(~CI 2HC1 Byproducts appearing in small quanti.~~as in the reaction between phosphorus tri-- chloride and alcohols include monoalkylphosphite and phosphorous acid, forme~ as a result of the reaction between dialkyphosphite and hydrogen chloride. Dialkyphosphites car_~be produced from PC13 and alcohols by both cyclic and continuous processes (18). Lower dialkylphosphites may be purified by distillation in a vacuum using a contin- uous-action film evaporator at a res:.dual pressure of 1-5 a�n Hg. Trialkyphosphites may be industrially obtained by reacting phosphorus trichloride and alcohols in tt~e presence of hydrogen c~hloride acceptors (22-24) (a~nonium, ammoniate (23) and tertiary amines (24)) and by an ester interchar+ge reaction per- formed with triarylphosphites and alcohols (25). The latter reaction proceeds in _ the presence of alkaline catalysts at high temperature. Figure 16 shows the basic flowchart for production of trimethylphosphite out of methanol and triphenylphosphite (25). The purity of trimethylphosphite obtained by this method is 98 percent, and its yield is 80-85 percent. This yield is achieved after several recyclings of triphenyl- phosphite. Another interesting method of obtaining trialkyphosphites is to react alcohols with triaminophosphines: 3ROH (R;N~~P (RO),P 3R~NF1 The o~dest method is to react phosphorus trichloride with sadium or magnesium alco~ holates, but the tr,ialkylphosphite yields do not exceed 61 percent of theoretical. ~ 110 ~ ~OR OFFIC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 _ . :IAL ' )NLY ~ 2 3 y f !1 ~ 1S 9 - 14 ~ 6 ~Z 10 � 7 B - Figure 16. Basic Flowchart for Production of Tri.methylphosphite Out of = Methanol and 'rriphenylphosphite: ?--triphenylphosphite container; 2--methanol contaiiier; 3--catalyst (sodium methylate) containpr; 4,5--metering units; 6--reactor-mixer; 7--pump;. 8--tunnel reactor; 9--evaporator; 10--vat residue collector; 11--column for separation of inethanol and trimethylphosphite from phenol and triphenylphosphite; 12--column for separation of inethanol and trimethylphosphite; 13--trimethylphosphite collector; 14--column for separation of phenol and triphenyl- ~ phosphite; 15--phenol collector Dialkylthiophosphites may be obtained bx reacting hydrogen sulfide with trialkyl- phosphites in the presence of organic bases (26), and trialkyltrithiophosphites can be obtained from mercaptans and trialkyphosphites in the prese~nce of ~inc or cadmium acetates (27). However, the best industrial method of obtaining trialkytrithiophos- phites is to react phosphorus trichloride with mercaptans. In this reaction, equi- molar quantities of these sul~stances are heated. This is the way the preparation merfos is obtained industrially: PCI~ 3C~EioSH (C~EfoS)~P -F 3HCI '~Yis-(2,4-dichloropherioxyet:zyl)-phosnhite(falone) is a thick oily liquid with a mild odor, it does not sublimate without decomp~sing in a low vacuum, it is practically insoluble in wat~r, and it is freely soluble in organic solvents. ~ts LDSp in rats is 850 mg/kg. ' Oxidation of the preparation produces the appropriate phosphate~: (2,�1�CI~C6f~I,OCF1,CHz0)~P (2,4-CIzCeH~OCHzCH~O)~PO When it interacts with water, falone first transforms into the corresponding dialkyl- - phosphit~ which, on being hydroiyzed and oxidized, produces 2,4-dichlorophenoxy- ethanol and phosphoric acid. - 111 FOR OF'FICIA~, USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL. USE ONLY The action of falone in soil is apparently based on its transformation into 2,4-D. Falone is recommended against weeds in corn, potatoes, strawberries and some other crops at consumption norms from 4 to 8 kg/ha. Aqueous emulsions of the preparation are usually used to process soil. Falone is obtained by reacting phosphorus trichlor:.de with 2,4-dichlorophenoxyethanol in the presence of pyridine, dimethylaniline or other tertiary amines: ~C' + 3 / OCHzCti~Oti 3C H N~ OCFIzCE{s0 ' ~ \ I I CI CI CI CI , Following separatior: of pyridine hydrochloride, the reaction product is used without further purification to make emulsion concentrate. Di-(2,4-dichlorophenox;iethyl)-phosphite also has herbicidal properties, but its activity is inferior to that oi: falone. Tributyltrithiophosphite (merfos, foleksj is a light oily liquid with a boiling point of 150-152�C at. 2 mm Hq, It is almost insoluble in water, and it is freely soluble in organic solvents. Its LDSp in rats is 350 mg/kg. The preparation is used to defoliate cotton in the form of aqueous emulsions at con- sumption norms of 1-2 kg/ha. In texms o~ the speed of its action and the resulting effect, merfos is one of the best defoliants. Merfos is slowly oxidized by atmospheric oxygen to tributyltrithiophosphate; this reaction goes faster in the presence of heat, and it may be used as an intermediate step in acquisition of tributyltrithiophosphate and in production of S,S,S-tributyl- trithiophosphate in industry. Tributyltrithiophosphate enjoys extensive use as a defoliant of cotton and other crops. It is marketed as butifos and DEF. It is an oily liquid with an unoleasant odor; its boiling point is 150�C at 0.3 mm Hg; its LDSp in experimental animals is 170-250 mg/kg. Impurities contained in the technical-grade preparation include a small quantity (up to 10 percent) of tributyltrithiophosphite and dibutyldisulfide. It is used as oil solutions or emulsio:~ concentrates at consumption norms of 1-1.5 kg/ha. Some homologues of inerf~s and butifos have been proposed as defoliants, but they have not as yet enjoyed practical application. Because merfos and butifos are readily oxidized by various oxidants, they may be neutralized by oxidizing and chlorinating them with calcium and alkali metal hypo- chlorites. However, it should ae kept in mind that in a number of cases hjpochlorites react with these cle~foliants very violently, with ignition occurring. 112 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAI. USE ONLY Phosphoric Acid~Derivatives As we proceed from phosphites to phosphates, the insecticidal and acaricidal activity of the compound rises. Mixed esters of phosphoric acid, where one of the ester . radicals is acidic, are especially active. The higher the dissociation constant of such an alcohol or phenol (or acid), the more toxic the compound is to insects and ~nimals. Thus for example, in the series 0,0-diethyl-O-4-chlorophenylphosphate, 0,0-diethyl-O-2,4-dichlorophenylphosphate and 0,0-diethyl-O-2,4,5-trichlorophenyl- ~hosphate, the last ester exhibits the greatest insecticidal activity (the dissocia- tion consta.nts of 4-chlorophenol, 2,4-dichlorophenol and 2,4,5-trichlorophenol are ~.1�10-10, 3.1�10-8 and 4.26�10-8). Dialkylfluorophospha"tes as well as fluorophos- phoric acid amides are highly toxic. However, when the length of alkyl radicals ~n phosphoric acid esters and amides is increased, toxicity to animals decreases. Maximum toxicity for many mixed esters of phosphoric acid is achieved with diethyl derivatives, but exceptions are observed as well. As a rule dimethylphosphates are significantly less toxic, apparently due to their hiqh alkylating capacity in relation ~o various nitrogen and sulfur compounds present in biological substrates, and their high rate of hydrolysis. Not only the nature of the substituent in the aromatic radical but also its position has a great influence on the toxicity of mixed phosphate to insects and ticks. Insecti- cidal properties are increased the most when nitro- and methylmercapto groups are introduced into the aromatic radical. In general the activity of arylphosphate with _ substituents at position 4 is higher than that of arylphosphates with the substituents = at positions 2 and 3. Systematic study of the biological activity of different mixed alinhatic-aromatic phos- = phates showed that some of them may be of practical interest as insecticides (28-30), fungicides (31) and herbicides (33). In particular, herbicidal action is exhibited by tris-(butyoxyethyl)-phosphate (34). High biological activity is exhibited by some phosphates obtained from oximes of benzaldehyde and acetophenone derivatives (35) containing different substituents in the aromatic ring. C~clic ester XIII, obtained from phosphorus chloroxide and hexa- chlorophene, has herbicidal action (36}; CI , CI _ ~ CI ~ O - E{zC CI ~ p% ~'Oli , / ~f CI xiii Mixed esters and esteramides of phosphoric acid possessing various heterocyclic radicals have significant insecticidal and acaricidal activity (37-40,42-45), while - benzofurazan derivatives have nematocida~ action (41). Dialkylhalopyridy: phosphates 113 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02109: CIA-RDP82-00854R000500040001-1 FOR OFFICIAL USE ONLY are good insecticides with moderate toxicity to homeotheruu.c animals. An examQle is preparation dauks-217 (0,0-dimethyl-0-(3,5,6-~trichloropyridyl)-phosphate). Its LD;~ in rats is 869 mg/kg (42,43). _ Among mixed esters of phosphoric aci3, various enol phosrhates have been subjected to the deepest study in recent years; many of them have achieved e:ttensive practical application in agriculture and in the control of synanthropic insects. Table 44. shows some phosphoric acid esters that have achieved some sort of application in agriculture. _ As we can see from Table 44 vinylphosphates containing various substituents in the vinyl group have enjoyed the widest use. Perkov's reaction (47) is a general method of obtaining O,O-dialkyl-O-vinylphosphate--interaction of a-halocarbonyl compounds - with tr~alkylphosphites: (I20),P R"COCFiCIit' (RO)iP0'=C(i!2' RCI b R" This reaction proceeds easily with both aliphatic and aroma.tic carboxylic acid - aldehydes, ketones, esters and amides. 0,0-Dialkyl-O-vinylphosphates may also be obtained by reactin~ dialkylchlorophosphates , with the appropriate enols in the presence of hydrogen chloride acceptors (4). Both _ inorganic and organic bases may be used as hydrogen chloride acceptors. RC=CHR' -F (R"O),PCI (R"0)s~ i=CHR' ~H (5 R _ Acquisition of dialkylvinylphosphates by reacting vinylphosphoric acid ahlorides _ with the appropriate alcohols in the presence of hydrogen chloride acceptors has been described in patents (49): RCIi=COPCI, + ~R"OH (R"O),PUC=Cti[t 2HC1 R~ } ~ . _ The vinyldichlorophosphates required for this reaction are obtained from phosphorus chloroxide and enols, for example acetoacetate: - CH,CUCFI,COOC,H~ POCt~ C~HbOCOCF(=COPC1~ NC! H,G ~ � 114 F~R OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R004500040001-1 ~ Table 44. Phosphoric Acid Esters Chemical Name Foxmula � Synonyms 0,0-Di.methyl-0-(2,2-di- (Cf1,0),POCH=CI Dichlorophos, DDVP, ~chlorovinyl-phosphate l5 nuvan, vapona, � nogos _ _ ~ CH,O~ PO Ca�2(Cti,O)=POCH=CCI, Nestan CCI j=CHO~~ ? ~ 0,0-Dimethyl-0- (1, 2-di- (CH,O)=POC[~CCI,Br Naled, dibrom, ~bromo-2,2-dichloroethyl)- ~ ~ nikabrom ,phosphate g~ O,O-Dieth~rl-0- (2, 2-di- (C=H~O),POC=CCI, Fosfinon chloro-l-S -chloroethoxy- ~ OCH,CH,CI _ vinyl)-phosphate _ ~ 0,0-Dimethyl-0- (1-methyl- (~H~O)7POC~CHCOOCH, y Mevinphos, -2-carbomethoxyvinyl)- 0 ~Fi, phosdrin � - phosphate . 0,0-Dimethyl-0- [1-methyl- (~H,O),POC=CHCOOCHC6H, Ciodrin -2-(carboxy-a-phenyl- H, - ethyl)-vinyl]-phosphate 0,0-Dimpthyl-0- [1-methyl- ~ (CFi,O)~~ ~ CHCONE(CEJ, Azodrin, -2-(methylcarbamoyl)- y nuvacron =vinyl]-phosphate ' 0,0-Dimethyl-O-[1-methyl- Bidrin, -2- (dimethylcarbamoyl) - (CIi,O),POC=CHCON(CH,), carbicron, =vinyl}-phosphate ~ ~j~~ ektafos 0,0-Limethyl-0- [1-methyl- (CH~O)zHOC~CCICON(C~He)~ Phosphamidon, -2-chloro-2-(diethyl- g ~H dimecron, dovip carbamoyl)-vinyl]-phosphate ' 0, 0-Dimethyl-O- (1-carbo- (CH,O)~POC=CFtC00CH~ Bamil methoxymethyl-2-carbo- ~ ~HzC(~UCH, methoxyvinyl)-phosphate 115 . _ FOR OF'~'IC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 - FUR OFFICIAL USE ONLY - That Have Attained Use as Pesticides LD50 - in Rats ~ (Orally) - Boiling mq/kg Point, �C LD50 in . (At In- Solubil- Rabbits dicated Melting ity in (Subcutan- ~ _ Pressure); Point, Water, eously), mm Hg �C mc7/liter mg/kg Use. Forms of A~plication and Consumption Norins - - 74~~~' _ Contact insecticide. Aerosol preparations, ~ granr~les, e.c. [emulsion concentrates]; 0.2-1 kg/ha Contact and intestinal insecticide. Controls ~3-~ 40~ 3~ ectoparasites and synanthropic insects. 34W Insecticide, weak fungicide. E.c. Used in 1!0(0,2b) 2~,5-27,b Insolubl 430 greenhouses. I100 129 - Poor 6 8 Insecticide with broad range of action. , . � 9.? ~Q~~,Z~ _~fi Insecticide with short active period. 50$ e.c. Good 6-? 33,8 - . 135(0,03) _ Insecticide to control ectoparasites in.;~nimal 1~ 1~ husbandry. E. c. 385 Insecticide and acaricide with broad.spectrum - 63-65 ~ of action. Controls cotton pests. 20 and:60~ 25-30 GO�~ ~ water-soluble e.c.; 0.25-O.S kg/ha. - (Techni- cal yra~3e) : . . . , ~-9i - ~og ~ ~ Insecticide and acaricide with broad spectrum 22b of action. Water-soluble concentrate; ~ 0.25-0.5 kg/ha . II6(0,2) _ Insecticide with broad spectrum of actiori:' Mixes ~8-27 Various forms; 0.2-1 kg/ha. _ 630 _ _ Insecticide, 25$ w.p. [wettable powder7 ( 2). ~ , 116 � . FOR OFF'ICIAL USE ONLY ' APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/49: CIA-RDP82-00850R040500040001-1 ~ , Chemical Name Fonaula Synonyms , 0,0-Diethyl-O- [2-chloro-l- (~:,I~`O),PaC=CtICI Birlane, supona, ~-(2~,4'-dichlorophenyl)- ~ ~ , sapekron, chl~r- ~-vinyl]-phosphate, ~ ~ I fenvinphos ~ I 0,0-Dimethyl-0- [2-chloro= (CI{,O),PUC=CFIC1 Gardona, tetrachlor- ~-1-{2~,4',5'-trichlorophenyl) p vinphos, rabon : -vinyl ] -phosphate . 0 , /CI ~ I CI~ CI 0,0-Dimethyl-(N-isopropoxy- (Cf~~p)rpNHCOOC~H~-iso Avenin carbamoyl)-phosphate ~ ~ 0,0-Dimethyl- (N-isopropoxy- (CH,U),~ NCOOC,f~i,-iso Dimufos ~-N-methylcarbamoyl)-phosphat O ~H, . Bis-(dimethylamido)-fluoro- ((CH,),NJ,PF Dimefox, pestox, phosphate ~ khanan, terrasytam O-Methyl-0-(2-chloro-4-tert- ~ Ruelene =butylphenyl)-methylamido~ CH~U~ PO / ~ C(~H~)~ phosphate Ct I,NtI~ b CI~ 0~, 0-Dimethyl-0- (6- chloro- HOE-2982 -bicyclo[3,2,OJheptadien - (~~1,0),PO -1,5-y1-5)-phosphate ~ ~ ~ IJ I ~ 117 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 ' FOR OFF[CIAL USE ONLY LD50 , - in Rats (Orally) Boiling mg/kg Point,�C LDSp in (At Indi- Solubil- Rabbits _ cated Melting ity- (Subcutan- Pressure), Point, Water, eously)~ ~ mm Hcr �C ma/liter mq/kg Use. Forn.s of Application and Consumption Norms ~~p - 145 24-39 Insecticide controlling soil-inhabiting pests. (0,001) ~gp_400 e.c., granules; 0.5-1 kg/ha � - 97-98 ~ ~ ~60p_bOpp Insecticide wit:h broad spectrum of action. ~pp 24~ e.c., w.p., granules; 0.5-1.5 kg/ha - - Boor� 5000 Systemic insecticide controlling beet pests. Seed disinfectant Systemic insecticde against various insects. Ii4-115 - ~cor E.c. . , (3) 125(2) - ;o~, ~_~,b Systemic insecticide for soil application. 5 In gelatinous capsules and in other forms. 117-118 G2-62,5 U,S~ f,6U-t000 Insecticides cont~ollinq animal ectoparasites. 0,01 Systemic insecticide with short-term action. - ~Liquid poor `~8-~~~ Controls vegetable pests. 110 ~ FOIt OFFiC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 _ :n` . ~ - K~ Chemical Name _ Formula Synonyms 3,0-Diethyl-N-(1,3-dithio-~ S Tsiolan, ditiolen, lani.mido) -phosphate (C,H~O),P-N=l~ iminofosfat ~ O,O-Diethyl-N-(5-methyl- S Dithiolane =1, 3-dithiolanimido) -phos- (CsHeO)~P-N=I~-~~ phate ~ . . O,O-Bis- -chloroethyl~) -0- (CICH,CH,O),P-O-i i i~ Haloxon -(3-chloro-4-methylcoumari- ~ ~ nyl-7)-phosphate ~ ~ CI ~ ' CH, - OrMethyl-N-methylami.do-O- ~ OGH San-52 ~ -(2-diethylamino-6-methyl- O ~ � 135-03 pyrimidinyl-4)-phosphate ~NHCH, - N~ r (C~H~1zN~ 'N ~Ctl~ N - 5- (Trimethyoxyphosphazo) - ~ ~N-CeH~ SGA-18796 -4-bromo- 2-phenylpyridazi- ( C[i,0 ),P~N none-3 ( Br - (5-Amino-3-phenyl-lH-1,.2,4- I(CH,),NJ~~N_N Triamfos� vepsin -triazolyl-1)-bis-(dimethyl- ~ C~H. amido)-phosphate H=N~~ ~ N 119 - FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 _ ~ FOR OFFICIAL USE ONLY ~50 _ in Rats . (Orally) Boiling ~q~g Point,�C LD50 in (At Indi- Solu- Ra.bbits cated Melting bility Subcutan- Pressure),Pwint, Water, eously), mm Hg "C mq/liter mg/kg Use. Forms of Application and Consumption Norms , I 15--I t8 37-45 Poor 8,9 Insecticide with broad spectrum of action (~.~Q-') 17 contralling cotton pests. E.c., granules; 0.5-1 kg/ha. . ~ - 120 Poor 12 Insecticide with broad spect,rum of action con- trolling cotton pests. 2S$ e.c., 10$ granulss. 9~ Poor ~ Antihelminthic , . - 93,5-94,5 - ~~-~5~ Insecticide and acaricide. Working concen- trations 0.025-0.2$. _ gg_gg 2!U - Herbicide controlling weeds in sugar beets. - 166-170 250 23-27 r^unqicide against powdery mildews. 25~ w.p. I500 10~' e. c. 120 ~ ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 The reaction proceeds at low temperature a.n the presence of tertiary amines, and the obtained product is placed into reaction with alcohols without separation. Vinylphosphates can also be obtained starting with dialkylphosphites and halocarbonyl compounds in the presence of bases (50). In this case the reaction proceeds in two " stages: In the first stage dialkylphosphite is joined to the halocarbonyl compound to.form phosphonate, and in the second, hydrogen halide is split off to form dialkyl- vinylphosphate: R RCUCIIIY + (~(U121'tlo (RO)7I~OCHC:(R' (RO)IP~OC=CHR, ~ -iix x ~ OFI U 1~ ..,,r Among the pesticides shown in Table 44, dichlorophos, phosphamidon, bidrin, gardona and ruelene have enjoyed the widest use. Their properties will be described in greater detail below. O,0-Dimethyl-O-{2,2-dichlorovinyl')-phosphate (dichlorophos) is a colorless liquid - with a boiling point of 35�C at 0.05 mm Hg, 53�C at 0.2 mm Hg and 74�C at 1 mm Hg. Vapor pressure at 20�C is 1.2�10-2, at 30�C it is 3.0�10'~2 and at 40�C it is 7.0�10-~ mm Hg; volatility is 145 mg/m3 at 20�C, 350 mg/m3 at 30�C and 800 mg/m3 at 40�C; d4~ 1.420, n~~ 1.4541 (see also Table 44). It is readily soluble in most organic solvents. At 20�C, 50 percent of dichlorophos hydrolyzes in 61.5 days, while at - 70�C 50 percent hydrolyzes in 25 mi.nutes. Hydrolysis proceeds faster in acid or alkaline media. Hydrolysis proceeds as follows: ~ _ (CH,O),~ li CHCI=CfiO {CEI~O);PO(.H CCI~ Hz0 - U CFI,O~ PUCH=CC1, CH,OH t10~~ Next the acid ester is hydrolyzed~to phosphoric acid. A similar reaction also pro- ceeds in various plant and animal organisms (55). Dichlorophos easily binds with bromine at its double bond to form another insecticide-- dibrom: ~ (CEI,O),f~OCN=CCI, Hr~ (CH,O)=POCHCCI~~c a b Dr 121 ~ FOR OFFIC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R004500040001-1 FOR OFFICIAL USE ONLY When heated with calcium and dialkylphosphoric acid salts, dichlorophos forms binary compounds (56) having insecticidal properties (57,59). Insecticidal compounds are also obtained by heating dichlorophos together with calcium chloride:~ 4(CH~O),~ CH =CCIz -F C~CIz ((CH,O)(CCIz=CHO)POO 1?Cn � 2(CI1,0)il'OCIf=CC~s ~ 1 0 = Two methods of obtaining dichlorophos are described in the literature. 1. Splitting off hydrogen chloride from chlorofos in aqueous solution by the action of alk~li (51,53) ; (CH,O)~PCHCCI, KOFI (CH,O)zPOCI~i=CCI~ -I- KCI fi20 ~bH ~ = It is best to perform the reaction in a biphasal system (water and an immiscible orqanic solvent) in such a way that dichlorophos would be continually rAmoved as - it is formed; in this case the dichlorophos yield may reach 80-85 percent of theo- retical. Following distillation in a vacuum, the concentration of the target sub- stance reaches 93-97 percent, depending on the purity of the initial chlorofos. 2. The second method is based on reacting chloral with trimethylphosphite (52): (CH~O)~P CCI~CHO (CH,O)zPOCH=CCI~ CH,C{ 4 O _ When the reaction is performed in a low vacuum and a temperature of about 40�C, the - dichlorophos yield exceeds 99 percent. - The maximum permissible concentration of dichlorophos in air has been set at 0.2 mg/m3 (54). When traces of moisture are present in stored dichlorophos, the latter decomposes to release acid products that catalyze the further decomposition of the preparation. � In order to stabilize the technical-qrade product, small quantities of epichloro- = hydrin (2-4 percent) are added to it to bind the acid substances and improve the storage conditions. It would be best to store the preparation in glass or metallic enameled containers. 122 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 ~E ONLY ~ ~ 'Symmetrical homologues of dichlorophos are significantly less toxic to insects. The following have recently been proposed as insecticides: 0,0-dimethyl-0-(2-chloro-2- -fluorovinyl)-phosphate (60), O-methyl-0-butyl-0-(2,2-dichlorovinyl)-phosphate (61), 0-(2'-bromoethyl)-O-alkyl-0-2,2-dichlorovinyl)-phosphate (62) and some others {63). b,0-Dimethyl-0-[1-methyl-2-chloro-2-(N,N-diethylcarbamoyl)-vinyl]-phosphate (phos- phamidon) is a colorless liquid freely soluble in water, alcohol and acetone, and _ ~poorly soluble in�~saturated hydrocarbons; its boiling point is 70�C at 0.01 ~n Hg, its vapor pressi~re at 20�C is 2.5�10'S mm Hq, and its volatility is 0.41 mg/m3 (see 'also Table 44) . Phosphamidon is resistant to neutral and weakly acid aqueous solu~:ions, while it undergoes hydrolysis quickly in an alkaline medium. In plants, phosphamidon breaks down as follows (64): - O CH~ CI (CH~O)zPOC~~CON(C=H6)s ~ . ~ (CFI~O)~POFI -I- CF~~COCHCICON(C~He)~ (CH~O)zPOC~CCONHCzNd - p O ~ti, CI _ ~ 1 ! ~ . 0 ~ CH~COCN;CI COi -I- (CzHb)sNH (CH~O),P011 CH,COCHCICO!JHC=H~ ~ CH,COCH,CI CO, C,lI6NH, _ Despite the relatively high toxicity of phosphamidon to animals, it is used as a systemic insecticide to control sucking pests of cotton and other crops. It is also effective against some gnawing pests (for example the Colorado beetle). The best way to obtain phosphamidon is to react trimethylphosphite with dichloro- acetoacetic acid diethylamide: (CIf,O),P Ct1,COCCI,CON(C=(f,)~ (CFI~O),~OC=CCICON(C,116)i CF{,CI C CH, The reaction proceeds readily when ~n equimolar quantity of trimethylphosphite is added to boiling dichloroacetoacet.'.c acid diethylamide solution in chlorobenzene. With this method the phosphamidon yield attains 83 percent. 123 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY Dichloroacetoacetic acid diethylami.de required for synthesis of phosphami.don is ob- - tained with a yield of more than 90 percent of theoretical by chlorination of diethylacetoacetamide by sulfuryl chloride (65): CH,COCHiCON(C,H6), 2SOzC1= CH,COCCI,CON(C,H6~ 2HCI -I- 2S0, Chlorination may also be performed by chlorine in the presence of urea in a water or water-alcohol medi~un (66) . ~ 0,0-Dimethyl-0-[1-methyl-2-(N,N-dimethylcarbamoyl)-vinyl]-phosphate (bidrin) is an active sy:~temic insecticide. It is a liquid that mixes with water at all dilution ratios; d}~ 1.22 (see also Table 44). At pH 9 and at 37�C, 50 percent of the preparation hydrolyzes in 50 days, while at ' = pH 1 the same amount hydrolyzes in 100 days. ~ - Bidrin is recommended against variolxs plant pests at consumption norms from 0.25 to 1 kg/ha, and against some gnawing plant pests. The metabolism of this compound in plant and anir.~al organisms proceeds simi.larly as with metabolism of phosphamidon (67,68). ~ Bidrin is synthesized by Perkov's reaction out of monochloroacetoacetic acid dimethyl- _ amide and trimethylphosphite: ~ . (CH30)~P CH~COCHCICON(C1i,), (C~i~O)zPOC=CHCON(CEI~), CN~CI O CH~ The closest analogue, azodrin, is obtained in similar fashion (69). Its chemical properties are similar to those of bidrin. A large number of analoques and homologues of bidrin and azodrin have been synthesized (70-75), containing, in the vinyl group, not only a carbamoyl (70,73) but also carbo- alkoxy and carboaryloxy groups (71,72,74,75). � O,U-Dimethyl-0-[2-chloro-l-(2~,4',5~-trichlorophenyl)-vinyl]-phosphate (gardona) is a promising insecticide against many insects. It is active against a large number of gnawing plant pests, and its toxicity to homeothermic animals is low (76-78). The trcros-isomer (in which the positions of the chlorine atom and the trichloro- phenyl group are switched)~ which is a crystalline substance with a melting point of 97-98�C (see als o Table 44), is used against plant pests and animal ectoparasites. The compound is freely soluble in organic solvents; its vapor pressure at 20�C is - 4.2�10'S mm Hg. In acid and neutral media gardona hydrolyzes slowly--at 50�C and 124 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007142/09: CIA-RDP82-40854R040500040001-1 1 ;IAL USE ONLY :pH 7 its half-life is 1,300 hours, and at pH 10.5 it is 80 hours. It is used in - various fozms. The metabolism of gardona in different species of organisms may be diagrammed as follows (76,77,79): �p c~ i,o~ tl (CII,O)~NOC=CtIC1 ~PO-C=CHC1 ' , / I10 ~ CI . ~ I ~ ( CI CI ~ ' 1 ~ . CW,CI CFI~ CH, ~O ~O HO-~H G CI CI ~ I ~ / ~ ~ / ~ ' CI CI CI CI CI CI i ~ i HzOH CHzOH CO Ff0-CH j CI / CI - j ~ ~ ~ Glucoronides CI�~~ CI/~ - CI 1 1 COOH ~ ! 10CH - ~ j CI ~ I ~ CI CI Gardona may be obtained by any of the methods described above for obtaining.enol phosphates, to include the reaction between pentachloroacetophenone and trimethyl- phosphite (47,76,80-83,86), between pentachloroacetophenone and dimethylphosphite in the presence of bases (84), and between tetrachloroacetophenone and dimethyl- chlorophosphate in the presence of bases (48,85). 125 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OFFICIAL USE ONLY The pentachloroacetophenone required for synthesis of gardona is synthesized by the E'riedel-Crafts reaction out of 1,2,4-trichlorobenzene and dichloroacetyl chloride in the presence of anhydrous aluminum chloride (80,81,83,87): CI CI CCIzHCOCI CI ~-CI CI-~ \\-COCHCIz (iC( This reaction produces a mix~ure of isomers containing about 80 percent 2,4,5-isomer, 10 percent 2,3,6-isomer and 10 percent other isomers. The mixture is separated by isolating the needed isomer in the form of a methylketal (80,87), which at low temper- ature crystallizes readily out of pentane (melting point 110-111�C). Ketone is re- _ generated from monoketal by simple heating in a vacuum (87): CI ~ /OCH~ CI- ~ ~ -COCHCIz CH~OH ~ CI ' " C-CNCIs ~ ~OH C~~ CI A large number of other enol phosphates containing aromatic radicals in the vinyl group have been synthesized and proposed far use as insecticides, but they have not as yet achieved practical application (88,89). Dimufos is an interesting new low-toxicity insecticide that can be obtained with a good yield from trimethylphosphite and N-methyl-N-chloroisopropylcarbamate (90): COOC,Ii,�u3o - (CH~O)~P uso-Caf IrOCONCICN~ CH~N-P(OCH~)~ CH~~ 1 ' ~ This preparation is proving to be successful in tests against beet pests and other plant pests (91) . - O-Methyl-0-(2-chloro-4-tert-butylphenyl)-N-methylamidophosphate (ruelene~ (see also - Table 44) is used against tapeworms in domesticated animals and gadflies as a feed additive. T'he consumption norms for different animals vary within 37-150 mg of the preparation per kq live weight. Good results can also be achieved aqainst gadflies by spraying animals with G.25-0.37 percent solutions. The preparation does not accumulate in the animal's organs, and it decomposes quickly. Ruelene may be obtained by reacting 2-chloro-4-tert-butylphenol with 0-methyl-N- -methylamidochlorophosphate in the presence of bases, or by reactinq 2-chloro-4- -tert-butylphenyldichlorophosphate with methanol and methylamine: 126 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/49: CIA-RDP82-00850R040500040001-1 _ ~ ~ CH,O~ ~~O (CI-f~),C ~ ~ ONa P CH,NH~ ~CI G O ~ (CH~),C ~ ~ OF~CI, CH,NH, CH,OH - - ` . ~ C1 ~ - ~~OCH, I-?. (CH,)aC / \ -0~ _ ~NNCH, CI _ The seconri reaction is usually performed in hydrophobic organic solvent, using anhydrous methylamxne. The 2-chloro-4-tert-butylphenyldichlorophosphate needed for the reaction is formed _ with a yield of up to 80 percent by reacting 2-chloro-4-tez~t-butylphenol with excess phosphorus chlorox'ide in.the presence of calciinn chloride or anhydrous magnesium chloride: O . {CFI~)~C ~ ~ O[t POCI~ (Cl~~)~C ~ ~ O~CI~ ? HCI CI This reaction.proceeds with prolonqed boiling. 2-Chloro-4-tert-butylphenol may be obtained at a satisfactory yield by chlorinatinq tert-butylphenol or condensing isobutylene with o-chlorophenol in the presence of various catalysts. The product usually marketed is 92 percent pure. In addition to the use of phosphoric acid derivatives as insecticides and acaricides, �se of some amides of phosphoric acid has been proposed for sexual sterilization of insects. The deepest research has been conducted on derivatives of ethylenimine, such as tris-(ethylenimido)-phosphate (TEPA, aphoxide), its methyl homologue (metepa, inetafoksid),�(tris-ethylenimido)-thiophosphate (thio-TEPA), its methyl homologue ~(metiotefa), hexa-(ethylenimido)-cyclotriphosghazine (apholate) and hexamethyltri- amidophosphate (EiI~A) : ~ FizC~ Cti~-HC~ I N P=0 I N P=O N:C~ , H3C~ , TEPA metepa ' H,C~ CH,-HC~ N P=S ( N P=S N, I ~ , H=C~ ~ thio-TEPA metiotepa 127 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY PR: N~ ~ ~ ~ ~j ~(CFr~)~ NI~P=o RfP~ipRs apholate tIMPA ~CFI= = R= -N ' ~ ~Cfi~ . When these compounds are fed to insects, they do not produce normal progeny. These compounds should be used to control only those species of i.nsects,which produce large populations within a single season. ' ~ These compounds are toxic and dangerous to vertebrate animals and man, for which reason their use is very limited for the moment, and they have essentially not gone beyc~nd the stage of production experiments. Thiophosphoric Acid Derivatives Substitution of one of the oxygen atoms by sulfur in phosphoric acid derivatives causes a significant decrease in the compound's toxicity to ma~nals without signi- ficantly changing its insecticidal and acaricidal activity, though there are excep- _ tions to this general rule. In this connection derivatives of thiophosphoric acid are broadly employed in agriculture to control pl~nt pests. As we know, thiophosphoric acid derivatives may have a thion.(I) or thiol structure (II) : - S O (R6)~P~ (RO),P~ ~ ~ ~OR' ~SR' ~ !t . mhiol derivatives of thiophosphoric acid are more toxic to mammals. _ Thion derivatives regroup into thiol isomers when heated or when brouqht in contact with certain reaqents. This reaction is known in the literature as Pishchemuka regrouping. Dependinq on the conditions and the reagents employed, the simplest derivatives of thiophosphoric acid (salts for example) are capable of forming either thiol or thion isomers, due to the dual reaction capacity of thiophosphoric acid derivatives stemminq from tautomeric transforniation~: RO~P/S ~ RO~P/O R~o~ ~`oH R'o~~ ~sti . - 128 FOR OF~`IC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R004500040001-1 It is mainly the mixed esters of thiophasphoric acid with the general farmulas III-VII that are used as pesticides. Here, R and R'--lower aliphatic radical, Ar --aromatic or heterocyclic radicals containing different substituents in the aromatic or hetero- - cyclic ring, and R"--aliphatic, aromatic or heterocyclic radical: ~ RO~ /S RO~ /O . P P ~ R'0~ ~OAr R'O~ ~SFY u~ iv RO~ /S ~ R~~ /O RO~ /O P P P R'0~ ~OCH,CH~SR" R'O~ ~SCN,Ci~ITSR" R'O~ ~SCH,COOR" ~ y vi vn :;0~ /S RS~ /O RO~ /O P P P R'NF1~ ~OAr R'O~ ~NHR" R'O~ ~SCH,Ar - ~ vui i~c .x ~iixed esteramides of thiophosphoric acid (VIII and IX~ are also used.as pesticides, but these groups contain fewer representatives. Mixed esters of thiophosphoric acid with general formula X have recently come into use against plant diseases. A larqe number of compounds containing the most varied substituents in the arematic - radical, to include one halogen atom in the ortho, metha and pa,rrt positions, two halogen atoms in different positions and three halogen atoms, have been described _ amonq mixed esters of thiophosphoric acid with general formula III. Amonq the trihaloaryl-0,0-dialkylthiophosphates, those offering the qreatest interest include 2,5-dichloro-4-bromophenyl- (94), 2,4-dibromo-5-chlorophenyl- (92,93), 2,5-dichloro= -4-iodophenyl- (95-97) and haloalkylphenyl-0,0-dialkylthiophosphates (98). Esters t:ave also been described containing, in the aromatic radical, nitro (99-105), cyan (106), acyl (107-111), dialkylaminomethyl (112), carbalkoxyl (113), thiocarbamido (114), carbamoylamido (115), trifluoromethyl (116), alkylsulfide (117-123), sulfamide (124-127) and sulfon groups (128-13Q). In addition mixed esters of thi~ophosphoric _ acid made from bis-phenols containing a sulfide and a disulfide group have been de- scribed (131-135). The following generalizations may be made about this series. 1. The strongest insecticides and acaricides are mixed esters of thiophosphoric acid in which R and R~ are lower aliphatic radicals with the number of carbon atoms ~.otaling not more than four; in this case compounds containing two ethyl radicals ar one methyl and one ethyl radical exhibit maximum activity. 0,0-dimethyl-0-ary1 esters of thiophosphoric acid are minimally toxic to mam~nals. 2. Pti.xed aliphatic-aromatic esters of thiophosphoric acid not containing functional groups in the aromatic ra~ical exhibit low insecticidal activity. - 3. Among substituted 0,0-dialkyl-O-aryl esters of thiophosphoric acid, esters con- taining a nitro qrvup at position 4 in the aromatic ring have maximum insecticidal dctivity. Esters containing a cyan, sulfide, sulfoxide or a sulfon group at position 4 exhibit rather high activity. However, most insecticidal compounds of this series are also relatively highly toxic to mauIInals. Compounds with other substituents are less effective. The corresponding 2- and 3-substituted compounds have weaker in- ~ecticidal action. 129 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02109: CIA-RDP82-00854R000500040001-1 FOR OFFICIAL USE ONLY 4. Introduction of a second substituent in the aromatic radical somewhat reduces the compound's toxicity to mammals without significantly reducing its insecticidal activity. In this case the position of the substituents has a great influence. Thus~introduction of an alkyl group or a halogen atom at position 3 of an initial ~ 4-nitro- or 4-methylthiophenol decreases toxicity to vertebrates and does not reduce the insecticidal activity of the compound, while introduction of these substituents at position 2 reduces the biological activity of the preparations in all respects. Compounds also exhibit satisfactory insecticidal activity wher.i they contain sub- stituents in positions 2, 4, 5: for example 0,0-dimethyl-0-(2,4,5-trichlorophenyl)- -thiophosphate and 0,0-dimethyl-0-(2,5-dichloro-4-bromophenyl)-thiophosphate, the toxicity of these compounds to mammals being negligible. 5. Presence of more than three substituents in the aromatic radical reduces the compound's insecticidal activity; sometimes the preparation's nature of action changes as well. Thus 0,0-dialkyl-0-2,3,4,5,6-pentachlorophenyl)-thiophosphates exhibit fungicidal activity, though not strongly enough for practical use. - 7. As we proceed from compounds with the general formula III to compounds with fonnula VIII, in many cases the insecticidal activity persists (136-139), but this group's fungicidal activity is significantly higher, and some alkylamido-O-alkyl-O- . -(2-nitroaryl)-thiophosphates have been proposed for practical use as herbicides (140,141). Haloarylamidothiophosphates, the preparation tsitron being an example, have herbicidal properties. ~ 8. 0,0-dialkyl-S-arylthiophosphates in many cases have not only insecticidal but also fungicidal action (142-144). However, their toxicity to horieothermic animals is higher than that of the corresponding thionphosphates. 9. 0,0-dialkyl-0-arylcyanoxime thiophosphates (145-148) have high insecticidal activity. The new insecticide foksim (145) is an example of such compounds. Some compounds of this type also have fungicidal action (148). Some phospharylated (at the N) N-methyl-0-arylcarbamates also have selective toxicity (149) . 10. 0,0-dialkyl-S-benzylthiophosphates, both simple and containing various sub- stituents in the aromatic radical, have high fungicidal activity (150-1~62). Similar properties are also possessed by 0-alkylalkylamido-S-benzothiophosphates and their homologues (152,155,156) and 0,0-dialkyl-S-arylthioalkylthiophosphates (160). ' 11. 0-Alkyl-0-aryl-N-alkylamidothiophosphates (163) have noticeable fungicidal ~ activity. 12. The pesticidal activity of diaryl-0-alkylthiophosphates and triarylthiophos- phates is significantly lower than that of 0-0-dialkyl-0-aryl-thiophosphate, though there are indications in the literature that triarylthiophosphates do have pesti- cidal activity (164). Some alkyldiarylthiophosphat~s have been proposed as zoocides (165). 130 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00854R000500040001-1 13. Cyclic thiophosphates obtained from salicyl alcohol (166-170) and pyrocatechol derivatives (171) are also active insecticides. 14. There are indications that compounds with qeneral formula XI have nematocidal action (172 ) ~ RO~ / O~ ~Oa S~p~O p~S xi _ . t. . 15. It would b.e,~interesting to note that 0-alkyl-S-alkyl-0--axylthiophosphates exhibit high insecticidal activity but are rather toxic to homeothermic animals (173-175). ~ 16. In most cases substitution of an aromatic radical by a heterocyclic radical also produces active insecticides, examples of which would be diazinon, dursban, tsinofox, azuntol, sayfos and others. Mixed esters and esteramides containing the most diverse heterocyclic radicals have been studied, to include mixed esters of ~ thiophosphoric acid and derivatives of thiophene (176), pyridine (177-183), _ � quinoli.ne (184), imidazole (185), benzimidazole (186,187), thiazole (188), pyri- . dazinone (189-191), oxycoumarin (192-193), triazole (194-196), pyrimidine (197-207), 'benzoxazine (208,213), benzotriazine (214-216), benzofurazan (217,218), 1,3,4-thia- ~ diazole (219), benzothiadiazole (220), dithiane ~221,222), quinoxaline (223-228) 'and others (229,230). Most nitrogenous heterocycl~ic compounds have not only in-_ secticidal but also fungicidal action, though just a few substances in this class have achieved practical use as fungicides thus far. 17. Among the homologues of the O,0-dialkyl-0-arylthiophosphates, methyl esters lhave the least toxicity in relation to homeothertnic animals, owing to their high alkylating capacity, as a consequence of which they break down faster in the bodies `of homeothermic animals. This is true for practically all series of mixed es.ters � 'of the acids of phosphorus; in this case mixed esters of dithiophosphoric acid `have a higher alkylating capacity, and owinq to this they are even less toxic to ~homeothermic animals. Thiol isomers have a lower alkylatinq capacity, and are more 'toxic. 'Some preparations in this ciass which have achieved practical use are given in 'Table 45. The following general dependencies between activity and structure are ohserved for compounds with qeneral formulas V and VI: - 1. When the total number of carbon atoms in R and R' is more than four, the com- pound's insecticidal activity decreases. 2. When the number of inethylene groups between phosphorus and sulfur atoms is ~more than four, the compound's activity declines sharply. Maximum activity is seen in compounds containing one or twn methylene groups. 131 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007142/09: CIA-RDP82-40854R040500040001-1 ~ FOR OFFICIAL USE ONLY Table 45. Aryl and Heterocyclic Derivatives Chemi.cal Name Forn~ula Synonyu~s _ 0,0-Dimethyl-O- (4-nitrophenyl)- ~Cy~p~spOCeH~N0=-4 ~taphos, methylpara- -thiophosphate ~ thion, metacide, folidol, vofatoks O-O-Diethyl-O- (4-nitrophenyl) - (CzF(60)zPOCeH~NOz-4 Thiophos, parathion, -thiophosphate p E-605 S 0-Methyl-O-ethyl-O- (4-nitro- CH,O~ Thiophos N~, methyl- phenyl)-thiophosphate POCeH,NO,�4 ethylthiophos, C,H,O~~ methylethylpara- thion O,O-dimethyl-0- (4-nitro-3-methyl- ~CIi~O)=POCeH~NOz-4-CH,-3 ~tilintrofos, - phenyl)-thiophosphate ~ sumition, metation, - ~ , fenitrotion 0, 0-Dimethyl-O- (4-nitro-3- (CIi,O),POC6H,NOz�4-CI-3 Chlorthion -chl~rophenyl)-thiophosphate ~ (CH,O)sPOCdH~NO~�4�Cl-2 O,0-Dimethyl-O-(4-nitro-2- Dicapthion, isochlor- , -chlorophenyl)-thiophosphate ~ thion O,0-Diethyl-O- (2,4-dichloro- (CiH`O)~POC`I~,CI~�2,4 ~s-13, dikhlorfention phenyl)-thiophosphate ~ 0,0-Dimethyl-0-(2,4,5-trichloro- fCt1,0),POC~N,Ct,-2e4,5 g,o~el, ~rolene, ~ phenyl)-thiophosphate ~ korlan, nankor, trikhlosznetafos, etrolene, Dow ET-14, . Dow ET-57 - 0-Methyl-O-ethyl-O-2,4,5-tri- CH~O~POCeFi?CI~-2,4,5 Trikhlormetafos-3 chlorophenyl)-thiophosphate C,H~O ~S 0,0-Dimethyl-0- (2, 5-dichloro-4- (CH,O),PO(:efi~Cl~-2,5-Dr-4 gromofos, neksion -bromophenyl)-thiosphosphate S 132 FOR OFFICIAL USF ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R004500040001-1 o� Thiophosphoric Acid Used as Pesticides LD50 in Rats (Orally) $oiling tng/kg $oi.nt, �C LDS 0 ~ _ j(At Indi- ~ - ~ Solu- Rabbits - dicated Melting. ~ii.lity (Cutane- - Pressure),Point, Water, ously). .mm/Hg �C mq/liter mg/kq _ Use. Forms of Application and Consumption Norms - ~09 35-36 65 2~60 Contact insecticide with broad spectrum of _ 2pp-3pp action. E. c. , w.p. , dusts; 0. 2-1 kg/ha. - 113 6,1 24 g_12 Contact insecticide with broad spectrum of 90-50 action. E.c., w.p., dusts, granules; 0.2-1 kg/ha. 118 6-8 Contact insecticide with broad spectrum of - ~~'12~ 40-i~ action. E.c. ; 0.2-1 kg/ha. 95 - ~ 242-433 Contact insecticide with broad spectrum of (0,01) 3ppp action. E.c. Intended for ultralow volume spraying; 0.2-1 kg/ha. 136 21 ~0 ~p_ggp Contact insecticide. E.c., dusts, w.p. ~~'2~ 1500 - b2-63 35 331)-400 � ~ Insecticide. - 108 � - 245 270 Nematocide. 75$ E. c. � (U~01) 6 000 ~7 41 44 400-3000 Insecticide controlliny animal ectoparasites. ` (0.01) 1800=-2000 127 - 40 32l}-800 Contact insecticide controlling plant pests (0,15) and animal ectoparasites. E.c. 110-142 5~1 90 2000--400~ Contact insecticide with broad spectrum of '(0,01) 3200 action. E.c., w.p., granules. 133 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-00850R000500040001-1 - FOR OFFICIAL USE ONLY Chemical Name Formula Synonyms 0,0-Diethyl-0- (2,5-dichloro- (CztidO),POCBIi,CI; 2,5-[ir-4 Bromofos-etil, _ -4-bromophenyl)-thiophos- ~ neksagan phate 0,0-Dimethyl-0-(2,5-dichloro- (~~~~~U),i OC~II,CI,-2,5-(-4 Iodfenfos, iodofos, -4-iodophenyl)-thiophosphate ~ nuvanol-N 0,0-Diethyl-0-(2,5-dichloro- (C,H60)~POC,FI,CI,�2,5-1-4 Ts-8874 -4-iodophenyl)-thiophosphate ~ " 0,0-Dimethyl-0- (4-cyanophenol) - (C[i,U)=~OCaH,CN-4 Cyanox -thiophosphate 0,0-Dimethyl-O- (3-methyl- (CH,O),POCst-I,-CH,-3-SCH,-4 ~baycid, baytex, fenthion, -4-methylmercaptophenyl)- ~ su7.'fidofos -thiophosphate _ 0,0-Diethyl-0-(2,5-dichlozo-4- (C~i~(60)s~OCbtizCl~�2,5�SCI-1,�4 5-2957 - -methylmercaptophenyl)-thio- S phosphate ~ ~ 0,0-Diethyl-O- (4-methyl- (C,H6U),~OCat1~SCi-i,-4 Fensulfothion sulfinylphenyl)-thiophosphate p . Bis- [O,O-d~.methylthiophos- (CFI,O)tPUCtlH~�nl S Abat, difos phoryl-0-phenyl-4-)~sulfide [ ~ J ~ : 0,0-Di.methyl-S-(4-chlarophenyl) (CN,O)z~SC6F1,C1-4 Funtion -thiosphosphate p a-Methyl-N-isoprop~~lamido-0- ly(3�-C,H,NH Tsitron ; - (2, 4-dichlorophenyl) -thio~ \POC6FI~CIt'Z,4 phosphate /M C(I,O g . 0,0-Diethyl-N-phthalimido- ~p Dowco-199 thiophosphate / ~ N-�~(OCzFIb), \I ~ CO S i _ I34 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 L~50 in Rats . (Orally) Boiling mg/kg point,�C LD50 ~ '(At Indi- Solu- Rabbits dicated Melting bi].ity Cutane- ~ Pressure),Point,! Water, ~ously), am Hq �C ~mct/liter mq/kg Use. Foxms of Application and Consumption Nor,ns 122-123 - 2 270 ~ Contact insecticide with broad spectrum of (O,OU3) 1366 action. - 74 2 2100 Insecticide with broad spectrum of action. W.p., e.c. - 47-~18 - l40 Contact insecticide. 30$ e.c.; 2-4 kg/ha.. 19-15 - 996 Contact insecticide. 50`s e.c.; 0.5-1 kg/ha. ~U9 - ~ 54 241-316 ~pntact insecticide controlling plant pests ~ (0,01) 341 and animal parasites. ~ ; - Liquid - 13 Insecticide with broad spectrum of action. 50$ e.c. (0,01) ~ 2,2-~0,5 Nematocide. 10~ granules. 3,5 i - 3p-3p,5 - 2000-2300 Insecticide controlling mosquitoes. i ~ 970-1900 ''101-106 _ Zn- 125 I Insecticide controlling soil pests. solu- 50$ e. c. , 2~ dust. 1 ble 51,4 5 270 Herbicide. Used to coritrol undesirable vege- tation among ornamental plants; 10-20 kg/ha - 93-84 500 Fungicide. 1 ~ 1.35 FOR OFF[CIaL USE ONLY ' APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 FOR OFFICIAL USE ONLY � ~ - Chemical Name Formula _ Synonym$ 0-Methyl-N-methylamido-0- CH,NH C~ Dowco-109, narlen -(2-chloro-4-tert-butyl- \ . - phenyl)-thiophosphate /P~-" ~ C(CH,), - CH~O S � ~ 0,0-Diethylphosphoryl-0- (C~H~O)=PON=CCeH~ Foksim, valekson -(a-cyanobenzaldoxime) ~ ~N 0,0-Diethyl-S-benzylthio- (C=H60)=PSCEi~CeHd Ketatsin phosphate ~ 0,0-Diisopropyl-S-benzyl- (u3aC,Ft~~),PSCH,CaHa Ketatsin-P thiophosphate o ~ 0,0-Diethyl-S- (4-chlorobenzyl) (C,H~O),I' SCEI=CaH,CI Danifos _ -thiophosphate p ~ 0,0-Diethyl-0-(3,5,6-tri- Dursban chloropyridyl)-thiophosphate S ~ I (CsH~O=)~ ~ N Cl O,0-Diethyl-0-pyridazinyl-2)- N Zinophos, thionazin -thiophosphate S ~ I (C,H~O)sP0 0,0--Diethyl-0-(2-isopropyl-4- ~ ~ Diazinon, basudin, -methylpyrimidyl-6)-thio- ekzodin phosphate g ~N ~ (C,fi,O):P~~ N ~CH(CH,)z , I36 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 ~so in Rats - (Orally) Boiling mg/kg Ppint, �C LDS p in - (At Indi- : Solu- Rabbits dicated Meltinq bility Cutane- P~essure), Point, Water, ously); man Hq �C. 'mg/liter mg/kg Use. Forms of Application and Consumption Norms l03-I15 - 7 7pp-Spp Antihelminthic. - (0,01) ~ 102 3-4 7 ~ Insecticide ti~ith broad spectrum of action, ~ (0.0t1 including against soil pests. 50$ e.c., ~ 40$ w.p., 5~ granules.~ ; 3~ Fungicide controlling (pirikulyariya) in rice. (0.05) . 176 - 60000 620 Funqicide controlling (pirikulyariya) in rice. 17~ granules, 68$ e.c., 2~ dust. . - - 40 17 Insecticide and fungicide. 50~ e.c.~ 41,5-43 2 135-I63 Insecticide with broad spectrum of action. - I000-2000 Various forms; 0. 5-1 kg/ha. ~ ~0 ~~qQ 12 Nematocide. E.c., 10$ granules. (O,W I ) ' ~25 - 40 120-220 Insecticide with broad spectrum of action. ~ ~ ~ 450-900 Various forms; 0.3-1 kg/ha. ~ ~ ~ 137 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 FOR OFFICIAL USE ONLY Chemical Name Formula Synonyms 0,0-Diethyl-0-(4-methyl- , ~y~ Potasan, E-838 coumarinyl-7)-thiophosphate ~ S ! I ~ (C:HeO)zPO~ ~ ~ ~ ! 0,0-Diethyl-O-(3-chloro-4- CH, Asuntol, resitox, -methylcoumarinyl-7)-thiophos- S ~ ~I muscatox, co-ral, phate ~ I ~ coumafos tC:~1s~)s~~ p . 0,0-Diethyl-O-(3,4-cyclo- ~ Dithion _ hexanocoumarinyl-7)-thio- S ~ - phosphate p f~:H`O),1~0~ Q ~ r ~ 0,0-Dimethyl-S-(~5-methoxy- ~ ~ ~ pyranyl-2-methyl)-thio- (CH,O)~PSCH,~ ~ ~ OCH, ~dotion, fosfopiran, phosphate eksotion N 0,0-Diethyl-0-(quinoxalyl-2)- S ~ I ~ Bayrusil (dietil- - -thiophosphate ~ C khinaldin) ~C~F~bO~s N / p /S 4,5-Benzo-2-methoxy-1,3,2- i ~p Salition -dioxaphosphorinanthion-2 ~ ~ ~~OCH, CH, 4,5-Cy~~lohexano-6-methyl-2- UK-2305 -chloro-1,3,2-dioxaphos- phorinanthion-2 ~jS i O ' 138 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02109: CIA-RDP82-00854R000500040001-1 LDSp in Rats (Orally) ~oiling mg/kg ~oint,�C LD50 ~ ;(At Indi- Solu- Rabbits cated Mel.ting bility Cutane- PressureJ, Point, Water, ously), mm Hq . �C ~mg/liter mg/kg Use. Forms of Application and Consumption Norms - 38 Poor 19-92 Selective insecticide controlling Colorado ! ~ beetle. ' ~ ~ _ ` ~ ~ i I - 95 1,5 100 Insecticide and antihelminthic. Use in animal husbandry. - ~ ~ ~ � - - ~-89 . Insecticide for animal husbandry. ; ~ ' - `~-91 ~ Systemic insecticide. 25$ w.p. 4p0-1000 . " ~ ~ Insecticide with broad spectrum of action. 25$ e.c., 5$ granules. - 54-55 - 91 Insecticide. W�p�, e.c. ~g _ _ ~qp Insecticide. (~~2) ' 139 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/49: CIA-RDP82-00850R040500040001-1 FOR OF'F'ICIAL USE ONLY ~ Chemical Name Formula Synonyms - 0,0-Diethy],-0- [1- (2 5 ~-di- ~ (~=H6p~spOC~CHCI Acton chlorophenyl)-2-chlorovinyl]- l -thiophosphate ~ C~N,CI,-7,5' i ~ (4-CICeH~O)zP-NHC=NH . 0,0-Bis-,~-chlorophenyl)-N- ~ ~H, _ . -acetinidinylthiophosphate ~ 0,0-Diethyl-O-(1-phenyl-1,2,4- CeH6-N-N S Khostation, fentri- -triazolyl-3)-thiophosphate I- II Y \N -Ot~(OC=Iis)~ a2ofos O,0-Diethyl-O-(5-methyl-4- CzHbOCO / N_N S ~ Afugan,. pirazofos, -carbethoxypyridopyrazolyl- ~ ~OP(OC?Hd), kuramil -9) -thiophosphate F~~~ N H~C~ ^ /OP(OCH,~ 0,0-Dimethyl-0-(2-diethyl- l~ S Pirimifos-metil, aktelli amino-6-methylpyrmidinyl- ~ YH -4)-thiophosphate N Cli ( ~ e)s H~C~, UP(OCzNs)~ 0,0-Diethyl-0-(2-diethyl- N~ ~ Pirimifos-etil, amino-6-methylpyrimidyl- ~ primitsid -4)thiephosphate N(C=~I~): CI 0 S-(6-Chloroxazolopyridinon- ~ i ~_0 SGA-18809 -2-y1-3-methyl)-0,0-di- ~ methylthiophosphate N ~Ei~SP(OCH~)~ q ~ 0 O- (5-Chloro-l-isopropyl- ~~'(OC,H~)~ -1,2,4-triazolyl-3)-0,0- N ~ S SGA-12223 -diethylthiophosphate (CH~),CH-N / N _ I 140 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 - LD50 i.n Rats iorally) Hbilinq mq/kg 1~bint, �C ~50 in , (~1t Indi- Solu- Rabbits dicated Nf~elting bility Cutane- Ptes'sure), Point ~ Water, ously), , mm Hg �C mg/liter mg/kg Use. Forms of A lication and Cons pp umption Norms 145 26 - 146 Insecticide and acaricide. E.c. ~ (0.005) - 104-106 - 3.?-7,8 Zoocide. Used in baits. - Decon~ _ ses 82 Insecticide, acaricide, nematocide. E.c. . h~n sub limated - 60-b1 190-832 Fungicide. E. c. - Liquid - 2060 Insecticide and acaricide. E.c. - Liquid - ~~-192 Insecticide and acaricide. E.c. - 89 Insecticide with broad spectrum of action. Various forms. ~ - Liquid - ~ Insecticide with broad spectrum of action, including against soil pests. t t ; ~ 141 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 - FOR OFFICIAL USE ONLY 3. Oxidation of sulfur in a carbon radical to a sulfoxide group or formation of a sulfonium compound increases the compound's toxicity, especially in the latter - case. 4. Introduction of different substituents into R" also sometimes produces active _ compounds (231,232). 5. Practically all preparations with structure V and VI have systemic action, with the contact action of thion isomers being somewhat weaker than that of thiol isomers. 6. Substitution of sulfur by nitrogen results in compounds toxic to both insects and ticks on one hand and mammals on the other. 7. Increasing the number of carbon atoms in Rr' to more than three reduces the compound's insecticidal activity. 8. Compounds in which R" is represented by aromatic radicals exhibit lower insecti- cidal activity than do compounds of the aliphatic series. , , 9. Introduction of hydrocarbon radicals into an ethylene radical also produces active compounds (233). 10. Substitution of sulfide sulfur by oxygen as a rule raises the compound's phytocidal activity, especially if an aromatic residue is bound to the oxygen - (234-236). 11. O,S-dialkylamidothiophosphates (237-242) also have high insecticidal activity; however, these compounds are rather highly toxic to homeothermic animals. Plhen the amide group is acylated by carboxylic acids the compound's toxicity to ~ animals decreases significantly (242). Acylated dialkylhydrazidothiophosphates also have pesticidal activity (243). . 12. Diamidoal;cylthiophosphates, triamidothiophosphates and mixed alkyldiamidothio- phosphates have a broad spectrum of pesticidal activity. Fungicides (163), nemato- cides (244), sexual sterilizers (245) and herbicides (246) have been found among these groups of compounds. 0,0-Dialkyl-S-thiocyanatomethylthiophosphaL-es are also active pesticides (247). _ 13. O,O-Dialkyl-S-vinylthiophosphates and O,0-dialkyl-S-vinylthiophosphates with various substituents in the vinyl radical are also active insecticides (248-253). 14. Mixed esters of thiophosphoric acid containing a carbalkoxyl and a carbamoyl group in one of the hydrocarbon radicals have high insecticidal activity as well (254-255). It should be noted, however, that the toxicity of this type of compounds is higher in most cases than that of the corresponding dithiophosphates. ~ Compounds which have come into practical use are shown in Table 46. 142 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 ` Table 46. Aliphatic Derivatives of � 'r~:. Chemical Name Formula Synonyms O,0-Dimethyl-0- (2-methylmercapto- (CH,O),I~OCH,CH,SCH, Tinoks (mixture of both ~ . ethyl)-thiophosphate S compounds, 30-40:60-70 _ O,0-Dimethyl-S-(2-methylmercapto- � respectively) ethyl) -thiophosphate (~H,O)=PSCH,CH,SCH, - 1 o ~ ~,0-Dimethyl-0- (2-ethylmercapto- (CH,O)~POCH,CH,SC,H~ Methyl-mercaptophos, ethyl)-thiophosphate S methyl-demeton, methyl- 0,0-Dimethyl-S-(2-ethylmercapto- systox (mixture of both ~ eth 1)-thio hos hate (~H,O)~pSCH,CHzSC,H~ Y P P ~ compounds, 70:30 re- p spectively) 0,0-Dimethyl-S- (2-ethylmercapto- (CIi,O)=PSCH~CH,SC=H~ Meta-systox I, ethyl)-thiophosphate 0 demeton-S-methyl 0,0-Dimethyl-S- (2-ethylsulfinyl- (CH,O)~PSCH=CN,SC=H~ Meta-systox R, ethyl)-thiophosphate ~ ~ demeton-0-methylsulfoxid~ O,n-Dimethyl-S- (2-ethylsulfonyl- (CH~O),PSCH,CH~SO~CzH~ Demeton-S-methylsulfone ethyl)-thiophosphate 0 0,0-Dimethyl-S- (1-ethylsulfinyl- (~H,O),~SCHCN,~ ,H~ iyeta-systox S propyl-2)-thiophosphate 0 CH, b, 0-Diethyl-0- ( 2-ethylmercapto- ~~~H`O),POCH~CH,SC,H~ ~~ton, systox, mer- ethyl)-thiophosphate ~ captophos (iaixture of b,0-Diethyl-S-(2-ethylmercapto- both compounds, 70:30 ethyl)-thiophosphate (~zH�O)~~SCH~CH~SC~H~ respectively) O d,0-Diethyl-S- (2-diethylamino- (C~H60)=PSCH,CH~N(C=H~)~ p,m,i.ton, tetram, ethyl)-thiophosphate.�oxalate ~.fi00CCOOH inferno, metramac 0,0-Dimethyl-S- (carbethoxymethyl) (C~i,O},PSCH,COOC,H~ Metilatsetofos ~ -thiophosphate ~ q ~ O 0,0-Diethyl-S-(carbethoxymethyl)- (C~HbO)~PSCH~COOC~H~ Atsetofos '-thiophosr~hate ~ ~ O,0-Dimethyl-S-(N-methylcarbamoyl (Cti,O),~SCH,CONHCH, Ometoat, folimat ~methyl)-thiophosphate 143 . FOR OFF'ICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE ONLY Thiophosp;zoric Acid Used as Pesticides LD50 in Rats (Orally) ` Boiling mq~kg . Point,�C LDSp in (At Indi- Solubil- Rabbits cated Melting ity- Subcutan- Pressure), Point, Water, eously), _~nm-HQ_~_mQ/liter mg/kg Use. Forms of Application and Consumption Norms 115 - 50U b0 Systemic insecticide and acaricide. E.c.; ~2~ 0.5-1 kg/ha. 109 - 2000 qp ~ l2) ~ 140 ~3 S stemic insecticide and acaricide. 3p-50~ (0.5) e.c.; 0.5-1 kg/ha. IuY - 3300 40-60 ~0~4) ' 80-l00 (4na cMecEi) - Systemic insecticide ~d acaricide. E.c.; . 0.5-1 kg/ha. (0,01) Mixes � 65-75 Systemic insecticide and acaricide. 25-50~ e.c.; 0.5-1 kg/ha. - ~ ~ 40 ~ Systemic insecticide and acaricide. Used in mixture with azinphos-methyl. E.c., w.p. 115 - Good ~ 105 Systemi.c insecticide and acaricide. 50$ e:c.; (0,02) 0.5-1 kg/ha. - ~a' - ~ 7-10 Systemic insecticide and acaricide. 30-50$ (0~~) e. c. ; 0. 3-1 kg/ha. _ _ ~ ~ _ (0~2~~1 Good 3-7 Systemic insecticide and acaricide. - ~~s - ~od - 1000 Contact insecticide. E.c., dust. ,~p~~~ ~20 - ~ood 300_~pp Contact insecticide. E. c. , dust. (0,16) H _ Decom- - ~od 5p Systemic acaricide and insecticide. 50~ e.c.; poses 700 up to 1 kg/ha. Iwhen ~ distilled 144 - FOR OFFIC[AL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 Chemical Name Fortnula Synonyms 0,0-Dimethyl-S- [2- (N-methyl- 0 NSCII UI SC}ICONHCH Vamidotior~, kil'val'., carbamoylethylmercapto) - ~ ' ` ' I ' trutsidor -ethyl]-thiophosphate U , CH, ~ . . 0-Methyl-S-Methylamidothio- C H,O~ Tamaron, monitor phosphate /~NH, Cf1~S ~ Q,S-Dimethyl-N-acetylamido- CH,O~ Ortho-12420 thiophosphate PNHCOCH, _ CN'S~O . C,H~Ntf H ' b1-Ethylamido-0-methyl-O- ~ j San. 52-139 - [1-methyl-2- (carbisopropoxy) - ~ POC=~-COOC,FI,�u3o -vinyl ] -thiophosphate ~f~'~/y~ ~H~ 145 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFF'ICIAL USE ONLY ~ LDS 0 in Rats (Orally) ~ Boiling mg/kg Point,�C LDSp in (At In- Solubil- Rabbits dicated Melting ity- (Subcutan- Pressure),Point, Water, eously), mm Ha . �C . mg/liter mg/kg Use. Forms of Application and Consumption Norms ~ - 4G-48 Good 64-105 Systemic insecticide and acaricide. 40$ e.c.; t l#U 0. 3-1 kq/ha. - a'~,5 Good ~ Systemi.c acaricide and insecticide. E.c., ~ 18 granules. " 8p t;oad 8GG-945 Insecticide. 75$ w.p. 2000 87-$y - 0,5~ IIO-120 Insecticide. 25~ e.c., 10$ - - (0.005) granules . . 12b0 - 146 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 The following reactions are the principal methods of obtaining thiophcsphat~s III and V: ~ Ro~ g R~~ 1 ~ PCI HOAr POAr R'0~ R~~ S - PSCi~ ? ArOH K} ArOPCI~ ? HCI s N . - ArOPCI~ ? 2ROH (ROhPOAr. The first of these reactions proceeds readily when both organic and inorganic bases ~re used as hydrogen chloride acceptors. The best orqanic bases to use are tertiary ~mines, for example triethylamine or pyridine. The reaction proceeds with high yields in the presence of caustic alkali or alkali metal carbonates. The best results are obtained with potash, especially when the process is carried out in a solution of aliphatic ketones (acetone, methylethyllsetone). The reaction may also be,carried aut in the presence of catalytic quantities of tertiary amine, followed by satura- tion of the reaction medium with s~dium or magnesitun chloride (256). C~ood yields of mixed esters of thiophosphoric acid may be obtained by performing the reaction in an aqueous medium in the presence of surfactants and in organic solvents. Thfhhen the process is performed in organic solvents, the resulting preparations are purer as a rule, but the process is more camplex because the solvent must be dis- tilled away in a rather high vacuum, and film-type continuous-action evaporators must b~e:used. The reason for this is that many mixed esters of thiophosphoric acid can ~e- compose when heated at 80-140�C for a lonq period of time; moreover such decomposi.tion may proceed spontanzously with an explosion occurring. Mixed~esters o� thiophosphoric acid containing a nitro group in the aromatic radical decompose especially readily. F~owever, when sufficiently pure phenols and dialkylchlorothiophosphates are used in an aqueous medium, mixed thiophosphates can be obtained with good yields and with. ~ target substance concentration greater than 90 percent. The process would ~st be carried out at 50-100�C, and with rather intensive mixinq to maintain a constant _ pH in the medium. An, aqueous solution of alkali metal phenolate is placed in a reactor containing an effective agitator, and after the solution is raised to the required optimum temperature, dialkylchlorothiophosphate is added gradually. Be- cause dialkylchlorothiophosphate undergoes partial hydrolysis, the mediiuri's pH c~hanges rather quickiy; alkali is added to the reaction mixture to keep the pH con- stant. The optimum pH varies for different phenols. After the reaction ends, the oily layer is separated away and washed with an aqueous alkali solution (to remove phenol that had nat entered into the reaction). After it is dried, it is used to make the required form of the preparation. qne of the most important conditions of storing mixed esters of thiophosphoric acid - is absence of moisture, inas~uch as the compound may undergo hydrolysis, and when inetallic containers are used colloids may iorm, resulting in gelatinization of the 147 - FOR OFFICIAL USF ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00854R000500040001-1 FOR OFFICIAL USE ONLY preparation which makes it difficult to use. Nor must the preparation cont~in sig- nificant quantities of trialkylthiophosphates, especially trimethylthiophosphates. 'Phe dialkylchlorothiophosphates required for the synthetic processes described above ~~re obtained at good yields as follows: S PSCI~ ItOH ROPCI, I~iCI g RD S ROIPCI= -I- R'OH ~PCI . R' O~ The reaction between PSC13 and alcohols proceeds readily in response to slight heating, and the alkyldichlorothiophosghate yield is not less than 90 percent of theoretical. Alkyldichlorothiophosphates are allowed to react with alcohols at tem- peratures from -5 to 0�C while stirring vigorously. Both tertiary amines and caustic alkali can be used to bind hydrogen chloride, and when dimethylchlorothioptiosphate is the target substance, 40 percent aqueous sodium hydroxide solution can be used. Mixed dialkylchlorothiophosphates in which a methyl group is one of the ester radicals form with a yield close to 90 percent. High yields of dialkylchlorothiophosphates are also obtained by reacting alkyldi- chlorothiophosphates with sodium or magnesium alcoholates: S S R0~ ROIPCIi R'OM R~O/PCI MCl The optimum temperature for a reaction with sodium alcoholate is from -10 to -15�C. At higher temperatures the yield decreases and a significant quantity of trialkyl- thiophosphates fonns. Synthesis of dialkylchlorothi.ophosphates from magnesium alco- holates is relatively simple, and it proceeds at higher temperature. A good method of obtaining dialkylchlorothiophosphates is chlorination df dialkyl- - dithiophosphoric acids (257~ or bis-(dialkylthiophosphone)-disulfides: ~ (RO)zPSti ? Ci, (RU)2II CI HCI S S S ((RO)~IIS1 CI, 2(RO)~IICI 2S L S S In the presence of excess chlorine, sulfur chloride is obtained as a byproduct. Chlorination may be carried out not only with chlorine but also with various chlori- nating agents, to include phosphorus pentachlaride, sulfur chloride and dichloride, ~ 148 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/49: CIA-RDP82-00850R040500040001-1 sulfuryl chloride and other similar compounds. The reaction is carried out at lower tamperatures, both with and without various organic solvents. It would be convenient to perform the reactioz~ with chlorine, and then.remove sulfur chloride by treating - the product with H2S. In this case sulfur chloride transforms into elemental sulfur, which is easily separated from dialkylchlorothiophosphate by simple filtration. The yield of dialkylchlorothiophosphate in this method is about 90 percent; the concen- tration of the target product is more than 90 percent (269). This is a convenient method for obtaining dialkylchlorothiophospliates with identical ~iydrocarbon radicals; if dia~kylchlorothiophosphates with different radicals are required, it would be better to use the reaction with PSC13, described above. In turn, PSC13 can be abtained industrially at a quantitative yield by passing PClg vapor througY. melted sulfur to which alkali metal polysulfides are added as catalysts (258). A flowchart for production of PSC13 is shown in Figure 17 (258). 1 3 _ ~ 9 ,o s t S 8 1 ~ 4 6 1! 12 Figure 17. Flowchart for Production of Phosphorus Thiotrichloride: 1--PC13 gaging tank; 2--P~13 evaporator; 3--sulfur gaging tank; 4--reaction columns; 5--.i.r coolers; 6--condensate collectors; 7--distillation vat; 8--rectification column; 9--fractionating colwnn; 10--cooler; 11--PClg-PSClg mixture receiver; 12--PSClg receivers Aryldichlorothiophosphates are fozmed with prolonged heating (not less than 10 hours) at 110-115�C togetner ~ith the appropriate phenol and excess PSClg, in the presence af small quantities of potassium chloride or anhydrous magnesium chloride. After the reaction ends, excess PSC13 is distilled away in a water bath in a vacuum, and the aryldichlorothiophosphate is su~jected to further processing (26~)). To obtain dialkylaryltY,iophosphates, aryldichlorothiophosphate is reacted wi.th the alcoholates of the appro~riate~ alcohols. Alcohol can also be used in the presence ur a hydrogen ch~oride acceptor, but in this case the yield of dialkylarylthio- - phosphates is lower. 149 FOR OFF[CIAL TJSE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY 0-Aryl-O-alkyl-N-alkylamidothiophosphates are synthesized by reacting amines with aryldichlorothiophosphates in the appropriate alcohol: S I~ Ar0 /S ArOPCIz ROI~I 3R'NHz ~ ~P~ . 2R'NH~ � FiCI R0~ ~NHR' Thiolphosphates ~V, VI and VII are usually obtained by reacting dialkylthiophosphoric acid salts with halogen derivatives: R0~ ,o R0~ /o P R CI P NaCI R'0~ ~SNa R'O~ ~SR" This reaction proceeds readily with most dialkylthiophosphates, with dimethylthio- = phosphate being an exception. Methylation proceeds in reactions of the latter, and a significant quantity of trimethylthiolphosphate is formed as a byproduct (261). Some of the most important derivatives of thio phosphoric acid are described in - greater detail below. - 0,0-Dimethyl-0-(4-nitrophenyl)-thiophosphate (metaphos) is a white crystalline _ substance; its vapor pressure at 20�C is 0.97�10-5 mm Hg; its volatility is 0.14 mg/m3; d4~ 1.358; rt~j5 1.5515. It is poorly soluble in ~araffin hydrocarbons and readily soluble in aromatic hydrocarbons and in most organic solvents (see also Table 45), The ra~e of hydrolysis of inetaphos is significantly higher than that of thiophas; At 20�C and pH 1-5, 50 percent of the preparation hydrolyzes in 175 days, while at 70�C it takes 11 hours. The rate of hydrolysis in an alkaline medium is even greater. Relatively speaking, metaphos is thermally unstable, and when heated to 140-160�C it transforms almost completely into the corresponding thiol isomer; sometimes an explosion occurs, and a porous mass containing a large quantity of carbon forms: ia-~6o ~c ~H'~\ (Cfi,O),POC6H~N0;-4 --y. POC~H~NO,-4 ~ CH,S~~ This reaction also proceeds when an alcohol solution of inetaphns is heated for a long period of ti.me at 100�C. The products of thermal decompositzon of inetaphos have also found to include trimethylsulfonium salts, obtained as a result of ~ methylation of dimethylsulfide; the latter possibly forms from 0-methyl-S-methyl-0,4- -nitropheny~thiophosphate. Metaphos is a strong alkylating agent and is capable of methylating sulfides, amines, phosphines, thiourea, and many other compounds, . 150 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE ONLY (CH~O)zPOCeH~NOz-4 ? (C,Haj,N -r ' ~ " ~ CH,S~ - . . ((CzNel~~`ICH~j POCeH~NOI-4 _ 0/O - The high methylating capability of inetaphos is possibly a cause of its lower toxicity to mananals, si.nce part of the preparation is broken down by demethylation prior to . ~eaching the reactive centers, of cholinesterase (261). - In all other chemical properties metaphos is similar to thiophos. The toxicity of inetaphos to homeotherms is siqnificantly lower (LL~Sp 25-50 mg/kg); in comparison with thiophos it does not ~enetrate throuqh skin as easily, which makes work with it less difficult. Z'he iaaximum pezmissible concentration of inetaphos in air i.s 0.1 mg/m3. Metaphos is marketed as emulsions, wettable powders and flusts.� When selecting fillers for dusts and wettable powders, it should be ]cept in mind that even weakly alkaline fillers are ill-suited, since metaphos (and thiophos as well) breaks~down relatively _ quickly in these filters and loses its insecticidal properties. ~ The preparation is used aqainst a broad range of plant pests, similarly as with thio- ' phos. Because it is less toxic to.mammals, metaphos is gradually supplanting thio- , phos. World production of inetaphos is higher than thiophos production, and it is exhibiting a tendency toward further gr~wth. � . ; Metaphos may be synthesized by all of the methods described above for~obtaining i , mixed aliphatic-aromatic esters of thiophosphoric acid. The most important in- i dustrial. method of obtaining metaphos is to react dimethylchlorothiophosphate with p-nitrophenol in the presence of hydrogen chloride acceptors or with sodium p-nitro- phenylate; the reaction is performed in water in the presence of emulsifiers (for example ammonium naphthenate or amines) and in organic solvents. Chlorobenzene, ! xylol or aliphatic ketones (acetone and methylethylketone) are used most often. I . i When the reaction is carried out in organic solvents, the solvent must subsequently ~ be distilled away, which must be done at the lowest possible temperature in continu- ' I ous-action film evaporators. Otherwise the metaphos may break down, sometimes even ~ with an explosion. . Preparation containing up to 96-98 percent 0,0-dimethyl-0-(4-nitrophenyl)-thi.ophos- - phate is obtained by reacting dimethylchlorothiophosphate with p-nitrophenol in the presence of anhydrous potash in acetone, usinq sufficiently pure initial products. For c.onvenience of handlinq and transportation, this product is diluted with 10-15 percent xylol. . When the reaction is performed in an aqueous medium, the resulting preparation con- tains SS-90 percent tar.get s~bstance. With different methods, the metaphos yields vazy within 75-90 percent of theoretical. 151 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007142/09: CIA-RDP82-40854R040500040001-1 F~DR OFFICIAL USE ONLY Impurities in the technical-grade preparation include small quantities of p-nitro- phenol, O-methyl-0,0-bis-(4-nitrophenyl)-thiophosphate and trimethylthiophosphate. In addition preparations obtained in organic solvents also contain O,~-dimethyl-0- -(4-nitrophenyl)-thiophosphate as an impurity. ~i ~ The insecticidal properties of all metaphos isomers have been studied, to include the and forms of O,S-dimethyl-O-(4-nitrophenyl)-thiophosphates, of which the left isomer has been found to be more toacic to animals (LDSp in rats is 25 mg/kg, while the toxicity of the right isomer is 135 mg/kg). Of the three thiophosphates with sulfur in different positions, the most toxic is 0,0-dimethyl-S-(4-nitrophenyl)- -thiophosphate (the LDSp in mice is 7.5 mg/kg). 0,0-Dimethyl-O-(4-nitro-3-methylphenyl)-thiophosphate (metilnitrofos) is a light- colored liquid with unpleasant odor; its vapor pressure at 20� is 6.0�10'6 mm Hg; i2~ volatility is 0.09 mg/m3; its viscosity at 30�C is 20.8 centipoise; d4~ 1:308; ; nD 1.5505. It is freely soluble in most organic solvents, it mixes in all ratios with methyl and ethyl alcohols, alkylacetates (262,263), ketones and aromatic hydro- carbons. Its solubility is about 4 percent in kerose ne and about 7 percent in - petroleum ether (see also Table 45). Its LD50 in various E,xperimental animals is within 142-1,000 mg/kg. Its nature of action upon animals is similar to that of inetaphos. Metilnitrofos is practially indistinguishable from metaphos in its chemical proper- ~ ties, but its rate of hydrolysis by water and alkaliS is somewhat lower. Thus it takes 5 minutes for 50 percent of inetaphos to be hydrolyzed in 0.1 N sodium hydroxide solution at30�C, while metilnitrofos takes 12 minutes. This preparation's thermal stability is also not very high, and when heated above - 100�C it undergoes Pishchemuka isomerization and may explode as it decomposes. In ~ this connection overheating of the preparation should be avoided, both during its production and during storage. The preparation must be stored in enamel, aluminum = or glass containers. Iron promotes this preparation's decomposition, as~is true with most other organophosphorus compounds. . 0,0-Dimethyl-0-(4-nitro-3-methylphenyl)-thiophosphate is obtained by condensation of dimethylchlorothiophosphate with sodium 4-nitro-3-methylphenolate in an aque^~~s medium, or with nitrocresol itself in the presence of anhydrous potash in zc�+~^n~ - or methylethylketone: (Cti,O)~~CI NO, ~ ~ ONa _ $ H~C ~ ---r (l:lf~O)iPU ~ ~ -N0: IVaCI ~ CH~ It is very difficult to synthesize 4-nitro-3-methylphenol, since as with direct nitration of m-cresol, a mixture of 4-nitro- and 6-nitro-isomers contai.ning not more than 60 percent of the needed product forms. 152 - � FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407102/09: CIA-RDP82-00850R000500440001-1 . FOR OFFICIAL USE ONLY Sufficiently pure 4-nitro-3-methylphenol can be iso~ated either by nitration of esters of m-cresol and carboxylic acids or by oxidation of the appropriate nitroso- phenol (272 ) : li, Oti ~ H,C / OH ~o~ HsC / O \ J H N O= i~'e/ ON O,N ~ However, up to 30 percent of valuable m-cresol is lost in both methods of obtaining 4-nitro-3-methylphenol. Systematic investigation of the insecticidal properties of mixtures of various c~ompounds showed that O,0-dimethyl-0-(6-nitro-3-methylphenyl)-thiophosphate is an active synergist i.n relation to many organophosphorus insecticides--thiophos, ~etaphos, thiophos-ME and 0,0-dimethyl-0-(4-nitro-3-methylphenyl)-thiophosphate. When mixed at a 1:1 ratio with 0,0-dimethyl-O-(6-nitro-3-methylphenyl)-thiophosphate, each of these organophosphorus compounds is active ~at the same concentrations as the pure compound on its own. A mixture of O,0-dimethyl-0-(4-nitro-3-methylphenyl)-thio- phosphate and 6-nitro isomer, which is obtained by reacting dimethylchlorothiophos- phate with isomeric nitrocresols--products of direct nitration of m-cresol by nitric acid--has been proposed for use in agriculture. In terms of its insecticidal and acaricidal activity this mixture is practically indistinguisl:able from pure 0,0-dimethyl-0-(4-nitro-3-methylphenyl)-thiophosphate. This preparation is called metilnitrofos in the USSR (264,265). Metilnitrofos and its analogues are marketed in the foxm of a 50 percent emulsion concentrate and as a preparation for ultralow volume spraying. 0,0-Dunethyl-0-(2,4,5-trichlurophenyl)-thiophosphate (ronnel, trikh.lormetafos) is a white crystalline substance; d4~ 1.4850; vapor pressure at 25�C is 0.8�10-3 ~n Hg. It is readily soluble in most organic solvents (see also Table 45). Trikhlormetafos is stable at temperatures up to 80�C. In weakly alkaline medium it hydrolyzes ta form predominantly O-methyl-0-(2,4,5-trichlorophenyl)-thiophosphoric acid, while in a highly alkaline medium it fozms predominantly 0,0-dimethylthiophosphoric acid: ' CI~ . CI1~0 ' ~PO- ~ -CI CH,ON _ HD~S CI ~ (CH,O),PO- ~ ~ -CI - CI . ~ ` Ci /OH (CIi,O}~P~~ HO- ~ ~ -CI S . ' ~ ' CI - In the bodies of cows and rats about half of the administered preparation is eli.minated with urine as 0-methyl-O-(2,4,5-trichlorophenyl)-thiophosphoric acid, while in the bodies of insects it breaks down predominantly into dimethylthio- phosphoric acid and 2,4,5-trichlorophenol. 153 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY Trikhlormetafos is characterized as mildly toxic to homeothermic animals, and it is used agai.nst ectoparasites of farm animals, both as topical emulsions and as feed additives. The LDSp in animals is within 400-3,000 mg/kg. Several methods of obtaining trikhlormetafos have been described, the most important ones of which are: = 1. Reacting sodium 2,4,5-trichlorophem late with dimethylchlorothiophosghate in an aqueous medium in the presence of emulsifiers: CI C~ /CI ~ (CEi,O),P~~ -t- Na0 _ CI (CH,O),i0 ~ CI NaCI S S CI CI In this reaction the yield of trikhlormetafos is 85-90 percent of theoretical; it contains a certain quantity of 2,4,5-trichlorophenol as an impurity; the latter can be washed away with a small quantity of sodium hydroxide. 2, R~acting dimethylchlorothiophosnhate with 2,4,5-trichlorophenol in methylethylketone in the presence of finely pulverized potash, the yield being up to SO percent. 3. Methanolizing O-(2,4,5-trichlorophenyl)-dichlorothiophosphate in the presence of sodium hydroxide: ,Cl CI- ~ ~ -OPCI, ? 2CH~OF1 2N~ ON - ~,Y ~ (CH,O)zP0-" "--CI 2NaC1 -1- 2H,0 . . ~ . The O-(2,4,5-trichlorophenyl)-dichlorothiophosphate needed for this synthesis is obtained in the following reaction: 154 ~ - FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 . FOR OFF[CIAL USE ONLY - CI CI ~ MQCIz S CI ~ ~ OH PCI~ CI ~ ~ OPCI~ CI CI CI _ CI ~ `-OPCI~ i - . ~ , CI 0-(2,4,5-trichlorophenyl)-dichlorophosphite is formed with a yield of about 90 percent when 2;4,5-trichlorophenol is heated for a long period~of time with phosphorus tri~ - cl~loride (in great excess) in the presence of a catalytic quantity of anhydrous magnesium chloride. Sulfur is attached without isolating 0-(2,4,5-trichlorphenyl)- -dichlorophosphite in pure form, and it is only after the second.reactionthat the phosphorus trichloride is distilled away. The removed phosphorus trichloride is returned to the acquisition process of 0-(2,4,5-trichlorophenyl)-dichlorophosphite Volatile impurities can be removed from trikh�lormetafos by dis�tillation with live steam (266,267).. ~ T~e preparation is marketed in the USA with two degrees of purity: Ninety eight- ninety nine percent main ingredient, and about 55 percent main ingredient. O-Methyl-0-ethyl-0-(2,4,5-trichlorophenyl)-thiophosphate (trikhlormetafos-3) is the closest homologue of trikhlormetafos, and it was first synthesized and proposed for agricultural use in the Soviet Union. It is a colorless oily liquid having a vapor pressure at 20�C of about 0.6�10'3 mm Hq; its volatility is about 8 mg/m3; d~~ 1.4345;' n4~ 1.5520 (see also Table 45). It is freely soluble in most organic solvents, and - its solubility in water is 40 mg/l~iter. Its LDSp in various experimental animals is 330-800 mg/kg. - mrikhlormetafos-3 is used against insects and flies serving as a public health nuisance. It is applied topically and administered gastrically at consumption norms on�the order of 35-40 mg/kg animal live weight to control the cattle fly. At such doses the preparation 'is eliminated relatively quickly from the animal body, and it cloes not remain in milk and meat. I.t is also recommended against plant pests, and it is effective against many suckin~ insects and ticks at a 0.1 percent concentrat~ion. _ At these concentrations it does not injure plants (in contrast to ronnel, which is hiqhly phytocidal). It is marketed in the form of 30 and 50 percent emulsion concentrates containing _ emulsifiers in addition to the active ingredient. The main method of obtaining trikhlormetafos-3 is to react 0-methyl-0-ethylchloro- thiophosphate with sodium 2,4,5-trichlorophenylate in an aqueous medium in the presence of emulsifiers (the yield is 85 percent): . 155 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 FOR OFFICIAL US~ ONLY CI C~ ~ CF1,0. ~ CH,O~ _ ~ PCI -i- Na0 CI PO- CI NaCI C'H6~/S C~H6~/S . CI CI T'he impurities in trikhlorm~etafos-3 include small quantities of 2,4,5-trichlorophenol, dimethylethylthiophosphate and some other compounds. The purity of the initial sub- stances, and primarily of inethylethylchlorothiophosphate and 2,4,5-trichlorophenol, has great significance to the quality of the preparation obtained. The former must not contain diethylchlorothiophosphate impurities while the latter must not contain dichlorophenols and isomeric trichlorophenols. Phenols can be removed from trikhlor- metafos-3 by washing it with aqueous alkali solutions, while tri~ethylthiophosphate and other volatile impurities can be removed by distillation with live steam (266). Trikhlormetafos-3 is similar in chemical properties to ronnel, but it differs from the latter in being more resistant to hydrolysis and reacting more slowly with amines. Hydrolysis of trikhlormetafos proceed similarly as with hydrolysis of ronnel. O,0-Diethyl-0-(2,4,5-trichlorophenyl)-thiophosphate is significantly more toxic to mammals than ronnel and trikhlormetafos-3. 0,0-Dimethyl-0-(2,5-dichloro-4-bromophenyl)-thiophosphate (bromofos) is a white crystalline substance; its vapor pressure at 20�C is 1.3�10-4 mm Hg;~its solubility in organic solvents at 20�C is (in gm per 100 gm): 109 in acetone, 21 in diesel - fuel, 8 i.n isopropyl alcohol, 10 in methano]., 120 in methylethylketone, 90 in xylol, 98 in chlorobenzene and 112 in methylene chloride .(see aTso Table 45). In an alkaline medium broinofos hydrolyzes similarly as with ronnel to form 0,0-di- methylthiophosphoric acid, 2,5-dichloro-4-bromophenol,~0-methyl-O-(2,5-dichloro-4- -bromophenyl)-thiophosphoric acid and methanol. . . I y ~cii,o~~P-o- _ ~ iizo -I ~ ~ ~i c~ ~ s - ~cf~,o),~f + }~o- ~ ~ -a~ ~Oli - Cl ~ ' , CI . . � CH,O~ P-O- ~ ~ kir + CIi,ON . HO~S ~ CI 156 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2447/02/09: CIA-RDP82-00850R000500444441-1 FOR OFFIC[AL USE ONLY - At 22�C and pH 13, 50 percent of the preparation hydrolyzes in 3.5 hours. On plants, bromofos decomposes practically completely in 13-20 days, 3epending on the plant species. Bromofos is a mildly toxic preparation: Its LDSp to various animal species is within 2,000-4,OOO.mg/kg. ~ Bromofos may be synthesized by all of the methods described for ronnel. The greatest - difficulty lies in making 2,5-dichloro-4-bromophenol which apparently would best be obtained by bromination of 2,5-dichlorophenol. In turn, 2,5-dichlorophenol can be forn~ed by saponification of 1,2~,4-trichlorobenzene Yiy sodium hydroxide in methanol at 160-190�C under pressure. In this case a mixture of 2,4- and 2,5-dichlorophenols is ~ p~oduced, which is then separated by fractional precipitation out of alkaline solu- tions, since the two compounds have different dissociation constants, or they may be separated by complexinq with.urea (270,271). ~ Bromofos has been proposed for use against the most diverse species of insect pests, - to include flies and other insects causing a public health nuisance. It is used as - 20 and 25 percent emulsion concentrates, as 5 percent granulated preparations and as aerosols. The nearest homologue of bromofos is bromofos-etil, [O,0-diethyl-0-(2,5-dichloro-4- -bromophenyl)-thiophosphate], which is an oily liquid; its vapor pressure at 30�C is 4. 2� 10~ 5 mm Hg ( see also Table 45) . ' Its LDSp in rats is 238 mg/kg. B,romofos-etil is close to bromofos in its insecticidal activity. The preparation iodfenfos (iodofos), or O,0-dimethyl-O-(2,5-dichloro-4-iodophenyl)-thiophosphate, w~ich has been recommended in animal husbandry to control a number of flying insects Gsee Table 71) [table not reproduced], has a wide.spectrum of action and a long time of action. ~ 0,0-Dimethyl-0-(4-methylmercapto-3-methylphenyl)-thiophosphate (lebaycid) is~a colorless oil; its vapor pressure at 20�C is 3�10-5 mm Hg. Its volatility is 0.46 mg/m3. It is freely soluble in most organic solvents, including alcohols, ethers, esters and halogen derivatives of aromatic and aliphatic hydrocarbons, and it is poorly soluble in petroleum ether (see also Table 45). Its LDSp in rats is 215-245 mg/kg. - Lebaycid is more resistant to hydrolysis and heating than metaphos. At 80�C 50 per- cent of the.preparation hydroly~es in an acid medi~n in 36 hours, and in an alkaline medium in 95 minutes. When it reacts with oxidizers, lebaycid oxidizes first to sulfoxide.and then to sulfone: ~ � ' H~C H~C (CI1,0)1f~-O " " SCFI~ (CHlO),P-0 " " SCI~1~ II ~ h ~1 S ~ S U H,C H,C O O ---..(CII,o)~I~-O- ~ ~ SCH, (r.ti,0)zP-O ~ ~ SCH, II N fl - II S O O O 157 FOR OFFICIAL US~ ONLY . APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 . FOR OFFiC[AL USE ONLY Then oxidizers split off the thion sulfur from sulfone, which transforms into the appropriate phosphate.~ ..In natural conditions lebaycid is stable, and it may persist for a long period of time. In terms of its toxicity to insects, lebaycid is similar to chlorofos, but its selectivity is lower, since its toxicity to mammals is higher~. In anin?als and on plants, lebaycid oxidizes to sulfone, which then hydrolyzes and breaks down into products harmless to animals. It is marketed~in the form of a 50 percent emulsion concentrate, a 25 percent ~ wettable powde1�and a 3 percent dust. ~ Lebaycid is obtained with a 90 percent yield (of theoretical) by reacting 4-methyl- mercapto-3-methylphenol with dimethylchlorothiophosphate in methylethylketone at _ 60�C in the presence of finely pulverized potash. The 4-methylmercapto-3-methylphenol required for this purpose is synthesized out of dimethylsulfoxide'and m-cresol (268): OH OH OH ' / HCI / / (CH,)zS0 -i- I ~ _ci~,ci~ ~ ~ CI{~ ~ CH, ~ CFi~ . 'S(CH,)~ CI~ SCH~ 4-Methylmercapto-3-methylphenol can also be obtained by reacting dimethyldisulfide ~ and sul'furyl chloride with m-cresol. A large number of analogues and homologues of lebaycid have been synthesizeiz and studied, but most compounds are~more~toxic to anin~als than lebaycid. In particular both O,0-dimethyl-0-(4-methylmercaPtophenyl)-thiophosphate and its oxygen analogue - are more toxic. When a methyl group or a halogen atom is introduced in many mixed thiophosphates at the~meta-position in relation to the ester group, toxicity to vertebrates decreases while comparatively little change occurs in insecticidal properties (see metilnitrofos,chlorthion, ronnel, trikhlormetafos-3, bromafos). In addition to mixed esters of thiophosphoric acid containinq aromatic radicals, mixed thiophosphates in the heterocyclic series have enjoyed some use as insecticides and acaricides. Certain representatives of this series are effective, and they are used on a broad scale. 0,0-Diethyl-0-(2-isopropyl-4-methylpyrimidyl-6)-thiophosphate (diazinon) is a color- less oil with a boiling point of 89�C at 0.1 mm Hg; its vapor pressure at 20�C is 8.4�10'S mm Hg; its volatility is 1.39 mg/m3; d4~ 1.115. It is readily soluble in most organic solvents (see also Table 45). Its LDSp in various experimental animals is 76-320 mg/kg. . ' 158 ~ FOIt OFFICIAL USE ONLY ' APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFF!CIAL USE ONLY In tenns of its hydrolyti~c stability diazinon is inferior to thiophos. In an acid medium it hydrolyzes 12 times more quickly than thiophos, while in an alkaline medium hydrolysis proceeds at practically the same rate. In excess water the main hydrolysis products of diazinon are diethylthiophosphoric acid and 2-isopropyl-4-methyl-6-oxy- pyrimidine, but when water is lacking in an acid medium, a small quantity of tetra- ethyldithio- and tetraethylthiopyrophosphates forms. Diazinon is marketed as emulsion concentrates, wettable powders, dusts and granulated preparations, and it is used against various plant pests and animal parasites. Despite fts relatively high toxicity to mammals, diazinon is believed to be a safe prepara- tion in most countries, and it is usually classified as a group III toxic compound. Diazinon is obtained with an 85 percent yield (of theoretical) by reacting 2-iso- . propyl-4-methyl-6-oxypyrimidine with diethylchlorothiophosphate in the presence of potash: � ' C(i~ Cfl~ S I ( N N ~ x,co, g i` N (C,It6U),I~CI I ~ - _ ~ c~i~i o . ~-o~ ~ c ti - � Z80 C~I1~ N Olf a)i ~J ZSO The reaction proceeds well in dimethylfonnamide solution at 50-60�C. 2-Isopropyl-4-methyl-6-oxypyrimidine may be synthesized with satisfactory yields - by the following pathway: ~ /NH � HCI Nt~, (Cliz),CHCN HCI -I- C~(~OH (CH~)zCHC ~OCH, . CHi � ~ /NH �.HCI c~i,cocri,coocH,; N~ (CH,)~Ct~IC ~ ( ~ ~ ~Nti, , NaOH 2SP~aH~~ N ~OH 0,0-Diethyl-O-(3,5,6-trichloropyridyl)-thiophosphate (dursban) is a white crystalline substance; its vapor pressure at 25�C is 1.9�10-5 mm Hg. It is readily soluble in most organic solvents (see also Table 45). Its LD50 in rats is 150 mg/kg, and in guinea pigs it is 500 mg/kg. - In acid and alkaline media the preparation is slowly hydrolyzed by water to form diethylthiophosphoric and ethylthiophosphoric acid and trichloroxypyridine. When oxidized, it may transform into the corresponding phosphate. 159 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY Dursban is an active insecticide used against sucking and gnawing insect pests as well as aqainst household parasites. Z'he preparation's active life on various surfaces is 6-11 weeks, but its life on plant leaves is shorter, apparently due to - its fast hy~rolys.;~s by enzymes, though on cereal grain plants the preparation's life is several weeks. Dursban is especially effective against mosquito larvae. When applied to marshes at a consumption norm of 0.5 kg/ha, it caused 100 percent death - of mosquitoes in 2 months. There are indications that dursban is effective against~soil-inhabiting plant pests. Dursban is synthesized by reacting the sodium salt of diethylchlorothiophosphate in dimethylforntamide : - S CI Ci CI / CI p S ~ lC7tie0),PCI -1' ~ ( ~ ~ CI Ne0 N CI (C~~~eO)~P- N In this reaction the yield of the preparation is 80-85 percent. In turn, 3,5,6-tri- chloro-2-oxypyridine is formed by saponification of 2,3,5,6-tetrachloropyridine by _ sodium hydroxiae at high temperature. ~ 0,0-Diethyl-O-(3-chloro-4-methylcoumarinyl-7)-thiophosphate (asuntol) is a white crystalline substance; d4~ 1.474 (see also Table 45). " Asuntol is poorly.soluble in most organic solvents~, and it is rather soluble :ln the lower carhoxylic acid~esters and ketones. Its LDSp~in different experimental animals is 55-200 mg/kg. - Asuntol is resistant to hydrolysis in alkaline and acid media, and it withstands ~ boiling in 8 percent ~oda solution far 2 hours. It interacts with diluted and concentrated alkali in ditferent ways. Dilute potassium hydraxide breaks open the pyran ring. Following subsequent oxidation the ring once again closes, and the initial product returns to its initial form. How- ever, when it is subjected to the prolonged action'of dilute alkali, the ring opens and the ethoxy grnup partially splits off; this process is irreversible. Asuntol breaks down when heated in concentrated ~lkali: 160 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY ~ ' ~ KOH: PHIZ C~Hs~~ p- / OI( ~ HO~S ~ . C~CCOOK H,~ ~I . ~ C H~0)P-O O (C,H~O),~-O OK ~ i ~ / I KOH: PHe-14 ~ I � ~ / ~ Hci ~ C=CCOOK CH~ I~~~ CI HO / % COOK I KoH cor.C. ~GzH~O):pOK ~i- I ~CE! . i u ~ S ~ ' ,When oxidized by nitric acid or other oxidants, asuntol forms 0,0-diethyl-O-(3-chloro- -4-methylcoumarinyl-7-)-phosphate, known in the literature as coroxon: O ~ , IC:H~~)~P-O / j 0 ~o~ ~~~H~~~~p-~~ / I% ~ - I~ ~ ~ ~ ~ ~ ci ct , H~ H' ' ~ ~ . I Asuntol is a valuable insecticide aqainst ectoparasitss of domesticated animals. _ In the a~i.mal body it breaks down quickly, transforming into diethyl- and ethylthio- phosphoric and -phosphoric acids, as well as H3P04. Owing to its low toxicity to ~ fish, asuntol is also of interest as a resource against mosquito larvae. I It is obtained with a yield of more than 90 percent by reacting diethylchloro- thiophosphate with 3-chloro-7-oxy-4-methylcoumarin in the presence of potash: i. HO / ~ /O K (Cztl60)tP-OY / ~ /O - (CzHe4)1PC1 \\(/Y ~ I ~ s~ ci ~ ~ ci : c}t, cH, _ O,0-Dieth~l-0-(quinoxalyl-2)-thiophosphate (bayrusil) is a white crystalline sub- stance; d4~ 1.230. ~It is readily soluble in most organic solvents (see also ~ Table 45). It decomposes when heated to 120�C. Its LDSp in rats is 66 mg/kg; ,its LDSp i.n the goldfish and carp with an exposure time of 96 hours is 1-10 mg/liter. 161 FOR OFFIC[AL USE ONLY ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 N'OK OM'FIClAL USE UNLY It is used as 25 percent emulsion concentrate and 5 percent granules to control plant sucking pests. Bayrusil is obtained by condensation of diethylchlorophosphate with alkaline deriva- tives of 2-oxyquinoxaline (225,273): - N N ~ CX ~ , + ~~zH~o~~p~~ CX + K~, N Oh S lY ~II ~OCzlia)s S . The methyl homologue of bayrusil., which is a white crystalline substance with a meltinq point of 51�C, is obtained similarly. This preparation is known as metilkhinalfos. Its LDSp is 900 mg/kg (orally) and 2,500 mg/kg (cutaneously). It is undergoing testing as a contact insecticide with a rather broad spectrum of action. Its relatively low thermal stability is a shortcoming. Thus a 30�C it may decompose down to 10 percent within 1 week, obviously due to its high alkylating capacity. Preparations containing substituents in the aromatic ring are more stable (224) : O,0-diethylthiophosphoryl-0-(a-cyanobenzaldoxime) (foksim) is an insecticide with a broad spectrum of action against sucking and gnawing plant pes~s (see Table 45). It is marketed under the name of baytion as an agent against storehouse pests. It is suitable aqainst pests inhabiting the soil; in this case it is used in the form of granules embedded in soil. Foksim is photochemically unstable, owing to which its - life is relativety short when sprayed on plants. It is hydrolyzed by water and alkali. ~ Foksim is obtained by reacting diethylchlorothiophosphate with the oxime form of a-benzoylcyanida in the presence of hydrogen chloride acceptors (146,147): (C~I~SO)jII~CI IION=C-Caf~ib (CzHbO),PON=C-C6116 S ~N S GN Foksim is a promising substitute for some organochloride preparations, and in this respect it dessrves the most meticulous study upon various objects. Because dialkylarylthiophosphates are extensively used against various harmful insects and ticks, the metabolism of most thiophosphates in various species of living organisms and in the environment has been studied (274,275). Compounds that have been studied include abat (274,276), bromofos (277,278), dazonit (279), diazinon (274,280-283), dursban (274,284-287), chlor`~.hion, coumaphos,thiophos, meta- rhos, triichlormetafas, zinopl~os, lebaycin, 'tsitron, V'i's-12,+netilni~trofos etc. (274) . 162 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OFFICIAL USE ONLY ' Investigation of the metabolism of a large number of mixed esters of thiophosphoric acid in various media showed that the metabolism of these compounds proceeds in two , basic directions: hydrolysis and oxidation. Depending on the structure and reactivity of the initial substan.ce, either hydrolysis or oxidation occurs first, but in some cases these processes occur simultaneously (275). Hydrolysis may occur at the P-OAr bond (or at the oxygen atom bound to the heterocycle) or at the P-OAlk bond; as a rule the rate of hydrolysis is somewhat higher in the first case than in the = second; however, in some cases these reactions proceed concurrently, though at different rates. Oxidation occurs first at the thion sulfur. If sulfide sulfur is ~ present in the ester molecule, sulfoxides and sulfones form, after which the mole- cule undergoes destruction. Aromatic and heterocyclic residues may enter into a reaction with carbohydrates to form the appropriate glucuronates. However, in many cases the organophosphorus compound may decompose all the way down - to the simplest pxoducts. This is what happens, for example, in photochemical de- composition of one of the most persistent organophosphorus insecticides--dursban (287). This decomposition occurs as follows: ci ~ ci t~ o Eio ~ ori ~ ~ ~ ~ ~ -~~,~~5~,,~0~~ . ~ CI N OII (UCzf IS) ~ HO N OH ' S _ EIO / OH Iol ~ O~ ~ OH Acyclic proctucts ~ N i ; It would be interesting to note that hydrolysis af organophosphorus compounds is accelerated in the presence of copper salts (289). The metabolism of thiophos may be diagrammed as follows: 163 FOR OFFICIA~. USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 FOR OFF(C[AL USE ONLY (C~H~O)zPOCeH~NO~�4 (CiH~O),POC6H~NH,-4 - ~ ~ ~ ~ - (C~H~O)zPOCsE~I~NO~-4 (C,HaO)=POC6H~NH=�4 ~ l ! , ~ OH I HOCaH~NO,�4 { 1 ~ HO I OH _ (CzHdO)=POFI -i (C,N60),~ OH HOCa~~NHz-4 ~ ~ HOOC 0 OCeH~NH~ ( 1 H~PO~ C,HbO\ %S ~ P HO~ ~OCeH~NO~-4 ~ i _ C,H,O~ /0 P � HO~ ~OCdH,NO,�4 The metabolism of other thiophosphates proceeds in similar fashion.. Investigation of the metabolism of ic?:sim showed that isomerization is the first event to occur in response to light; this is followed by decamposition resulting in tetraethylpyrophosphate and tetraethylthiopyrophosphate (288): (C,HaO)~PON=CC,H6 (C~H60)~ i SN=CCaH~ ~ ~N O ~N I ~ (('~H`O);P~--O-P(OC.H~)s (CzH60)=P-O-P(OC,H6)i - p ~ ~ ~ Fukuto et al. (288a) observed interesting thermal regrouping of oxime phosphates: (Cz f{`p),pO-N=C-Ar ---i (CsH~O)=P-NAr ~ 0 GH~ O COCH~ 164 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407102/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE ONLY _ Mixed aliphatic esters of thiophosphoric acid are of significant interest as systemic insecticides, amonq which mercaptophos, methyl-mercaptophos and its sulfoxide and sulfone, and vamidotion have enjoyed rather broad application. Due to the hiqh toxicity of inercaptophos to animals, its use has recently decreased significantly, While the other preparations are enjoying rather broad use. Methyl-mercaptophos is a methyl homologue of inercaptophos. Technical-grade methyl- mercaptophos is a mixture of the thioZ (30 percent) and thion (70 percent) isomers _ of O,0-di.methyl-2-ethylmercaptoethylthiophosphate. The thion isomer of inethyl-mercaptophos is a liquid with~a aharacteristic unpleasant odor;~its vapor pressure at 20� is 1.85�10-5 ~n Hg; its volatility is 23.3 mg/m3; d4~ 1.1904. It is freely soluble in most orqanic solvents (see also Table 46). - The thiol isomer of.methyl-mercaptophos is a liquid; its vapor pressure at 20�C is 3.6�10-4 mm Hg; its volatility is 4.5 mg/m3; d~6 1.207. It is freely soluble in organic solvents (see also Table 46). The chemical stability of inethyl-mercaptophos is lower than that of inercaptophos. Thus for example methyl-mercaptophos is saponified at pH 3 and 70�C in 4.9 hours, while mercaptophos takes 10 hours; the difference is even more sic~nificant in an alkaline medium. - R,egrouping of the thion isomer into the thiol isomer also proceeds faster. While it takes 91 days for the thion isomer of inercaptophos to transform at 40�C into a mixture containinq 90 percent thion and 10 percent thiol isomer, the thion isomer of methyl-mercaptophos undergoes 10 percent isomerization under the same condit'ions in 8 days. In the presence of traces of water, methyl-mercaptophos may enter into an inter~-- ' molecular methylation reaction: , (CH~O),PSCH,CN,SC,H~ ~ ~ ~ . ' ~ C({~ p~ - (CH~O)zPSCH~CH~SC~H~ ' PSCFf,CH,SC,t~lb _ ~ ( ~ ~H, ~ which in a number of cases is a reason for the product's spoilage during long-tern~ - storage. Metallic iron and some of its compounds have a negative influence on the stability of inethyl-mercaptophos, for which reason storas~e of this preparation in - iron containers is not recommended. It would be best of all to store methyl- _ mercaptophos in enamsled containers or in containers made from pure aluminum. Methyl-mercaptophos is less toxic than mercaptophos. The LD50 of the technical- grade preparation is within 80-100 mg/kg. The LD50 of the thion isomer is 180 mg/kg, while that of thiol isomer is 40 mg/kg. The maximum permissible concentra- tion in air is~0.1 mg/m3. ~ 165 ~ FOR OFFICIAL USE ONLY ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFF[C1AL USE ONLY - The metabolism of inethyl-mercaptophos in plants and insects proceeds similarly as with mercaptophos, except that when methyl-mercaptophos enters into plants, it quickly undergoes isomerization into the thiol isomer, which then undergoes metabolism similarly as with mercantophos. The oxidation products of the thion isomer of methyl-mercaptophos have not been observed, but they have been obtained syntheti- cally. Transformation and decomposition of inethyl-mercaptophos proceeds relatively quickly in plants, owing to which its life as an znsecticide does not usually exceed 3 weeks. The oxidation products of inethyl-mercaptophos and their toxici~y to rats are shown below: Boiling ' Point, �C LD50 Compound (mm Hg) mg/kg (CH~C),POCH,CtlzSOC,He . . . 95-96 (O,UI) 600 ~u s (CH,O)sPOCHzCHZSOzCzHb . . . 101 (0,01) 500 . II s (CH,O),uSCH,CH,SOC,Hb . . . 105 (0,01) 90 . , O ~ (CH,O),PSCII,CtIsSO,C,H` . . . 115 (0,01) q~ II Melting Point 0 52�C biethyl-mercaptophos is used as aqueous emulsions, and it is marketed in the form of concentrates containing 30 and 50 percent isomer mixtures. A synergist of inethyl- mercaptophos has been found in the USSR. It reduces the consumption norm for the preparation by 20-40 percent and reduces its toxicity by almost three times. This - preparation is knbwn as sinerfos. . Irh_thyl-mercaptophos is obtained by zeacting ~-oxydiethylsulfi3e and dimethylchloro- thiophosphate in the presence of hydrogen chloride acceptors (followed~by iso~neri- zation of part of the product into the thiol isomer): (CI-(,O)aPCI HOCH2CH~SC2H~ -1- NaOfi ~ (CFi,O)zPOCfiTCFIsSC,Hb NaCI -F- EIrO II s . ~ Impurities in the technical-grade prepar~=.tion include a small quantity of trimethyl- thiophosphate,.~ -oxydiethylsulfide and s~~me other thiophosphates. However, the total concentration of thiol and thion isomers is usually not less than 90 percent. - ~ 166 FOR JFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY Tinoks: A preparation marketed in the GDR under the name of tinoks is close~in properties to mzthyl-mercaptophos. The technical-grade preparation is a mixtuxe of the thiol (60-70 percent) and thion (30-40 percent) isomers of 0,0=dimethyl-0- -(2-methylmercap~oethyl)-thiophosphate. , ~ . The thion isomer is a liquid; its vapor pressure at 20�C is 28.4�10~4 mm Hg; its volatility is about 35 mq/m3;'d4~ 1.154. It is freely soluble in most organic solvents (see also Tab1e 46). Lts LDSp in rats is mAre than mg/]rg. ~ The thiol isomer is a liquid; it is freely soluble in most organic solvents (see also Table 46). Its LD50 in rats is about 40 mg/kq. Tinoks is similar to methyl-mercaptophos in its chemical properties, insecticidal activity and life. It is marketed in the form of a 50 percent emulsion concentrate. The methods by which tinoks is obtained are fully similar to those of obtaining mercaptopho~ ar.d methyl-mercaptophos. ~ 0,0-Dimethyl-S-(2-ethylmercaptoethyl)-thiophosphate (meta-systox I) is a systemic and contact fast-acting preparation. It is a thiol isomer of inethyl-mercaptophos. Without repeating the description of its properties, we will simply note that it is marketed as a 50 percent emulsion~concentrate. 7.'he best method of synthesizing meta-systox I is to react 2-chlorodiethylsulfide with salts of dirnethylthiolphosphoric acid: ~ ~SR ~ . (Cti~O)~f~~~ CICI-~zCI~~SC~H` (CH~O)z~ SCH,CI~I,SC~Hd KCI O ~ The yield of the thiol isomer of inethyl-mercaptophos with this method is not less than 85-90 percent. The reaction may be performed both in an aqueous medium and in organic solvents. 0,0-Dimethyl-S-ethylmercaptoethylthiophosphate is also formed by reacting trimethyl- thiophosphate with 2-chloro diethylsulfide while heating to a temperature somewhat above 100�C: (CII~O)~P=S CICIIiG~(zSC~H~ (CIi,Uj~iSCFIzCI~,SC,H~ C1t3C1 - 0 167 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-00850R000500040001-1 FOR O~'FICIAL USE ONLY Trimethylthiophosphate can be synthesized with very good yields out of inethyldichloro- . thiophosphate and methanol in the presence of sodium hydroxide: Cfi~Ou Clt 2CH~OH 2NaOH (CH,O)~~ 2NaCl 2Hs0 S S O,0-Di.methyl-S-(2-ethylsulfi.nylethyl)-thiophosphate (meta-systox R) is a yellow liquid with a mild odor; its volatility at 20�C is 0.09 mg/m3. Meta-systox R is ; freely soluble in water and poorly soluble in aliphatic hydrocarbons. It is freely soluble in methylene chloride and in halogen deriv~tives of aromatic hydrocarbons . (see also Table 46). In an acid medium it is more resistant to hydrolysis than methyl-mercaptophos, but in an alkaline medium it hydrolyzes faster than the latter. Meta-systox R is close in its insecticidal activity to methyl-mercaptophos, and it has a less pleasant odor. ~It is marketed in the form of a 25 percent concentrate, and it is used with an active irigredient concentration of 0.025 percent. The maxi- mum permissible quantity of residues in the USA is 0.75 mg/kg. its LD50 in rats is 65-75 mg/kg. ' Meta-systox R is obtained either by oxidation of the thiol isomer of inethyl-mercapto- phos by different oxidants (hydrogen peroxide, hypochlorites, bromine etc.) - (CH~O)zPSCIizCI{iSC~Hb (CN~O)zPSCfIzCH~SC,Hd . O O O or by reacting the salts of dimethylthiolphosphoric acid with 2-(ethylsulfinyl)- -ethylbromide (CEf~O)zPSK BrCI1zCHzSCjHs (CII~O)iPSCHzCN~SC=tla -I- KBr - O O 0 O ~ ~ ~ O,0-Dimethyl-S-[2-(N-methylcarbamoylethylmercapto)-ethyl]-thiophosphate (vamidotion) ; is a white crystalli.ne substance with a melting point of 46-48�C; the melting point ! of the technical-grade preparation is 33-38�C. It is freely soluble in water ~ (4 kg/liter), in acetone, methylethylketone, ethyl acetate and acetonitrile, and it is poorly soluble in hexane, cyclohexane and other paraffin and cycloparaffin ; hydrocarbons; its solubility in xylol is 125 gm/liter (see also Table 46). Vamidotion is somewhat more resistant to hydrolysis than methyl-mercaptophos and mercaptophos. Oxidants transform it first into sulfoxide and then into sulfone ~ (290). ~ 168 ~ FOA OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 FOR OFFICIAL USE ONL.Y The first metabolic product of vamidotian in plants is sulfoxide. Simultaneously with oxidation in plarits, the preparation undergaes hydrolysis to form dimethyl- phosphoric and phosphoric acid. ~he LD50 0~ vamidotion is (mg/kg): 64-100 in rats, 43-68 in mice and 85 in guinea pigs. The insecticidal activity of vamidotion is close to that of inethyl-mercaptophos, but it is significantly superior to the latter in the time of its action. Vamidotion is obtained by reacting anaaonium or alkali metal dimethylthiophosphate with a-(2-haloethylmercapto)-propiomethylamide: (CH~O),P~SNH~ CICHtCH,SCHCONHCH~ p CH, --Y (CFt,U),PSCHzCH~SCIICONHCI~I~ -E- NI~I,CI O CHi The greatest difficulties are encountered i:~ obtaini~ng a-(2-haloethylmercapto)- -propiomethylamide, which is synthesized as follows: HOCH~CI~I,SII KOH ? CH,Cl~ICICON}ICFi, , . -r HOCH,CII,SCFiCONHCH~ -I- H,O ? KC~ CFI~ ~ HOCH,CH~SCHCONHCI�(, SOG1 . ~H~ --r CICH,CH~SCNCONHCH, -F HCI ? SO~ . CH, ' Other ways of synthesizing this compound are possi.ble as well. Compounds containing an ester group in one of the ester radicals have also been - suggested as insecticides. The~greparations atsetofos and metilatsetofos a're. examples of such compounds. ~ 0,0-diethyl-S-(carbethoxymet~Xl)-thiophosphate (atsetofos) is~a colorless liquid _ with a specific unpleasant udor; its boiling point is 12~�C at 0.15 mm Hg; its vapor pressure at 20�C is about 7.5�10-4 mm Hg; d4~ 1.1840. It is freely soluble in water and in most organic solvents (see also Table 46). When the compound reacts with water in acid and alkaline media, it undergoes hydrolysis, with ester groups splitting off. Decomposition of this type of com- pound ~roceeds differently in homeothermic animals and insects, owing to which it - is less toxic to mammals while exhibit~ng high insecticidal activity. According - 169 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE ONLY to O'Brien's data, hydrolysis of the compour:d in homeothermic animals proceeds as (C~H60)~SCti~COOCzHi FitO --a (CzIt60)T~SCEf,COOH C,H60H while in insects an acetic.acid residue is split off and vitally important enzymes are inhibited. The compound's LDSp in various animals is 300-700 mg/kg. Atsetofos is a contact insecticide, but its activity is close to that of chlorophos. It.is oh~ained by reacting ethyl monochloroacetate with the ammonium salt of diethyl- thiophosphoric acid in a suitable organic solvent (benzene for example): (CtF(60)zl' SNH~ CICH~COOCzHb (CzFl60)zP~SC1i,COOCzF16 NH~CI . Q O The y ield of the target product in this reaction is close to 90 percent. As was noted earlier, mixed esters of thiophosphoric acid containing one aromatic and two different aliphatic radicals have recently been proposed as active insecti- cides and nematocides. An interesting method of obtaining these compounds is to react O-aryl-0,0-dialkylthioposphates.with alkali metal hydrosulfide and alkylhalide (173) : . ~ R0~ (RO)~POCsfI~ -F KSH POCtlH6 aSl[ ~ . KS/~ . R0~ RO~ ~ POCaEle R'X I(X POCslI~ KS~~ . R'S/O , I I , Di.thiophosphoric Acid Derivatives Besides thio,phosphoric acid derivatives, dithiophosphoric and trithiophosphoric acid derivatives also enjoy extensive us~~ as pesticides. Among derivatives of , dithiophosphoric ac?d, preparations used to control plant pests have the greatest significance, and it is only recently that fungicides and herbicides have been ' found among them. The general formulas of known pesticidal derivatives of dithiophosphoric acid are shown below: ~ ~ 170 FOR OFFICIAL USE OPiLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2447/02/09: CIA-RDP82-00850R000500444441-1 - FOR OFFICIAL USE ONLY RO~P/S RO~ /S P /R" - R'O~ ~S i HCOOR" R'O~ ~SCH=CON~R~~~ R - xit ~ x~ii ~ RO~ /S R0~ /S P ~ R'O~ ~SCHzSR"" R'O~ ~SCHzCF1tSR" . xtv X~ . Kp~p~s . RU~ /S P R'O~ ~SCHzN~tAr R'O~ ~SCHiAr - . xvi xvu RO~ /S (ArS)zP~02 . R 0 ~ ~ ~ A~s~ ~N~irt~ xvin xix where R, R'and R"--lower aliphatic radicals, R"'--hydrogen or some radical , Ar-- aromatic or heterocyclic radical, R~~"--aliphatic or aromatic radical. As we proceed from derivatives of thiophosphoric acid to the corresponding deriva- ' tives of dithiophosphoric acid, in most cases the toxicity of the compound decreases ~ i and its chemical stability increases. Owing to this its life in the field g~rows ; somewhat. Nbreover the range of action of the preparations changes as well. Many ; dithiophosphorio acid derivatives, especially those containing heterocyclic radicals, exhibit high activity not only against sucking plant pests but also against gnawinq insects. ~ . . . i ~ The following laws governing the dependence between biological.activity and struc- ture can be stated for the series af compounds with general formula XII: ; 1. All dithiophosphoric acid derivatives with this structure are less toxic to i ~ vertebrates t:~an are the corresponding derivatives of thiophosphoric and phosphoric acids. 2. ~lixed esters in which R and R' are methyl radi.cals are least toxic to vertebrates. ~ An increase in tYie number of carbon atoms in these radicals increases the toxicity of � : the compounds to vertebrates without increasing their insecticidal activity. Change in R'~~ has a less significant influence on the toxicity of mixed dithiophos- phates to vertebrates, but it has a significant effect on insecticidal and acaricidal properties. Compounds in which R"~ is an aromatic residue exhibit the highest activity. Introduction of a carbalkoxyl group into R"~ greatly reduces the compound's toxicity - to vertebrates and has almost no effect on insecticidal and acaricidal properties. This is valid for aliphatic derivatives, but not aromatic derivatives. 171 FOR OFFICIAL USE ONLY ~ ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2447/02/09: CIA-RDP82-00850R000500444441-1 F'OR OF'FICIA~ U~E ONLY The great difference in the toxicity of this group of mixed esters of dithiophos- phoric acid to insects and vertebrates can be explained by differences in the path- ways by which the preparations are metabolized in animals. 'I'hus for example, in the insect body carbofos transforms into a more-toxic ester of thi~phosphoric acid-- 0,0-dimethyl-S-(1,2-dicarbethoxyethyl)-thiophosphate, while in homeothermic animals the ester residue undergoes saponification (at the carboxyl group) to produce a com- pound that is practically nontoxic to animals (2,291): (CIi,O),PSCF{COOCzH` ~o? (Ctl,O)~PSCEiC00C,(ib S CfIrC00CzH~ - (7 CHzC00CzHe 1 tt,o (CII,O),PSCFICOOII }~~p (CH,O):PSCHCOOH I I SI CH~COOC,H~ S Ct12COOH Compounds with general formula XIII usually have not only contact but also systemic insecticidal action. ~ Compounds with general formula XIII in which R= R'=C~ig exhibit high insecticidal activity and moderate toxicity to mammals. Substitution of just one methyl group by an ethyl or otiher group containing a large number of carbon atoms sharply in- creases the compound's toxicity to mammals without significantly changing its insecti- - cidal activity. Thus for example, the LDSp of 0,0-dimethyl-S-(N-methylcarbamoyl- methyl)-dithiophosphate in rats is 250 mg/kg, while that of 0-methyl-0-ethyl-S-(N- ' -methylcarbamoylmethyl)-dithiophosphate is 12 mg/kg. Substitution of the methyl radical in the amide group by an ethyl radical does not significantly change the compouncl's toxicity to homeothermic animals, but enlarging the number of carbon atoms in the hydrocarbon radical at the nitrogen atom reduces the compound's insecticidal activity. Substitution of the second hydrogen atom at the nitrogen atom by hydrocarbon radicals also reduces the preparation's insectici- dal activity. When this hydrogen atom is substituted by a carbalkoxyl or formyl residue, the compound's activity against insects does not decrease, but its toxicity to mammals grows significantly. However, there are exceptions to this general rule (297 , 298) . Addition of a carboxyl or a carbamoyl group to the hydrocarbon radical at the nitro- gen atom produces acaricides and insecticides with highly selective action that are moderately toxic to homeothermic ani.mals (292,293). Compounds obtained by join- ing dialkyldithiophosphori.c acids to esters of cysteine (296) and acylated unsatu- rated amino acids also possess insecticidal properties. Insecticidal properties also persist when halogen atoms (~99), alkyl- and acylamino groups (300), cyano (301,302) and phenyl and carbalkoxy groups (303) are added to the hydrocarbon residue at the nitrogen atom. Substitution of hydrogen at the nitrogen atom by alkylsulfonyl and~arylsulfonyl groups (304), sulfonylamido and acylamido groups (305), alkylamino and dialkyl3cnino groups (306-308) and alkyl- and 172 FOR OFFICIAL USE ~NLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 - FOR OFFICIAL USE ONLY alkoxy groups (309,310). produces substances with sufficiently high acaricidal and insecticidal activity. In the last case, however, phytocidal activity rises somewhat. Phytocidal activity increases especially strongly when one of the alkoxyls at the phosphorus atom is substituted by an aryloxy residue (311). The resulting mixed dithiophosphates have herbicidal action. When an amide group is substituted bp a nitrogenous heterocyclic residue, herbicides form as well (312,313). Mixed esters of ethylene qlycol also have insecticidal action (314). O-Alkyl-N-alkyl- (dialkyl)amido-S-N-methylcarbamoylmethyldithiophosphates have not only insecticidal ar}d acaricidal action but also fungicidal properties (315-317). Compounds with general formula XIII enjoy rather broad use in agriculture as in- secticides and acaricides. Compounds with general formulas XIV and XV possess strong systemic acaricidal and insecticidal action. The basic principles concerning the dependence of insecticidal - and acaricidal activity on the structure oi these two groups of compounds may be stated as follows: 1. For compounds with generdl formt~la XIV, increasing the number of carbon atoms to more than two in all hydrocarbon radicals reduces toxicity to animals and to plant pests . The most toxic compound is the ester in which R= R~ = R~"~ = C2H5. Substitu- tion of R"" by an aromatic radical somewhat decreases toxicity to mamm~ls while ~aintaining acaricidal and insecticidal properties. 2. Of compounds with general formula XV, those with R= R' = CH3 are the least toxic to manunals. Substitution of one methyl radical by an ethyi or higher hydrocarbon residue sharply increases toxicity and somewhat intensifies insecticidal properties. When the total number of carbon atoms i.n the R and R' radicals increases over four, compounds with relatively low insecticidal activity form. 3. When various functional groups are introduced at R'~, compounds with high insecti- cidal and acaricidal activity form (318-321,324). Mixed esters of dithiophosphoric acid containing a carbalkoxyl or carbamide group at the methylene bridge have the highest activity (318-321). 4: The appropriate sulfoxides and sulfones have high insecticidal and acaricidal activity as well (322,323). 5. Compounds in which R" is a dialkyldithiophosphoric.residue also have acaricidal and insecticidal properties'(327-329). ~ 6. Substitution of sulfide sulfur by oxygen bound to an ar.yl group lead.s in most cases to higher phytocida~ activity (330,331). Some compounds of this type have been proposed as herbicides. _ 7. As we proceed from derivatives of dithiophosphoric acid to derivatives of tri- and - tetrathiophosphoric acids, the insecticidal and acaricidal properties diminish while fungicidal and phytocidal activity increases (316,317,332,333). 173 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42109: CIA-RDP82-00850R040500040001-1 FOR OFFIC[AL USE (~NLY g, when the carbon residue at the sulfide sulfur is substituted by a carbamic or di- alkyldithiocarbamic acid residue, the resulting suUstances have fungicidal proper- ties (334). 9. When the sulficle sulfur is substitutedbY an acylamino or an alkylamino group, the re- sulting substances have varying pesticidal activity (335-347). MixPd dithiophos- _ phates with carboxylic acid residues at the nitrogen atom have insecticidal and acaricidal properties (335-339); alkylamino derivatives also have similar properties (347). If the acyl group is a residue of an aliphatic sulfonic acid residue (340- ~ 342), the substance has insecticidal and acaricidal properties. But when an aromatic sulfonic acid residue is introduced, phytocidal activity rises and the substances ; exhibit herbicidal action. There are indications that 0,0-dialkyl-S-hydrazomethyl- dithiophosphates have not only insecticidal but also nematocidal action (348). Mixed di*_hiophosphates containing halogen atoms at one of their aliphatic radicals, for exanple O,0-dialkyl-S-(1,2,2-trihaloethyldithio)-phosphates and their homologues, are active insecticides (350,353-359). 0-Alkyl-S-alkyl-S-aryldithiophosphates are active ~ insecticides and fungicides (349,351,352,360-363), while 0,0-dialkyl-S-alkenyldi- thiophosphates obtained by attaching dialkyldithiophosphoric acids to butadiene and allenes have nematocidal properties (355). . Many amido esters of dithiophosphoric acid have fungicidal properties (163). Active _ fungicides exhibiting highly selective action i:nclude 0,0-dialkyl-S-benzyldithio- phosphates and especially 0-alkyl-S-alkyl-S-benzyldithiophosphates (364-372)--both unsubstituted and containing various substituents in the benzyl radical (367-372), and diamido-S-benzyldithiophosphates (373). O-Alkyl-S,S-diaryldithiophosphates, meanwhile, have fungicidal action (374-378). 0-Alkyl-S,S-dialkyldithiophosphates are rather active nematocides (375). Though a very larg~ number of various derivatives of dithiophosphoricl~~is still heterocyclic substitue~nntssh~~~eofow Wsengover.ningdthe dependencetofethe pesticidal impossible to deduce y - activity of the compounds on their structure. Dithiophosphoric acid derivatives that have achieved practical use against various harmful organisms are shown in Table 47. The principal methods of obtaining mixed esters of dithiophosphoric acid are as follows: ~ 1, Reacting dialkyldithiophosphoric acid salts with the appropriate halogen deriva- tives: ~ ~ (l20)~PSNa CICl~zll" (120),RSCHiR" NaCt - S S 174 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 FOR OFFICIAL USE ONLY Table 47. Dithiophosphoric Acid Chemical Name ~ ~ Formula Synonyms 0-Ethyl-S-S-dipropyldithio- C,H~OP(SC,H,), Mokap. phosphate ~ ~ Sodium 0,0-dibutyldithio- (C.HoO),PBNa~ Defoleks phosphate ~ ~ O~0-Dimethyl-S-(1,2-dicar- (CF130)=PSCHCOOCzHs ~rbofos, melathion, bethoxyethyl)-dithiaphosphate S ~H,COOC,H~ nhosphothion (CH,O),PSCH~CONHCH~ phos hamide, dimethoate, - 0,0-Dimethyl-S-(N-methyl- P carbamoylmethyl)-dithiophos- ~ rogor, Bi-58, fost~on phate MM, roxion,'perfekthion ' 0,0-Dimethyl-S- (N-ethylcarbamoyl (CN,O),PSCN,CONHC,H~ Fitios, B/77 methyl)-dithiophosphate 5 ~ 0,0-Diethyl-S- (N-isapropyl- (C=H~O)~PSCH=CONHCH(CH~)i protoat, fak-20 ; carbamoylmethyl)-dithiophos- ~ i phate . 0,0-Dimethyl-S[N-$-methoxyethyl)- ~CH,O),PSCH,CONHCH,CH,OCH, Tiokron, amidotion N ; carbamoylmethyl~-dithiophosphat S ' O,0-Dimethyl-S-(morpholidocarbo- (CH,O),PSCN,CON~\0 I~SorfAtion, ekatin-F, I ~ methyl)-dithiophosphate S ekatin-M 0, O-Dimethyl-S- (N-methyl-N- (CH,O),PSCF~~CONCHO Formothion, anthio - -formylcarbamoylmethyl)- ~ CH, dithiophosphate y Mekarbam, mur~otoks 0,0-Diethyl-S- (N-methyl-N- (C,H,O),PSCH,CONCOOC,H~ t -carbetho~cycarbamoylmethyl)- S ~H, . -dithiophosphate , . (C,H`O)~PSCH~SC,H` 0,0-Diethyl-S-ethylmercapto- ~ ~ Z"himet, phorate methyldithiophosphate . ((CH,),CtIOJ,PSC1i,SC,H~ Afidan O,0-Diisopropyl-S-ethylsulfinyl- N q methylda.thiophosphate ~ ~ ~ 175 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 - FOR OFFICIAL USE ONLY - Derivatives Used as Pesticides LD50 in Rats (Orally) Boiling mg/kg Point,�C Sol- LDSpin (At Indi- ubil- ~abbits cated M elting ity [Cutan- Pressure), Point Water, eously), _ mm Hg .�C mg/liter mq/kq Use. Forms of Application and~Consumption Nozms gg_g~ - .Poor 61,5 Nematocide and soil insecticide. E.c., granules. (0,2) _ - ~~ood ~ppp Defoliant, dessicant. 40~ aqueous solution; ~ 10-15 kg/ha. 12p 2,8-3,7 l46 1376 Insecticide and acaricide with broad spectrum ~p,2~ ~~pp of action. E.c., 90$ preparation for ultralow volume spraying; 1 kg/ha. . " l07 51-82 3900 2b0 Insecticide and acaricide with broad spectrum (0,05) gpp of action, has systemic action, e.c.; 0.3-1 kg/ha. 67-68 8b00 a80 Analogous with phosphamide. 136 28,8 2600 8~g Insecticide and acaricide with systemic action. (O,OI) 860 E.c., w.p; 0.3-1 ky/ha. - 48 9~ 600-660 Insecticide and acar.icide with systemic action. E.c.; 0.5-1 kg/ha. - 63-W 0,5~ t90. Contact and systemic insecticide and acaricide. ~ E.c.; 0.5-1 kg/ha. - 25-26 0,1~ 376 Insecticide and acaricide with systemic action. qpp_~gpp E. c. ; 0. 5-1 kg/ha. ~ l44 9 1000 36-39 Insecticide and acaricide. 40$ e.c. ; 0.1-0.2 (0,04) ~ kg/ha . - ~pp - 5p ~~~_2,3 Systemic ir.secticide for soil introduction. (0.4) 25~ e.c., p~wder made with activated charcoal. i:uicl " 8'~ Insecticide against soil pests. 5~ granules. . 1 - 176 FOR OFFICIAL USE .ONLY . APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 FOR OFFICIAL USE ONLY Chemical Name Formula Synonyms O,O-Di~thyl-S- (tert-butyl- (Czti,O),PSCH,SC(CH,), AC-92100 mercaptomethyl)-dithio.- phosphate S (C~i,O)zPSCHzSCdH~C!-4 O,0-Dimethyl-S-(4-chlo.rophenyl- ~ S Metiltrition mercaptomethyl)-dithiophosphate O,0-Diethyl-S- (4-chlorophenyl- (~sH60)z~SCI~~,SCeli,Cl-4 Trithion, carbopheno- mercaptomethyl)-dithiophosphate thion 0,0-Diethyl-S- (2,5-dichloro- (~:H60),PSCH,SCbH,CIz-2,6 Fenkapton pp~enylmercaptomethyl)-dithio- ~ ' phosphate ((C,E-160),PSJ,CH? Methylene-bis-S,S-[0,0-diethyl- Ethion, nialate, dithiophosphate] S diethion, metion, etikon (C~I,O),PSCHzCf~~SC,Fia 0,0-Dimethyl-S-(2-ethylmercapto- Tiometon, ekatin, intra- ethyl)-dithiophosphate S ~ tion, M-81, ekavit (C,Ff60),PSCt I,CHzSC,F[~ 0,~-Diethyl-S-(2-ethyZmercapto- ~ Di-syston, disulfoton, ethyl)-dithiophosphate M-74 CFi~O~ 0-Methyl-O-ethyl-S- (2-ethyl- PSCI(,CH,SC,F16 Teration mercaptoethyl) -dithiophosphate C,EIbO~s 0,0-Diethyl-S- (2-ethylsulfinyl- (C,ti,O),PSCFI,C[~I,SC,C~ Di-syston-S, di-syston ethyl)-dithiophosphate ~ ~ sulfoxide 0,0-Dimethyl-S- (a-carbethoxy~ (C~1,0),PSCIiC00C,F1~ Tsidial, paption, benzyl)-dithiophosphate ~U ~aHa elsan, fentoat ~ 0-Ethyl-N-butylamido-S-phenyl- ~s}~6~~ Fosbutil dithiophosphate P N 1 iC ~t~f. C6F1aS~S O-Ethyl-S,S-diphenyldithio- CzHeO�(SCef[6)= Khinozan, edifenfos phosphate p ~ 0,0-Dimethyl-S- (2-acetamido- (CE-i,0),IISCti,CH,NEiCOCH, p,minfos ethyl)-dithiophosphate S 0,0-Diisopropyl-S- (2-benzo- l(~i{a)sCtfOJ~PSCFI~CH~NNSO,CaN6 gensulid, betazan, sulfamidoethyl)-dithiophosphate S prefar 177 ~OR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 FOR OFFICIAL USE ONLY LD50 in Rats (Orally) Boilinq mg/kq Poiht,�C Solu- LDSOin (At Indi- bil- ~bits cated Melting ity (Cutan- Pressure),Point, Water, eously), mm Hg �C mg/liter mg/k.g Use. E'orms of Application and Consumption Nozms ~ ~i~.1 (0,01) I''U~? I I,~i Insecticide controlling soil pests. 5~ granules. 'j _g _ 12~ - I I~U Contact insecticide and acaricide. E.c., 25~ w.p. (U,01) ~ 13p - 2 10-30 Contact insecticide and acari.cide. E.c., 25$ w.p.; 0.5-1 kg/ha. 120 - Insol z~0-2G0 Acaracide. E.c., 20~ w.p.; 0.25-1 kg/ha. (O,OU I ) uble 16~t-165 - 2 55 Rcaracide and insecticide. E.c., w.p.; 0.5-1 (0,3) kg/ha. 104 - ~ Systemic acaricide and insecticide. 50$ e.c., (0,3) granu~s made with activated charcoal. 128 - 15 2,~-~2,5 Svstemic insecticide and acaricide. E.c., granules; 0.2-1 kg/ha. - - 3U ~,2-12,3 Systemic acaricide and insecticide controlling mites on hops. Preparation is introduced into soil. De~om- 100 3,G Systemic insecticide and acaricide. E.c., , poses ~ granules; 0.5-1 kg/ha. 70-80 17,5 Il 2~0-3n0 Insecticide with broad spectrum of action. (2,5 � 10 E.c. , granules. 15~-15t - 200 30p Fungicide. E.c. 1-2 kg/ha. (u,3) . - ~r~ _ Fungicide controlling (pirikulyariya) ir rice. (~~p~~ Insol- E.c.; 1-3 kg/ha. - �21-:.>:1 oor : 4U5 Systemic insecticide and acaricide. 40~ e.c. ; 0.5-1 kg/ha. �Liquid - 25 1900 Herbicide controlling annual weeds. E.c., . granules; 6-15 kg/ha. 178 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407102/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE QNLY Chemical Name Foxmula Synonyms ~ 0,0-Dimethyl~S-phthalimiuo- CO Phthalophos, - methyldithiophosphate (CH,O),P(S)SCHt~ \ I ~ imidan / . , 'CO . ~ CO ~ 0,0-Diethyl-S- (2-chloro-l- (CzlidO)zP-SCEi-N\ i~~ Dialifor, .torak _ phthalimidoethyl)-dithiophos- I~ phate . S CI~H, CO C H60)~PSCH� N- O,O-DiethylyS-(6-chl~robenzoxa- ( ' ~ Phosalone, zolone, zolinon-2- 1-3-meth 1)-dithio- ~ / rubitoks, benzofosfat phosphate ~ ~ _ 0,0-Dimethyl-S-(3,4-dihydro-4- (Cfl,O),PSCH,-Ni ~ ~ Gusathion, quthion, - -oxo-5,6-benzo-1,2,3-triaiinyl- II N\ azinphos-methyl - -3-methyl)-dithiophosphate 5 ~ ' ~ - O,O-Diethyl-S-(3,4-dihydro-4- CO (C7H60)~PSCti,-N~ ~ Azinfos, guzation-Kh, -r~x~-5,6-benzo-1,2,3,-triazinyl, II I ~ gution-K ~ - -3-methyl)-dithiophosphate S N~ i 0,0-Dimethyl-S-4,6-diamino-1,3,5- N /NH= Menazon, sayfos, -triazinyl-2-methyl) -dithio- � ~CH,O),PSCtiz--~~ ~N saphizon, azidition phosphate . II S N- NH~ - O, O-Diunethyl-S- (2-methoxy-1, 3, 4- (CH,O),PSCH,~ Metnidathion, ultracid, -thiadiazolon-5-yl-4-methyl)- S N-N supracide dithiophosphate p/ S/ ~OCE~, ~ 2,3-Bis-0,0-diethyldithiophos- S Delnav, sikaden, phoryl)-dioxane-1,4 p II rufos, kvimafos, SP(OC;fis), dioxathion, navadel CX o sr~~oc,�a,z u ~ _ s 0, O-Di- (n-propyl) -S- (2-methyl- pSC}itCON ~ S-19490 piperidyl-l-carbomethyl)- - -dithiophosphate S H,C~ ~ 179 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007142/09: CIA-RDP82-40854R040500040001-1 FOR OFFICIAL USE ONLY LD50 in Rats ~ (Orally) Boiling mg/k9 Point,�C Solu- LDSp in ~ (At Indi- biI- Rabbits cated Melting ity (Cutan-~ . Pressure), Point, Water, eou~ , mm Hq . �C mg/liter mg/icy _Use Forms of Application and Consumption Norms - 72-73 25 40-200 Insecticide with broad spectrum of action. ~ 3100~ E. c. , w. p. ; 0. 5-1 kg/ha. - 61-62 1 43-71 Insecticide and acaricide with broad spectrum 146 of action. 46~ e.c.; 0.5-1 kg/ha. - 47-48 10 135 Insecticide with broad spectrum of action. ~ 390 E.c., w.p.; 0.5-1 kg/ha. - 73-7q 30 II-20 Insecticida and acaricide with broad spectrum 88-200 of action. E.c., w.p.; 0.1-0.5 kg/ha. lll 53 - t2,5-17,5 Broad-spectrum insecticide and acaricide. 250 ( n E.c., w.p.; 0:1-0.5 kg/ha. 2 hr ) - - IfiO-iG2 0,:~ yU0 ~ Insecticide with systemic action ag~iinst aphids. W.p., granules; 0.5-1 kg/ha. - - 39-40 0,1~ 45-48 Insecticide and acari^ide with broad s~~ectrum ~ of action. 40$ e.c.; 0.5-1 kg/ha. Liquid 80-8I In- 23-43 Contact insecticide and acaricide. E.c., w.p�; ~ (cis (tran ~solu- up to 1 kg/ha. ~ isomer) isome ) ble . ~ ~ Selective herbicide controlling weeds growing - - 50 410 with rice. . . ~ 180 FOR OFF[C[Ati USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 - FOR OFFICiAL USE ONLY This reaction produces a good yield of O,O-dialkyl-S-benzyldithiophosphates (364-372, 380), dioxydihydrothienylmethyl-0,0-dialkyldithiophosphates (381), O,c?-dialkyl-S- -thienylsulfonyldithiophosphates (382), O,0-dialkyl-S-phthalimidoalkyldithiophos- phates (383-386), 0,0-dialkyl-S-benzoxazolinyl-2-methyldithiophosphates (388-392), 0,0--dialkyl-S-pyridylalkyldithiophosphates (387), 0,0-dialkyl-S-benzoxazolinyl-2- -chloroethyldithiophosphates (393), 0,0-dialkyl-S-(2-oxopyridyl-l-methyl)-dithio- phosphates (394), 0,0-dialkyl-S-carbamidomethyldithiophosphates (395-399), 0,0-di- alkyl-S-(1,2-oxazolyl-2-methyl)-dithiophosphates (400), 0,0-dialkyl-S-oxadiazolyl- methyldithiophosphates (401,402), 0,0-dialkyl-S-thiadiazolyl-3-methyldithiophosphate~ (403), O,O-dialkyl-S-triazinyldithiophosphates, 0,0-dialkyl-S-t~iazinylmethyldithio- phosphates (4OS) and a r.umber of otner heterocyclic compounds (406-414). In some cases not only salts but also free acids can be used. In this case the process is slower, and it requires a higher temperature: (RO)=I'SH + C~Crl~~t" ~ (RO):~scFt,R" + ~~C~ S S The reaction with salts is usually performed in an aqueous medium or in organic solvents, while the reaction with acids is performed without solvents. 2. Attachment of dialkyldithiophosphoric acids to unsaturated compounds: (RO),PSiI CHR' (RO)zPSCf(R' S CIIR' S CH=R' This reaction can be used to.obtain mixed dithiophosphates of the most diverse types (294,295,352,355,357,415-419), to include those containing heterocyclic radicals (419). The reaction is usually performed without solvent or in an apolar solvent. Sometimes excess reagent, to which dialkyldithiophosphoric acids join, ~ is used as the solvent. 3. Interaction between dialkylchlorothiophosphates and the appropriate thiols: ~ . (RO),II CI NaSR' (RO)z IISR' NaG . S S. This reaction proceeds readily in the presence of hydrogen chloride acceptors. Both caustic alkali and various organic bases can be used for this purpose. 4. Interacti~n between alkylphosphoric acid dichlorides anci mercaptans in the presence of hydrogen chloride acceptors (374-375): - ROPCI= 2R'SNa R0~(SR')z ZNaCI a 0 ~ ~ 181 FUR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFIC[AL USE ONLY The reaction between diphenyldisulfide and metallic sodium in the presence of alkyldichlorophosphate may be used to obtain 0-alkyl-S,S-diphenyldithiophosphates. The dialkyldithiophosphoric acids required for synthesis of mixed dithiophosphates can be obtained with a good yield.by reacting phosphorus pentasulfide with alcohols: P~S` 4ROH HzS . 2(RO),PSH S Trialkyldithiophosphate is fozmed in small quantities as a byproduct. The purity of the initial phosphorus pentasulfide is highly significant to synthesis of dialkyldithiophosphoric acids, since impurities ~ncrease the amount of byproducts, removal of which presents significant difficulties. t3sually, phosphorus pentasulfide . is obtained directly by reacting equimolar quantities of sulfur and yellow phosphorus at high temperature. When sufficiently pure initial substances are used, technical- grade phosphorus pentasulfide does not require further purification. When P2S5 must be purified, it is either crystallized out of carbon disulfi3e or it is subjected ~ to vacuum distillation. The basic flowchart for producing dialkyldithiophosphoric acids out of phosphorus - pentasulfide and.alcohol is shown in Figure 18 (420). ' _ ~ ~1~ 1 ~ ~ ! Z 4 ~3 To ad- sorber 6 . - - 8 S' . - --10 9 ' 11 Figure 18. Basic Flowchart for Dialkyldithiophosphoric Acid Production: ~ 1--P2S5 hopper; 2--worm feeder; 3--alcohol gaging tank; 4--reactor; S--agitator; 6--blade for additional mixing; 7--gas cooler; 8--valve; 9--separator; 10--receiver; 11--finished product collector Most -.ialkyldithiophosphates obtained by this method are sufficiently pure; however, - owing to its high alkylating capacity dimethyldithiophosphoric acid contains rather sizeable quantities of trimethyldithiophosphate. Trime}hyldithiophosphate may be separated away either by distillstion with live steam or by conversion o~ dimethyl- dithiophosphoric acid into a sodium or other salt, followed by separation of 182 ;v~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OFFICIAL USE 4NLY ' trimethyldithiophosphate by extraction with hydrophobic organic solvents (toluol, xylol etc.). Free acid is separated by the action of table salt upon concentrated sulfuric acid (421). This purification method can produce 95-100 percent dimethyl- dithiophosphoric acid. - The resulting trimethyldithiophosphate may be used to make dimethylchlorothio- phosphate: . (Cti,01z1~SCH, CI~ (CH~O)zPCI CHzSCI . S~ Dimethylchlorathiophosphate contains, as an impurity, a certain quantity of iso- meric O-methyl-S-methylchlorothiophosphate. ~ The most important representatives of these typ~s of compounds are presented below. 0,0-Dimethyl-S-(1,2-dicarbethoxyethyl)-dithiophosphate (carbofos, malathion) is a colorless liquid; d45 1 23, n~js 1.4985; vapor pressure at 20�C is 1.25�10-4 ~n Hg; volatility is 2.26 mg/m3. Carbofos is freely soluble in most organic solvents, with the exception of saturated hydrocarbons (see also Table 47). The LDSp in various experimental animals is 500-1,500 mg/kg. The maximum p~rmissible ~~oncentration is air is 0.5 mg/m3. When heated for a long period of time~at 150�C carbofos undergoes isomerization, transforming into the appropriate thiol isomer: CFI~O~ . (CI I,O)rPSC( ICOOCzFis ~PSCHCOOCiH~ ~ s~ ~~ti,coo~:,~i, c~~,s o ctt,cooc,tib . - At higher temperature this reaction proceeds violently,.arid a significant part of the product breaks down, sometimes even with an explosion. When impurities such as trimethyldithiophosphate, di.methyldithiophosphoric acid and some others are present int3~e preparation, intense decomposi.tion of carbofos may occur even at lower tempera- _ ture. ~ Hydrolysis of carbofos in acid and alkali media proceeds in different ways. While in an acid medium the main hydxolysis products are dimethyldithiophosphoric acid and mercaptosuccinate, in alkaline medium dimethyldithiophosphoric acid salts and a fumaric acid ester form: ~ Cf I2COOC,}I6 (C11,0)~POIi ~ II FISCHCOOCzHb ~ (CfI,U)1PSCIIc:OOClfi6 - S II I CIiCOOC,Ha S CII,COOCtH~ (CH,O)ziiSNa -F ~F~COOC H 9 6 $ 183 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/02/09: CIA-RDP82-00854R000500040001-1 - FnR OFFICIAL USE ONLY The reaction is used for quantitative polarographic determination o~ carbofos. When carbofos is oxidized by nitric acid or other strong oxidants, tha thionic sulfur atom splits off, and the corresponding thiolphosphoric ester forms: ~cti,o~z~s i t~cooc:Hb (CH~O)lPSCHCOOCzH6 p 1 $ CHzCOOCzH6 ' O HZCOOC1Hb _ When allowed to remain'in prolonged contact with iron or materials containing iron, carbofos breaks down and loses its insecticidal properties completely. In this connection it cannot be stored~.in iron containers. It is preserved best in glass containers. The preparation is marketed as an emulsion concentrate containing~30-60 ~~ercent active ingredient, an emulsifier and a solvent. Xylol is used as the solvent. The preparation is made for ultralow volume spraying as a 90-96 percent ccncentrate containing only an insignificant quantity of additives. Carbofos can also be used in the form of dusts or suspensions obtained from wettable powder. Usually carbofos is used in agriculture at a 0.2-0.25 percent concer:.tration (active ingredient). Residual quantities of carbofos have been established iTt the USSR at not more than 8 mg/kg. The main method of obtaining carbofos is to attach dimethyldithiophosphoric acid to maleic acid ester. The reaction proceeds very readily in the presence of basic catalysts, both in various organic solvents and without them: ~ (CII,O),PSff CFICOOCz1~6 (CH,O)zPSCHC00CzH~ ' S CIICOOCrHb ' S CTi~C00C,~16 This reaction may be combined with that of obtaining dimethyldithiophosphoric acid from methanol and phosphorus pent~-tsulfide. This process is performed in a diethyl- maleate medium. However sometimes ~he reaction (in the combined method~ proceeds ' so violently that the product undergoes spontaneous decomposition. Technical-grade carbofos obtained by this method contains small quantities of trimethyldithiophosphate, diethylmaleate and solvent. Xylol is usually used as the solvent for carbofos synthesis. The carbofos yield with this reaction is more than 80 percent of theoretical, but when condensation is combined with acquisition of dimethyldithiophosphoric acid, the yield is somewhat lower. The basic flowchart of ~btaining carbofos by this method is shown in Figure 19. 184 ~ FOR OFFICIAL USE ONLY ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 FOR OFFICIAL USE ONl.Y Z ~ ~ . (1) ~ , ~ 4 ~o~odaA s K aaKyyM� . Nacocy ~3}.. 6 ~B ~ ~ap . ~2 ~ Ha cK~ad tomoBoc2 . npcdync~~c~c ( 4 ~ . - Figure 19. Basic Flowchart for Production of Car~bofos: 1--gaging tank for dimethyldithiophosphoric acid; 2--gaging tank for diethyl- maleate; 3--cooler; 4--reactor; 5--methanol distillation col~amn; 6--heating zone; 7--cooler; 8--methanol collector Key: 1. Hot water 3. To vacuum pump ~ 2. Steam .4. To finished product storage Carbofos can also be obtained by prolonged boiling of a solution of sodium or potassium salts of dimethyldithiophosphori.c acid and.diethylsuccinate in alcohol or another polar solvent, but this method is more complex, and it is rarely used in practice: . (CH~O)~R'SK -4- t3rCbIC.00CiFis (CH~O)iPSCHC00C,Hs Ker S C!-i,COOC,Hs ~SI CH~COOCzH` Volatile impurities, including trimethyldithiophosphates, can be~removed from carbo- fos by distillation with live steam (422), while excess dimethyldithiophosphoric acid can be removed by washing with alkalis (423) or with sodium sulfide solution (424). Unreacted diethylmaleate is hydrolyzed (423). The unpleasant odor is re- moved by oxidizing the preparation with oxygen in the presence of heavy metals (425), or cumyl hyd~oxide is added (426-428). It should be noted that when carbofos is allowed to stand for a long period of time, the unpleasant odor returns. A large number of analoques and homologues of carbofos have been synthesized and studied, but most~of them are highly toxic to animals, owina to which they have not enjoyed much use. 0,0-Diethyl-S-(carbethoxymethyl)-dithiophosphate known in the literature as atsetion (boiling point 92�C at 0.01 mm Hg; d4~ 1.176; LDSp in rats 1,050-1,100 mg/kg), is of interest as a resource against flies. It is synthe- sized by reacting ethylmonachloroacetate with sodium diethyldi~hiophosphate in an aqueous medium while heating for. a short period of time: ~CpIISO~ZPSNiI CI1:11.Ct)OCzlf~ (Cz1160),PSCIizCUOC~tl6 NaCI S ~ ~ ~ FOR OFFICIALS USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/42/09: CIA-RDP82-40854R040500040001-1 FOR OFF~CIAL USE ONLY Although it is not in use, this preparation is of connsiderable theoretical interest, since its low toxicity to animals was predicted on the basis of research on the metabolism of organic phosphorus compounds. When the ester group in the acetic acid residue of atsetion and its homologues is substituted by an amide group, the compound's insecticidal activity rises dramati- cally; concurrently its toxicity to m~mmals increases as well. However, the incr~ase in toxicity to mammals is less significant, owing *_o which many such amides are of significant practical interest, and some of them are used in agriculture. Today seven preparations in this group of substances are in use, and a number of compounds are presently being studied. ~ 0,0-Dimethyl-S-(N-methylcarbamoylmethyl)-dithiophosphate (phosphamide) is a snow- white crystalline,substance; vapor pressure at 20�C is 8.5�10's ~r? Hg; volatility is 0.107 mg/m3. It is freely soluble in water and in most organic solvents, but it is poorly soluble in paraffin hydrocarbons (see also Table 47). The LDSp of pure preparation in rats is 250-265~mg/kg. Technical-grade preparat~.on is more toxic (LDSp 150-160 mg/kg) due to presence of impurities, the most important of which is 0,0-dimethyl-S,N-methylcarbamoylmethyl)-thiophosphate (LD50 in rats 55 mg/kg). ~Phosphamide is thermally unstable, and it decomposes when heated, primarily under,- ~ ~ going Pishchemuka isomerization: CH~O~ (CN;,O)sPSCHzCONHCN, PSCI~=CON1fCFt, _ . ~ S CH~S~O - The resulting O,S-dimethyl-S-(N-methylcarbamoylmethyl)-dithiophosphate is more toxic to mammals than the initial phosphamide (LDSp in rats'100 mg/kg). When oxidized by various oxidants or atmospheric oxygen (oxidation by atmospheric _ oxygen proceeds especially readily on the green leaves of plants), phosphamide trans- forms into 0,0-dimethyl-S-(N-methylcarbamoylmethyl)-thiophosphate: Cli O PSCFI CONHCIi, (CN,U)zPSCfi:CONHCH~ ~ ' ~ II ~ S ~ Hydrolysis of phosphamide proceeds most freely in an alkaline medium; in an acid medium it is more stable (at 70�C 50 percent of phosphamide undergoes saponification - in 0.8 hours at pH 9 and in 21 hours at pH 2). Metabolism of phosphamide apparently differs in plants and animals. The following flowchart may be suggested far metabc+lism in rats and cows on the basis of the products excreted: . ~ . 186 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407102/09: CIA-RDP82-00850R000500440001-1 FOR OFF[CIAL USE ONLY (c:1~1,0),f~SCH,CUNfICII, ~ ~ ' ~ ~ ~ CH,O~ _ (CH,O)zPSCH=COOH PSCtI,CUNfICtf, (CH,O)zPSH ~ S HO/ S S . . i . ~ ~ (CH,O),POH ~ 1 s _ . l ~ . (CH,O)~POH p 0 ! ~ ii,t~o~ The following flowchart may be suggested for plants: (Cti~017PSCHiC ~NHCH~ � ' 1 . ~ s - 1 ~ . ct.~,o~ (CN,O)~PSCIi~CONF~CH~ (CfI~O)zPOH PSCH~CON1(CH, O S HU~S ' ~ . . (Cfi,O),~ H ~ ~ H~pp~ F . . Depending on the consumption nozm, the preparation usually breaks down in a plant within 15-20 days. Of course this also depends on the nature of the plant and on the meteorological conditions. . PhosphamidE is relatively unsta.ble when stored, and it quickly decamposes, especially at hiqher temperature. Impurities.in phosghamide catalyze its decomposition. Preparation containing traces of organic bases decomposes at a high rate; decompo- sition of phosphami.de in the presence of bases is accompanied by alkylation. Solu- tions of phospham~.de in organic solvents are more stable. y Phosphamide reacts with phenols and alkylphenols to produce molecular~compounds that have been proposed for use as insectic?des (429-431).~ _ 187 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407102/09: CIA-RDP82-00850R000500440001-1 FOR OFFICIAL USE ONLY = Usually phosphamide is marketed as a 40 percent emulsion concentrate containing, i.n addition to the active ingredient, an emulsifier and organic solvent. It is used against herbiv~rous mites, aphids and other sucking plant pests at preparation consumption norms of 700-1,000 gm/ha (active ingredient). At higher concentrations phosphamide is phytocidal. _ The preparation's time of action is about 15 daps. In many covntries its life expectancy is set at 10-15 days. Phosphamide may be obtained by two methods: First, by reacting dimethyldithio- phosphoric acid salts with N-methylchloroacetamide: (CN,O)1PSK -I- CICIi,CONHCH, (CFI,O),PSCH,CONfICH, -F KCI S S This reaction is usually performed in a medium cnnsisting of water and some organic solvents. The product yield is 80-95 percent; the purity of the initial substances has great significance. Second, phosphamide may be obtained by reactinq 0,0-dimethyl-S-(carboxymethyl)- or S-(carbalkoxymethyl)-dithiophosphate with hydrated methylamine at low temperature (432): ~ (CH,O)1PSCH,COOC6Ha CH,NHz (Cf1~0)2~SCt{2CONHCH~ CBH60fi S S Both the phenyl and the ethyl esters are used. The phosphamide yield is more than 90 percent of theoretical; however, the phosphamide obtai.ned by this method is less stable. Stabilization of the preparation requires very careful removal of all impurities, and primarily excess methylamine, traces of which promote decomposi- ~ tion of phosphamide. As with most other organophosphorus compounds, storage of phosphamide in iron con- tainers is not recommended. Even stainless steel promotes faster decomposition of stored preparation. O,O-Dimethyl-S-[N-(S -zaethoxyethyl)-carbamoylmethyl]-dithiophosphate (tiokron) is crystalline when pure, with a melting point of 46�C. Technical-grade product is a liquid with unpleasant odor that cannot be distilled in a high vacuum. It is moderately soluble in water, and more so in alcohols and esters, while it is.poorly soluble in aliphatic hydrocarbons (see also Table 47). . The LDSp in rats is 600-660 mg/kg. Tiokron is similar in chemical properties to phosphamide. Tiokron is synthesized by reacting alkali metal or ammonium dimethyldithiophosphates with monochloroacetic acid methoxyethylamide: ' 188 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OFFiCIAL USE ONLY ~ _ (CH,O)yPSK CICHzCONHCIi=CN~OCH, ~ S . ~ (CH~O)=PSCHzCONHCFizCH70CH~ KCI ~ S Tiokron is a good contact acaricide and insecticide, having systemic action for 15-20 days. It is marketed in the form of an emulsion concentrate. At the moment the scale of this prepar~tion's use is not great, but it is doubtlessly interesting due to its low toxicity to animals and man. The metabolism of this preparation in plants is apparently similar to metabolism of phosphamide. O,O-Dimethyl-S-(N-methyl-N-formylcarbamoylmethyl)-dithiophosphate (formothion) is poorly soluble in water and readily soluble in organic solvents; C~46 1.361 (see also Table 47) . . Its LD~p in rats is 330 mg/kg. It is similar in chemical properties to phosphamide, but it is more stable when stored and heated. One of the principal metabolic products in the animal organism is 0,0-dimethyl-S-(carboxymethyl)-dithiophosphate, which is subsequently hydrolyzed - to dimethylthiophosphoric and phosphoric acids. Formothion is obtained by reacting dimethyldithiophosphoric acid salts with N-formyl- -N-methylchloroacetamide: ~ (Ct1,0)~PSK -f- CICH~CONCNO (CN~O),PSCH1CONCHO KCl S CH~ S CH~ It is marketed in the fozm of a 25 percent emulsion concentrate, and it is used agai.nst various sucking and,some gnawing plant pests at consumption nqrms of 0.5-1 kg/ha. ~ . O,0-Dimethyl-S-(2-ethylmercaptoethyl)-dithiophosphate (tiometon, preparation M-81) is a colorless oil with a strong and unpleasant odor; v~apor pressure at 20�C is 3�10'4 mm Hg; volatility is 4.0 mg/m3; d~~ 1.209. It is readily soluble in most organic solvents, with the exception of aliphatic and some alicyclic hydrocarbons (see also Table 4~). At normal temperature M-S1 is stable, but it may decompose when heated. The first s~age of thermal transformation is Pishchemuka regrouping. It is hydrolyzed with water similarly as with methyl-mercaptophos. Metabolism of M-S1 in plants is ~iagrammed below: 189 ~'OR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007142/09: CIA-RDP82-40854R040500040001-1 FOR OFFICIAL USE ONLY - (C1~~0),~SCH,CEi,SC,Hb . ~ ~ . (CE(~0)zPSGi~CkIiSC,[{6 (C~j~O)1PSCHzCHzSCzHs g ~ ~ ~ . 1 ~ ~ (CH~O)~PSCH,Cl~,SOzC,Hb (CH~O)z~ CHzCF{zSOzC~He ~ ~ ~ ~-s (CH~O)z uOEi 4~ ~ O - i { I,PO~ Its LDSp i.n various animals is 70-120 mg/kq. The maximum permissible concen~tration in air is 0.1 mg/m3� I M-81 is a good~systemic insecticide with approximately the same time of action as - ~methyl-mercaptophos, but its initial contact insecticidal activity is somewhat weaker. It is believed that its contact insecticidal properties manifest them- selves following transformation of part of the product into the thiol isomer of methyl-me.rcaptophos or its metabolites. Preparation M-81 is produced in the form of emulsion concentrates containing from 20 to 50 percent active ingredients, and in t~e form of granulated preparation. a ield of about 90 percent of theoret- The principal method of obtaining M-S1 with Y~ ical is to react dimethyldithiophosphoric acid salts with 2-chlorodiethylsulfide: PSNa CIC.11zt.II~SC1H~ jCli,U)iPSC~.IIlCII~S(:~E16 -1- NnC{ ~c:H,ol~q . ~ s The process is perfor~?ed both in an aqueous medium with vigorous aqitation and in organic solvents. 1~81 can also be synthesized by reacting 2-oxydiethyl~alfi~ol olhsulfochlorideio- phosphoric acid in the presence of~sodium hydroxide a p CH~O)~PSH -1- Cf1a ~ ~ SO,CI -I- 'lNaOH H4CN,CH7SCiH, -F ( Y . . S PSCH,CH,SC,Ha CH~ SO~tONa NaCI 2Hz0 (CH,U)~~ 190 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY . However, ~n this case the yield does not exceed 75-78 percent. It is believed that the 2-oxydiethylsulfide ester of p-toluol sulfonic acid is formed as an intermeaiate product in this process, but it has not yet been isolated in the course of the re- action. 0,0-Dimethyl-S-(a-carbethoxybenzyl)-dithiophosphate (tsidial) is an oily liquid with a characteristic unpleasant odor that decomposes when distilled in a vacuum. It is freely soluble in most ~rganic s~lvents and poorly soluble in water; d~~ 1.226. , Its ignition point is 168-172�C. Tsidial is thermally unstable, and when heated to 120�C for 110 hours it undergoes almost 50 percent decompositian. At 50�C it withstands 30-day heating without noticeable ~ecomposition (see also Table 47). Tsidial may manifest insecticidal action for 15-25 days. It is an insecticide with = a broad spectrum of action, and it is used against herbiverous mites and sucking insects, as well as against lea.f-miners. Tsidial also produces gaod results against the codling moth. . Tsidial is classified as a moderately *.oxic preparation to m.ammals: Its LD50 in rats is 250-300 mg/kg. - Tsidial is obtained by reacting alkali metal dimethyldithiophosphates with halophenyl- acetic acid esters (434,435). C6FIeC11CUUC1F16 (CH~O),PSNa --r (CH90)zPSCE-ICOOCzHb NaX X S S Celi~ This group of compounds may also be obtained with halopY:enylacetic acid. Subsequent esterification of the ~btained product by alcohol would be required (436-438): (~~~,~p)z{~tih C,IISc:I I(:UUEI (CII,U):u'S I:II~Uc)11 KDr II I ti Itir S t:,;HS (CII,O?,Pti(:Ill:l~Ull -I� IZUII (C11,(.)),i'Sl'iICUOIZ II,O b I� S Lai l6 S f.~l t, - The reaction is performed in an organic solvent medium at 70-90�C. Esterification may be performed without isolation of the intermediate product. This produces a preparation that does not contain impurities which would raise its toxicity. 0,0-Dimethyl-S-(N-phthalamidomethyl)-dithiophosphate (phthalophos) is a white - crystalline substance with a melting point o� 72-72.7�C. It is readily soluble in acetone, methylethylketone, cyclohexanone, methylene chloride, xylol and other organic solvents; aliphatic h,ydrocarbons, in which the preparation is poorly soluble, are an exception (see also Table 47). 191 ' FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY . Its LDSp in experimental anims.ls is 400-200 mq/kg. In ar? acid medium phthalophos is resistant to hjdrolysis, and at pH 4.5 it hydrolyzes to 50 percent i.n 15 days in an aqueous solution, while it takes 12 hours at pH 7 and. 4 hours at pH 8.3. The end products of hydrolysis are phthalimide, dimethylthiophos- phoric acid and formaldehyde: ' CO (CH,O)~ ~ SCHzN \ 2H10 / S CO CO (Cl-I,U),POH (IN CH~O ~ X~ . ~ - S ~o However, these products are subsequently capable of undergoing hydrolysis to ,phos- phoric and phthalic acids. . Oxidants also break down the preparation, with oxidation occurring primarily at the sulfur atom. , Phthalophos is marketed in the form of a 20 percent emulsion concentrate, a~0 percent - wettable ,powder and a 10 percent granulated preparation. It is recommended against various pests of cotton, frui.ts and other crops. Its use against the codling moth instead of DI7T~is of interest, since it is broken down relatively easily, and it . does not leave toxic residues on fruits. Phthalophos may be obtained as follows (386) (all stages of the process proceed with good yield): CO CO � ~ ~ tict _ Ct(~O I-IN/ \ FIOCH,N\ CO CO ' CO ICFI~OIs~ SNs C~ ~ g r \ cicti,N~ ~ (CFI~O)zPSCF{,N/ ~ \ ~ i M ~ ~ co � s co ~ Metabolism of phthalophos in different objECts may be generally diagrammed as foll~ws (274): ' 192 ~ FOR OFFICIAL USE ONLY � APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 _ FOR OFFICI~L USE ONLY (CHaO)iPSCF1~UCH~ CO S ~ ~ `NCH,OH f ~ i CO - CO CO ~ I \NCIizSP(O~li~)~ ~ ~ / ~ \NCH,SP(OCH,)~ ' C~ / p C~C ~ ~ . ~o S ~o 0 ~ ~ _ l~ - CO ~ / COOH / COOH . . / _ , C/\ ~NF, I COOH ~ I COOH ~o ~ ' I ~ pH . . ~ ~ ~ CONI{, COOH COOH ; C~ ~X o~~ ~ C~/\ HO CO _ COOH ~ . 1 1 / /CONF1, ~ _ ~ COOH ~ � ~ ~I. Y ~ II 4,0-Diethyl-S-(6-chlorobenzoxazolinon-2-yl-3-methyl~)-dithiophosphate (phosalone) is a white crystalline substance with the odor of garlic. Phosalone is poorly - soluble in water and freely soluble in many organic solvents (see also Table 47). Its LDSp in rats is 135 mg/kg, and in mice it is 180 mg/kg. In an acid medium phosalone is relatively stable, while hydrolysis proceeds rather quickly in an alkaline medium. The principal hydrolysis products are 6-chloro- benzoxazolone, diethylthiophosphoric acid and formaldehyde. When phosalone reacts with oxidants, first the thion sulfur breaks off and the preparation transforms into O,0-diethyl-S-(.6-chlorobenzoxazol~rr-2-yl-3-methyl)- -thiophosphate, which is relatively unstable and breaks down quickly. It is believed that this compound is the first metabolite of phosalone in plants. - Phosalone is recommended against pests of various crops, and it is a hiqhly promising sul~stitute o~f DDT and other persistent organochloride insecticides. It is also used as a seed disinfectant with the purpose of protecting plant sprouts against damage by harmful insects and mites. 193 ' FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R000540040001-1 FOR OFFICIAL USE ONLY Phosalone is obtained by condensation of sodium or ammonium diethyldithiophosphate with 6-chloro-3-chloromethylbenzoxazolone: NCH,CI . ' (CxHa~):~PSNa . _ CI p ~ S NCIIzSP(OCsEi6)~ -I- NaCI - ~~~Q/ ~p S CI ~ O The 3-chlorome~hul-6-chlorabenzoxazolone required for synthesis of phosalone is produced with a good yield by the action,of formalin and hydrochloric acid upon 6-chlorobenzoxazolone (392). The reaction may also be performed in one stage with- out isolation of 3-oxymethyl-6-chlorobenzoxazolone. In turn, 6-chlorobenzoxazolone ~ is obtained with a good yield by direct chlorination of benzoxazolone by chlorine in tetrachloroethane or tetrachloroethylene (433). Secause benzoxazolone and its di- and trichloro derivatives are readily soluble in tetrachloroethane, the purity of 6-chlorobenzoxazolone obtained by.direct chlorination of benzoxazolone in tetra- chloroethane is high, and follawing separation from the solvent, it may be used withc5ut further purification to make phosalone. . . Z~o methods have been described in the literature for acquiring benzoxazolone: - 1. Condensation of o-aminophenol with phosgene: / NH~ ~aOH / I VH . ~I COCIz C,/,. oH � � ~o 0 - which proceeds in an aqueous medium i.n the presence of sodium hydroxide as e~ hydro- gen chloride acceptor. 2. Condensation of o-aminophenol with urea: / NH~ / I-NH I . + NH,CONH= _sNri, 0~ ~ a o oF{ o This reaction p.roceeds at high temperature, and it is �usually performed in some sort of organic solvent. It may also be performed without the solvent, by simple heating of the melted components. The reaction time is about 6 hours. Benzoxazolone - may be purified by distillation in a vacuum. In the author's opinion the second method~of ob*_aining benzoxazolone is more convenient and economical, since cheap, available urea is used in place of expensive, toxic phosgene. 194 ~ FOR OFF[CiAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 FOR OFFICIAL USE ONLY ' The nearest analogue of phosalone is pregaration SGA-18809 isee Table 45), which is obtained as follows: ca: , H~a ~ ~ . CFIO ~ ~ O CI~ CI 2NIi~SO~H ociicti=cficocFto i~~ o ~ctio ~ c> _ ~/UII H1o / Oli c~r,~, i ~ ci, C~ CX . . CX ~ N NH N Nfl~ HiSO, N ~ I ' SO,H ~ ~ iCH~O1tN SNn CI~ ~ ~lit~~~ r/ o _ CO l~ ~C~ - 'N N11 ~ N , CIi~CI ' O ~ . CI\ i ~ � ~C~ N N CII,SP(OCH,)t . ~ � O . O,0-DimethYl-S-(3,4�-dihydro-4-oxo-5,6-banzo-1,2,3-triazinyl-3-methyl)-dithioph~spha:e (gusathion) is a~ahite crystalline substancF with 3 melting point of 73-74�C; vapor pressure at 20�C i:, 2.2�10'~ mm Hg; volatility :.4 0.004 mg/m3. W'hen heated in a high - vacuum it decompos~:~ to release gaseous products (see also Table 47). Gusathion is classiFied as a substa:ice highly toxic to mam~nals. Its LD50 in :~ice is 15-17 mg/kq. ~ Gusathion is stable in chem.ical respects, and it may persist at room temperat.ure in the absence of moisture for an unlimited time. In aqueous solution at pH 5 and 70�, gusathion saponifies to 50 percent at 8.9 hours, while at 20�C it takes 240 , days�. In an alkaline mediu~ gusathion decomposes several time.s faster. When sub- jected to careful hydrolysis in an acid medium, gusathion produces 3,4-dihydro-4- -oxo-1,2,3-bPazotriazine, while in an alkaline medium it produces its ~xymethyl derivative: - 195 FOR OFFICIAL USF UNLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONL~ l~rvc~i,sr~ocH,~z ~~,o i _ - ~ I ~ iN S -1CH~01~~511 ~ N � O . - I / NH / I NClia011 ~ CHzO ~ \ iN ~ ~N . - N . N Oxidants cause substitution of thion sulfur by oxygen to form P-O-gusathion. . Gusathion is reconanended against various plant pests. It produces good resu].ts on cotton, fruits and many other crops. It is marketed in the.form of emulsion ~oncen- trates and wettable powders intended for spraying as water suspensic~ns. - Gusathion is obtained by reacting N-halomethyl derivatives of benzohydrotriazinone with salts of dimethylclithiophosphoric acid: ~ ~ / NCH,SP(OCFl3)~ / ~ ~NCH~I3r ~ (CIi,O),PSNa -_N~B~ r ~ ( ~N ~ . ~ ~ I N N ~ ~J When the bromomethyl derivative is used, gusathion is formed with a practir.al qu~nti- ' tative yield. . The 4-oxo-3,4-dihydro-1,2,3-benzotriazine needed for synthesis of gusathion may be oki~tained from anthranylic acid amide and sodium nitrite in an acid medium. ~0,0-Dimethyl-S=(4,6-diamino-1,3,5-triazinyl-2-methyl)-dithiophospfiate (menazon) is a~white crystalline substance with a melting point of 160-162�C. 'It is poorly solu- ble in most orgari~c solvents {see 31so Table 47). Menazon is a systemic insectici.de with low toxicity to mananals. ~ Its LDSp is 900 mg/kg. , It is cdpable of penetrating �into plants through the root system.and ixaQartir~ in- secticidal properties to them for a long.period of tiiae. It is similar in ctiemical " properties to other dithiophosphates of this type. ~ Menazon is marketed ~n ~he form of 70 percent wettable powder and as g~anules to be introduced into soil. Especially good results have bzen enjoyed with this prepara- tion aqainst vectors of viruses causinq potato diseases. Menazon is obta.ined by reacting alkali metal or ammonium dimethyldithiophosphates with 4,6-diamino-2-chloromethyl-1,3,5-triazine: 196 ' 4 FOR OFFICIAL US~ ONLY ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OFFiC[AL USE ONLY . H~N~ / CH=CI (CH~O),PSCH~~ N\ /NH~ ~ II ? (CH~O)zPSNa ~ N~N ~ N~N - ~ ~ ~ NH, NH, In a number of countries the ~-~onn.for residual quantities of the pe~ticide has been se~ at 0.1 ~g/kq. Pyrophosphoric Acid Derivatives Produced in Germany in 1943, tetra,ethylpyrophosphate was the first organophosphorus insec~icide, known under the na..~,s of bladan and TEPP. After information on the ~ insecticidal properties of tetra~*-h_ylpyrophosphate and related compounds was ~ published, systematic research on the pesticidal properties of orqanic compounds of phosphorus began. A number of compounds ::�~re 2ound among the studied derivatives of pyrophospY:oric acid; some of them are still significant today. i Tlze following laws were established for the dependence between insecticidal activity ~ and structure of pyrophosphates. . The insecticidal activity of tetraalkyl;PYrophosphates decreases as the ester radical grows in size. The most active compound is tetraethylpyrophosphate, while thA activ-~ - ity of tetramethy~,PYrophosphate is somewhat lower. I � . ; Tetraalk.ylmonothiopyrophosphates exhibit greater insecticiclal activity than tetra- ~ alkyl,pYrophosphates, but their toxicity to mammals is concurrently higher. Add.i- tion of a second sulfur atom at the phosphorus atom reduces the compound's toxicity ~ to manunals~wi.thout noticeably decreasinq its insecticidal activity. i Addition o� a third sulfur atom to the phasphorus.~atom reduces the compound's insect- ~ . I icidal activity. Zhus for exampl.e, 0,0,0,0-tetraalkyldithiopyrophosphates have greater i insecticidal activity than do~0,0,0,0-tetraalkyltrithiopyrophosphates with the same ~ hydrocarbon� radicals. i Tetraalkydithiopyrophosphates containing different hydrocarbon radicals exhibit almost the same insecticidal activity as do the corresponding symmetrical tetra- ~ alkyldithiopyrophosphates with the same molecular weight. All pyrophosphates have stronq contact insecticidal action, and have practically ' ~ no systemic insecticidal action due to their low hydrolytic stability and fast decomposition on plants to form nontoxic products. Systemic activity appears as we proceed from pgrophosphoric acid esters to amides. Contact insecticidal activity decreases in this case. Pyrophosphoric acid octamethyltetramide has been proposed as a systemic insecticide. It does not have contact insecticidal activity, which is why it is used to protect mulberry trees from sucking pests. � Many general methods of obtaining esters and amides.~f pyrophosphoric, th~.o-, dithio- and trithiopyrophosphoric acids have been described in the� literature. We will note only the most.important methods, those having significance to pro- duction of ~this type of compounds. � ~ . 197 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R004500040001-1 ~ FOR OFFICIAL USE ONLY The principal methods of synthesiziag tetraalkylpyrophosphates are: 1. Reacting trialkylphosphates with phosphorus chloroxide or other acid chlorides: 5(RO)~PO -1- POCi~ 31R0)zP-O-~(OR)2 -F- 3RC1 d 2(RO)~PO SOCIi (R~)aP-O-P(OR)z 2RC! SO= ~ O ~.This reaction proceeds at relatively low temperature, and tetraalkylpyrophosphates foi-an with a satisfactory yield; however, the techniCal-grade product is somewhat _ contaminated by otlier derivatives of phosphoric acid. Dialkylchlorophosphate can also be used as an acid halide: (RO),P(:I (RO),P (RJ) ~-0-~(OR): RCI ~ O 2.. Reacting dialkylchlorophosphates with water in the presence of bases: ii,o ~ 2(RO),~ I (RO),~ 0-P(OR): v Both organic tertiary amines and alkali mEtal carbonates can be used as the bases. ~'his reaction produces the purest pre~arations with a good yield. This metYiod is also suitable for synthesis of symmetrical tetraalkyldithiopyrophosphat~s out of dialkylchlorothiophosphates: ~ u,o 2(RO)=~ CI (RO),~ O-P(OR)~ ~ g S When water is substituted by hydrogen sulfide, good yields oi tetraalkylthio- and tetralkyltrithiopyrophosphates can�be obtaineda - F~s~s 2FIC1 2(RU)sPCI (RO),~-S-P(OR), -I- ~ X X~U or S ~ 198 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/49: CIA-RDP82-00850R040500040001-1 FOR OFFICIAL USE ONLY Asymmetrical tetraalkylpyrophosphates form when dialkylphosphoric acids salts react with the corresponding dialDcychlorophosphates: - (RO)z~Cl NaSP(Olt'), NaCI (RU)zF~-S-q(UR')~ X . X This is a convenient method of obtaininy thio-, dithio- and trithiopyrophosphates._ - Asymmetrical ~tetraalkyldithiopyrophosphates are synthesized with a good yield by the following reaction: IRO),P (RO)iSS ~(RU11P-S-U(Ok), -i- RSS(UR)t L J: S Pyrophosphoric acid octamethyltetramide and its analogues are produced industrially by reacting tetramethyldiaminochlqrophosphate with water the presence of organic or inorganic bases: . ((CH~)sNJsNCI -F- ~~~s0 IICHa)xN)sP-O-P(N(CH~)�rIs .p ~ ~ ' i . j ' Tetraethyl pyrophosphate (TEPP) is a colorless li~uid with an unpleasant specific ' odor; its boiling point is 82�C at 0.05 mm Hg; d4 1.185; vapor pressure at 20�C is 1.55�10'4 mm Hg; volatility is.2.5 mg/m3. It mixes with water in all ratias, it is relatively soluble in alcohol, acetone, aromatic hyd�rocarbons and carbon tetra- chloride, and it is poorly soluble in getroleum ether and ligroin. ~ When heated to 170�C, TEPP decomposes to release ethylene; at 208-215�C decomposition i . proceeds very swiftly. ~ ! TEPP is quickly hydrolyzed by water, even at room temperature, to form diethylphos- ~ phoric acid, which is atoxic to both insects and animalss , ~ (C,tIsO)tP-U-P(OC.~Ife)z -F H~O 2((:zti6U)aPOF! . ~ ~ O ~ O Diethylphosphoric acid is decomposed practically completely by sunlight into phos- phoric acid, methane and carbon dioxide. Fonnation of the last two products pro- ceeds by way of acetaldehyde: ~ (C~i(6U1zPOfl (H,PO~ + 2CfI~CIiOJ Fi~PO, 2CH~ 2C0 h O 199 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFF'ICIAL USE ONLY ~ TEPP reacts readily with alcohols and amines, producing trialkylphos~hate and di- ethylphosphoric acid in the first case and diethylphosphoric acid amide and salt in the second. It enters into an interesting reaction with anhydrous hydrogen fluoride ~and potassium bifluoride, in which diethylfluorophosphate, which is toxic to ma~nals, forms. TEPP is characterized as being toxic to animals and man, for which reason it must behandled with great aaution. Its LD50 in rats is 1.2 mg/kg. �The insecticiaal ac- tivity of TEPP is close to three times weaker than that of thiophos, owing to which its use is continually decreasing. It is used in the form of aqueous solutions (0.2 percent) to control herbivorous mites and aphids. TEPP is syr.thesized by one of the general methods described above. Tetraet:~yldithiopyrophosphate (pirofos, sul'fotep, bladafum) is a colorless liquid with a boiling point of 92�C at 1~n Hg; at 20�C its vapor pressure is 1.7�10-4 ttan Hg. Volatility is 9 mg/m3; solubility in water is 25 mg/liter. It is readily soluble in most_organic solvents except aliphatic hydrocarbons. - Its LDSp in rats is about 5 mg/kg. Pirofos is close to thiophos in insecticidal activity. It is used in the FRG in , small quantities as a fumigant to control aphids in hc~houses. Pirofos is effective against mollusks and soft scales. It is obtain~d by one of the general methods de- scribed above. A large number of homologues and analogues of pirofos have been synthesized. The LDSp of tetraethylmonothiopyrophosphate is 0.5 mg/kg. - Tetra-n-propyldithiopyrophosphate (NPD) is a liquid k~ith a boiling point of 104�C at Q.O1 mm Hg. It is practically insoluble in water, readily soluble in most organic solvents and poorly soluble in petroleum ether ~nd ligr~in. 1 Its LDSp in rats is 100 mg/kg. NPD has moderate contact insecticidal activity, and it is marketed in the form of a 35 percent wettable powder and an 85 percent emulsion concentrate. It has been released as an experimental preparation in the USA. As with pirofos, it is resistar.t to hydrolysis, and its chemical reactions recall those of other pyrophosphates. Pyrophosphoric acid octamethyltetramide (octamethyl, Ot~A, pestox-III, schradan, sytam) is a colorless liquid with a boiling point of 126�C at 1 mm Hg; vapor _ pressure at 20�C is 6.5�10'4 nan Hg; volatility is 9.5 mg/m3. It crystallizes when cooled, with a melting point of about 20�C. Octamethyl mixes with water in all ratios: It is readily soluble in alcohols, ketones and halogen hydrocarbon deriva- tives, and it is poorly soluble in petroleum ether, kerosene and ligroin. � 200 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2047/02/09: CIA-RDP82-00850R000504040001-1 FOR OFFIC"_AL USE ONLY 7,'he aqueous solution of pure preparation is neutral,and it may be stored indefinitely without changing. Tn an acid medium octamethyl quickly decomposes, while in an alkaline medium it is more stable. Thus for example, 50 percent of the preparatiun hydrolyzes in neutral aqueous solution in 100 years, while it takes 200 minutes in 1 N HC1 solution and 70 days in 1 N sodium hydroxide solution. Its LD50 in rats is about 9 mg/kg. The :naximal permissible concentration in air is 0.02 mg/m3. ' Octamethyl has almost nc~ contact insecticidal activity, acting only as a systemic - insecticide by way of the plant. 'T'he reason for this is that it transforms into a more-toxic metabolite in plants and in the animal body. Metabolism of octamethyl in plants and in animals may be diagrammed as follows: (Ct1~):N ~N(CF1~)a ~p~ (CFI~)sN~ ~N(Ctla): ~P-O-P~ P-O-P ~CFI, (CN~),N~ I~ ~~N(CI l,)z (Cli~),N~ a ~~N ~ ~CIi~01i _ . il . ~ + ~cii,l~N~ /N(CH~)~ , Hydrolysis proceeds f'-O-[~ /CII~ (CI1~),N~~ Y ~N O - Octamethyl can be oxidized by potassium permanganate or other oxidants. Octamethyl is chlorinated to form, in the first stage of the process, the corres- ponding chloromethyl derivative. A total of four chlorine atoms can be introduced. Octamethyl is used on a minor scale as a long-acting systemic insecticide. It is used in the USSR to control sucking pests of the mulberry tree, since it is harmless to silkworms that feed on the leaves of the mu].berry tree. ~ The principal industrial method of producing octamethyl is to react tetramethyl- diamidochlorophosphates with water in the presence of tertiary amines, for example pyridine or, still better, tetraethylamine. Good yields are also obtained by re- acting tetramethyldiamidochlorophosphate with potash. Octamethyl can also be synthesized by reacting tetramethyldiamidoethylthiophosphate with tetramethyldiamido- chlorophosphate at 140�C: . ~lrFl~li~~su CI C~IisOpIN(CI1~)2~e ~ p O ll~Ha)sN~jP-O-P~N(Chl,):Ja CzllsCl 0 O 201 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONC.Y Phosphranic Acid Derivatives Active insecticides, acaricides, fungicides and herbicides have been found among the large number of alkyl- and arylphosphonic, alkylthio-, arylthio- and dithio- phosphonic, and dialkyl- and diarylphosphonic acid derivatives, but only a few com- pounds have found practical applications in agriculture. Most organophosphorus derivatives of this type are still in the research staqe. The toxicity of mi.xed esters of inethyl- and ethyl~thiophosphonic acids to homeothermic animals is hiqher i.n most cases than that of analoqous mixed esters of phosphoric acid (2), thougk~ there are exceptions as well. Toxicity decreases as the size of the hydrocarbon radical bound to phosphorus increases. The toxicity of alkylphos- ~ phonic acids is relatively low, and it depends to a great extent on which radicals . are bound to phosphorus. The corresponding derivatives of thio- and dithiophosphonic - acids exhibit extremely variable toxicity to mammals, which depends to a great extent on the structure of ester r~dicals (293,439-441). - Mixed esters of thio- and dithioalkylphosphonic acids have insecticidal and acaricidal action in most cases (442-455y; they are active aqainst soil-inY:abiting pests as well (453). Many amido esters of alkylphosphonic and thiophosphonic acids also have insecticidal and acaricidal properties (456-458). Epoxypropylphosphonic acid deriva- ~ tives have bactericidal action (460). It would be interesting to note that substi- tution of one of the ester radicals by a benzyl group causes fungicidal properties to arise in alkylthio- and alkyldithiophosphonates. Benzylthiophosphonates also have _ similar properties (461,462). Many mixed esters of alkylthio- and alkyldithiophosphonic acids containing different functional groups in both the ester radicals and the radical bound to phosphorus have ' insecticidal and acaricidal properties (443,465-469,471). Insecticidal properties have also been noted in methylphosphonate and methylthiaphosphonate.hydrazides (470). Substitution of hydrogen in the hydrocarbon radical at the phosphorus atom of alkyl- phosphonic acid derivatives by a halogen atom reduces toxicity to vertebrates. Thus for example, mixed esters and ester amides of chloromethyl-, chloromethylthio- and - chloromethyldithiophosphonic acids exhibit lower toxicity than the corresponding derivatives of inethyl-, methylthio- and methyldithiophosphonic acids (443,463,464). Ester amides of chloromethylthiophosphonic acid have herbicidal action, and they are recotmnended for use on rice and vegetables to control millet-lik~ weeds (464). It w~uld be interesting to note that accumulation of halogen atoms in the methyl group reduces the compound's herbicidal activity. Complete chloromethylthiophos- phonic acid amides are even less active, while the corresponding derivatives of chloromethylphosphonic acid are still less active (463,464). 2-Chloroethylphosphonic acid is an interesting plant growth regulator (472-476). It hastens maturation of fruits, and it causes leaf fall in a number of crops. _ The action of 2-chloroethylphosphonic acid and its acid esters is based on their decomposition and liberation of ethylene. Allyldithiophosphonates have nematacidal action (477,478). Alkoxyvinyldithiophos- phonates (479) and dialkoxythiophosphonacetates (480) have similar properties. Alkoxyvinyl-, alkylsulfonyl- and alkylsul�i.nyldithiophosphates have herbicidal action (481-486). Aminomathylphosphonates have herbicidal action as well (487). . 202 ~ FOR OFFICIAL USE ONLY ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2047/02/09: CIA-RDP82-00850R000504040001-1 FOR OFFICIAL USE ONLY . Addition of a hydroxyl radical at the carbon atom b.ound to phosphorus as a rule re- duces toxicity of esters and other derivatives of alkylphosphonic acids to mammals, though there are exceptions to this gener~l dependence. Enlargement of the hydrocarbon radical bound to phosphorus reduces the toxicity and insecticidal activity of the compound. For example the LD50 in rats (mg/kg~ is 2.5 for O-ethyl-0-(4-nitrophenyl)-methylthiophosphonate, 25 for 0-ethyl-0-(4-nitro- phenyl)-isopropylthiophosphonate and 250 for O-ethyl-0-(4-nitrophenyl)-n-hexylthio- phosphonate. Toxicity to mammals changes depending on the structure of ester radi- cals in the same order as for esters of phosplioric and thiophosphoric acid. Thus O-alkyl-O-(4-nitrophenyl) esters of alkylphosphonic acids are more toxic than the O-alkyl-0-(2,4,5-trichlorophenyl) esters of these acids. ~ As we proceed from alkylphosphonic, alkylthiophosphonic and alkyldithiophosphonic acids to the derivatives of arylphosphonic, arylthiophosphonic and aryldithiophos- phonic acids, toxicity to vertebrates decreases significantly, while in most cases the pesticidal properties persist. This is valid primarily in relation to mixed esters of arylphosphonic acids, which are less toxic than the corresponding esters of alkylphosphonic acids. Many phosphonic and thiophosphonic acids containing thiofuran (490,491), furan ~494), piperidine (489) and other heterocyclic residues are also active insecticides, acaricides and bactericides.. Some compounds of these series which have enjoyed some.practical use are shown in Table 48. The usual method of obtaining mixed esters af alkylphosphonic, alkylthiophosphonic and alkyldithiophosphonic acids is to react the appropriate acid chlorides with alcohols, phenols and mercaptans in the presence of hydrogen chloride acceptors (496-507): R-oii ~~H~ H~o:i ~UR' R~~~~~ -iici ~ R~~~I -HCi~ Rp\OR� X X X Tertiary amines, alkali and alkali-earth metal carbonates, caustic alkalis and other inorganic and organic bases may be used as hydrogen chlQride acceptors. Metallic capper is often used in.the reaction as a catalyst (496). Similarly as with mixed esters.of thiophosphoric acid, mixed esters of alkylthio- phosphonic acid are obtained in acetone or methylethylketone in the presence of potash or soda by prolonged boiling of the reaction mixture. The reaction with mercaptans is also performed in the presence of hydrogen chloride acceptors (507, 5~8), ~rhich are usually tertiary amines. /OR' it.,SH /OR' . RP R~~`CI -iici X\SR� 203 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500044441-1 FOR OFFIC~AL USE ONLY . Table 48. Derivatives of Alkyl- and Aryl- ~ Chemi.cal Name Formula Synonyms� . ~ Chlorofos, trichlorfon, 0, 0-Dimethyl- (1-oxy-2, 2, 2- (Cr[,O),P-CHCCI, -trichloroethyl)-phosphonate I~ IH dipterex, dylox, 0 b Bayer L-13/59, . ' meguvan, tugon O, 0-Dimethyl-l-bu*yroxy-2 , 2, 2- (CIi,O)~P-CHCC1, Butonate ~ -trichloroethylphosphonate O ~COC,H,�N 0- (2,4, 5-trichlorophenyl) -di- (C,H,I,POC~H,CI~�2,4,5 Agvitor ethylthiophosphinate . S O-Ethyl-0-(2,5-dichloro-4- ~'H6\ Ts-18244 ~ , POCaI~=C1~�2,5-1-4 - -iodophenyl)-ethylphosphonate C2HeO~M S 0-Ethyl-0-(2,4,5-trichloro- ~'H6\ Trikhloronat ~ phenyl ) -ethylthiophosphonate / ~ nC~H2Cl~-2,4,5 CsN.O S O-Ethyl-S-phenylethyldithio- ~~Hb~ Difonat phosphonate /PS~eti� C,HaO S _ O-Isobutyl-S-phthalimidomethyl~ ~?H`\ ~ ~ \ Kh-4543 ~ ethyldithiophosphonate ~ PSCH1N _ iso-~~i~,p~S \CO) i 2-Chloroethylphosphonic acid CICI ItCFI,(~(OFI), Ethrel, etef on . u . o O-(2,4-dichlorophenyl)-N- Izofos-2 -(isopropylamido)-chloro- CICH,~ POCaH,CI ~-2,4 methylthiophosphonate �iaa- C~fIrNH~S . - O- (2, 4-dichlorophenyl) -N- CICIi,~ - (sec-butylamido~) -chloro- POC,H,CIz-2,4 Izofos-1 methylthiophosphonate sec-�C~HoNti ~S 204 FOR OFFIC[AL USE ON~.Y APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 FOR OFFICIAL USE ONLY - phosphonic Acids Used as Pesticides � LD50 ~ in Rats (Orally) Boiling ~ mg/kg . Point,�C S~lu- LDSp in . (At Indi- ~ bil Rabbits cated Mel.ting ity (Cutan- Pressure), Point, Water, eously), .mm Hq �C mg/liter mg/kg Use. Forms of Application and Consumption Noz~ns 100 7:3-74 ~2~pp 660 Insecticide with broad spectrum of action, used ' (0,1) (8;3-84) ~ in agriculture, animal husbandry and ublic P health. Aqueous solutions, w.p., solutions for ultralow v~olume sprayinq. E.c. In agriculture, 0.5-2 kg/ha. . I(O,U3) 4 - Moderate 700 Contact i.nsecticide for animal husbanclry. _ E. c. - - Insol- 17 Insecticide controlling soil-inhabiting pests. uble - 60-67 0,2. . 40 Insecticide controlling soil-inhabiting pests. 40$ e.c., 5$ granules. ~ 108 - 5p 18-37,5 Insecfiicide controlling onion fly, cabbage - (0,01) . 341 magqot and carrot rust-fly. 50~ e. c. , _ ~ 2.5-7.5$ granules. 130 - Zp ~g,~ Insecticide controlling soil-inhabiting pests. (0,1) 147 E.c., granules. ~ ~ ~27-~28 58-60 12 75 Insecticide with broad spectrum of action. (I�10-0) 121 E.c., w.p. . . - 74-7b ~od 42?0 Plant growth requlator. In plants, releases b300 ethylene as the active agent. 24$ aqueous ~ solution. _ , . ~'~~-~`~Z - 2.4~ 315 Herbi~cide controlling millet-like weeds in rice ~~'b~ 1200-13U0 and vegetable crops. E.c.; 4-8 kg/ha. 134-135 _ - 425 Herbicide controlling millet-like weeds in (U,13) rice. ~E.c.; 4-6 kg/:za. I 205 FOR.OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/49: CIA-RDP82-00850R040500040001-1 FOR OFFiCIAL. USE ONLY Chemical Name Formula Synonyms O- (2-Chloro-4-methylphenyl)-N- CICIiZ~ Izofos-3 - (sec-butylamido) -chloro- PUC,H,CH,-4�CI�2 - methylthiophosphonate erop-C,HyNH~s - 0-Ethyl-0-(4-nitrophenyl)-phenyl- ' ~eE~d~ . EPN thiophosphonate POCaH~fVOi-4 C~H60'/S O-Ethyl-0-(4-cyanophenyl)-phenyl- ru~~a\ ~ Surecide _ thiophosphonate /~'~CBI~I~..N-4 C,I1�O S O-Ethyl-0-(2,4-dichlorophenyl)- Cef~e~ Ts-Seven , -phenylthiophosphonate POC6Fi,Cl~-2,4 C:Hsa/~ 0-Methyl-0-(2,5-dichloro-4- C,F~,~ V-506 -bromophenyl) -phenylthiophos- POC,H,C1~-2,5�Br�4 phonate ~Hs~/S - O-Ethyl-S-benzylphenylthio- C~H6~ Inezin ~ PSCFI,CaHe phosphonate ~ C~Hep1~ ~ (Fl0)zPCHtNliCl�I~COOH _ N-Phosphonomethylglycine ~ NOM-113 0-Ethylpropylphosphonic acid C,fi,~ NIA-10637 ~ POt~( C,HbO~~~ Propylphosphonic acid CH,Cf I,CI~I,P(ON)~ NIA-10656 ~ b S-(6-Chloroxazolopyridinon-2- CI~ SGA-16088 -yl-3-methyl)-0-methylethyl- . il dithiophosphonate N~ ~OCii~ ~H,S P~ . � S \CzF~` 206 ~ , FOR OFFiCIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 FOR OFFICIAL USE ONLY ~50 in Rats (Orally) Boiling m k Point,�C Solu- LDSp in {At Indi-, bil- Rabbits � _ cated Meltinq ity (Cutan- Pressure), Point, Water, eously), ' - mm Hg. �C mct/liter mg/]cg Use. Forms of Application and Consumption Norms 147-I48 - - b~~ Herbicide controlling ~llet-like weeds in rice (0,1) and vegetables. E.c.; 3-5 kg/ha. - - 3r Insol- g-~ Acaricide and insecticide. 25$ w.p.j u~ to _ uble 45 1 kg/ha.. ~ , _ 83 ~3.7 (in Insecticide and a~aricide with broad spectrum .mice) of action. 28.5~ e.c. L~'~' - " 274 Insecticide controlling soil-inhabiting pests. = oes 3$ dust; 1-3 kg/ha. ot istil 42 8 28 ~ ' Insecticide with broad spectrum o~ activn. : E.c.; 1-2 kg/ha. ~ - Li,quid 7 ~b0 Fungicide controlling (pirikulyariya) ~n rice. _ - FreP�~,y~ Pti-1d7.~ Herbicide used at consumption norms of 0. 5-1 � soln~le toxic kg/ha as amine salts. Used against perennials, including wheat-grass. _ iquid, Good 2~00 plant growth regulator. , oes � I rat . . isLil 3723 ~ - Good Plant growth regulator. ~ iquid ~ - 55-57 - 470. Contact and intestinal insecticide. Also ~ effective .against miners.~ ~ _ 207 FOR OFFII`,IAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R004500040001-1 FOR OFFiCIAL USE ONLY ~ Mixeri esters of alkylthio- and alkyldithiophosphonic.acids can be obtained from salts and~halogen derivativES (293,509). This reaction proceeds especially readily with thiophosphonic acid salts and halobenzyls (509), and especizlly the salts of alkyldithiophosphonic aci.d and varic~us derivatives of monochloroacetic acid (293): /OR, /pR~ Kp CICH~CONHR" RP NH,CI S~~SNFI~ S~SCH,CONfIR" ~ A similar reaction can be used to ob~ain ester amides of alkylphosphonic and alkyl- thi~phcsphonic acids (510). The alkylphosphonic, alkylthiophosphonic and alky.ldithiophosphonic acids zequired for the synthetic processes can be obtained by var.ious methods (22). Arbuzov's reaction and the Mikh~elis-Bekker reaction are among the most general methods of forming a C-P bond (511,512): . . (RO)aP -F ~i~X (RU),~R' R?C I (RO)1Pti0 R'X (RO),PR' + FIX , . h - U Both of these reactions are ideal methods of obtaining various esters of alkyl- phosphonic acids. Subsequent transformation of alkylphosphonates into mixed esters or into other derivatives presents certain difficulties due to the large numb~er of stages in the process, for which r~asons a number of other ~nethods of obtaining aliphatic compounds with a C-P bond have been developed. Among such me~hods, we ' should first mention the reaction between red pho~phorus and alkylhalides in the ~ presence of powdered copper, which proceeds at 300-360� in a flow-through systen, and produces satisfactory ~ields of alkyldichlorophosphines (22): RCI P RPCIz R,PCI ~ which can be used to easily'obtain alkylphosphonic and~alkylthiophosphonic acid chlorides: ~ RPCI, ~X~ RiCI, ~ X X=O, S 208 FOR OFFIC[AL USE OI~(LY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR nFFiCIAL USE ONLY ~ ~ Of even greater interest is the reaction between aZkylhalides and~yellow phosphorus in phosphorus trichloride, which proceeds at about 200�C under pressure i513): RCI -I- PCI, P --y RPCI, A similar reaction may be used to obtain phenylene-bis-dihalophosphines (514), which are also intermediate products useci in pesticide synthesis (515,516). All~yldichlorophosphir~es may also be obtained by reacting phosphorus trichZoride with trialkylaluminum: _ PCI~ AIR, RPCI~ -I- AICI, - The reaction should be performed in the presence of a large excess of phosphorus trichloride, since otherwise the products would be dialkylchlorophosphines and - trialkylphosphines. . ~ This reaction may be of siqnificant practical interest, considering the large amounts of trialkylaluminum produced. Alkylphosphonic acid chlorides may be obtained with a good yield by chlorophos- = phinating hydrocarbons (517): _ I~I . RH PCI, R[?~~~ -1- lic:l u Alkylphosphonic acid chlorides may also be transformed into alky.lthiophosphonic acid chlorides by the action of phosphorus pentasulfide: RPCI~ P~Se R~CI, -I- F'zOs . . ~ Alkyldichlorophosphines are also. obtained by reacting organic compounds of lead, mercury, magnesium and other metals with phosphorus trichloride, but these reactions cannot be used for industrial production. Many other particular methods of obtaining various alkylphosphonic acids are known. Thus for example, when phosphorus trichloride is,heated in an autoclave with paraform under pressure, a qoqd yield of chloromethylphosghonic acid is obtained: CHsO PC1~ CICNzPCIj - II ' 0 209 ' FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R040500040001-1 FOR OFFICIAL USE (DNLY N:iile dialkyloxymethylphosph~nate, which has insecticidal properties, is formed out of orthoformate and PC13 in.the.presence of anhydrous zinc chloride (518). Methyl- thiophosphonic acid chloranhydride is obtained as a mixture with dimethylthiophas- phinic acid chloride by heating di.methyldisulfide with phosphorus chloride to 300-400�C (519). A nua~ber of.other methods of obtaining alkylphosphonic and alkyl- thiophosphonic acid chlorides have been described (22). Various benzylphosphonic and benzothiophosphonic acids, the esters~of which~are fully analogous with alkylphosphonic acid dzrivatives, are obtained similarly as alkylphosphonic acids (520-523). Most suc:~ derivatives have fungicidal properties. - Esters and s~ther derivatives of arylphosphonic and arylthiophosphonic acids are also obtained by reacting actid chlorides of the corresponding acids with~alcohols, phenols or mercaptans in the presence of hydrogen chloride acceptors (524-536). The reaction proceeds in conditions similar to those described above for aliphatic com- pounds. The arylphosphonic and arylthiophosphonic acid chlorides required for this purpose are obtained as follows. A reaction is performe.d between~hydrocarbons and phosphorus trichloride at high temperature to obtain aryldichlorophosphines, which are then transformed by con- - ventional methods into arylphosphonic or arylthiophosphonic acid chlorides (22)� Aryldichlorophosphines are also obtained with satisfactory yields by reacting aromatic hydrocarbons or their derivatives with phosphorus trichloride in the presence of Lewis acids. . Mixed esters and ester amides of arylphosphonic and arylthiophosphonic acids are obtained with good yields by oxidation or by attachment of sulfur to the appro- priate esters or ester amides of arylphosphonous acid; the latter are formed by reactinq alcohols, phenols and mercaptans with aryldichlorophosphines in the presence of hydrogen chloride acceptors: - . ~OR ~ . . ArPCI, -F ROFI R'OH A~P~UR~ -i- 2HC1 OR ~xl ,OR ~ = ArP~ ArP X~OK' ~UR' ~ ~ ~(a~~ S . Compounds with the formula R~p=N-il R~, . X obtained from the amides of phosphonic acids and their derivatives, ha~~e been pro- posed as defoliants (537). 210 FOR OFFICIAL USE O1VLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOit OFFIC[AL USE ONLY Because a number of derivatives of phosphonic acids are enjoying extensive applica- tion, the metabolism of some preparations in various biological media has been - studied, to include chlorofos (274,538,53~), difonat (540,541), VTsS-506 (542) and other preparations of this type. It should be noted that the P-C bond is rather strong, and that during metabolism it is broken apart rather slowly; compounds having substituents such as halogen, hydroxyl and so on at the a-carbon atom are an Excep- tion. Such compounds break down rath~r quickly to form, in the end, phosphoric acid, which is assimilated completely by plants. The most important representatives of this type of compounds are presented below. 0,0-Dim~thyl-(1-oxy-2,2,2-trichloroethyl)-phosphonate (chlorofos) is a white _ crystalline powder; its solubility (gm/100 gm) is 12.3 in water, 15.2 in benzene and 75 in chtoroform. It is poorly soluble in paraffin hydrocarbons. Determination of the molecular weight of chlorofos showed that it is a dimeric compound. The vapor pressure of chlorofos at 20�C is 7.8�10'6 mm Hg. Its volatility is 0.11 mg/m3 (see also Table 48). _ Chlorofos is classified as a moderately toxic compound. Its LDg~ in rats is 560 mg/kg. The maximum permissible concentration in air is 0.5 mq/m . The preparation is broadly emploped against various plant pests (sucking and gnawing), to include eurygaster,codling moth, corn borer, various species of flies and the cattle fly. The ~attle fly is controlled by a special form of the preparation con- tainingchlorofos solution mixed with mineral oil and isopropyl or butyl alcohol. This solution penetrates quickly throuqh the animal's skin, which permits dramatic reduc~.ion of the dose of the preparation used to process the animals. Chlorofos is stable in an acid medium and undergoes fast hydrolysis in an alkaline medium; hydrolysis proceeds along two pathways. In an acid medium the first product of.hydrolysis is 0-methyl-(1-oxy-2,2,2-trichloroethyl)-phosphonic acid, which hydro- ~ lyzes further to phosphoric acid: HO~ ~ (Cll,O);.N--CIICCI~ f1,0 -r CFI,UII -I- ~P-CHCCI~ b UI~ , CliaO~~ OH . Chlorofos decomposes especially quickly when exposed to light in dilute solutions. In an alkaline medium chlorofos undergoes dehydrochlorination and concurrent re- groupinq. The principal reaction product is O,d-dimethyl-0-(2,2-dichlorovinyl)- phosphate (DDVP): - (CFI,O)~-CIICCi, KOH (CI~1,0)zPOCFi=CCIz KCI Hi0 Oli O Dichloroacetaldehyde, dimethylphosphoric acid and some ot}ier compounds are formed as products in side reactions (for example as a zesult of hydrolysis of Uu~7P). 211 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR O~'FICIAL US~ ONLY ' Chlorofos is a qood methylating agent, and for example it can react with potassium iodide to form methxliodide. When aqueous solutions of chlorofos are stored for a long~period of time, the pre- paration underqoes partial hydrolysis, owing to which the solution becomes acidic due to presence of phosphoric, dimethylphosphoric and hydrochloric acids. Storaqe of chlorofos in unlined iron cnntainers is not recomanended. R,educing agents also decompose chlorofos. Ztao methods can be used to obtain it on an industrial scale: 1. Condensation of dimethylphosphite wi*_h chloral: (CFI,O),PrtO ? CCI~CIiO (CIi,O),P-CHCCI~ , - b bH ~ The reaction proceeds at room temperature, and heat is liberateci. Chlorofos may be obtained with a practical quantitative yield. The purity of the initial dimethylphosphite has great significance in this method. - The purer the dimethylphosphite is, the grea~er is the yield and the better is the quality of the chlorofos. It is best to use distilled dimethylphosphite. It can be distilled in a film evaporator at 5-8 mm Hg. Such dimethylphosphite usually contains 93-96 percent pxincipal substance, and when it is used, 93-95 percent chloro- fos forms, with a small quantity of acidic impurities. When technical-grade undis- tilled dimethylphosphite is used, the concentration of the principal substance in the resulting chlorofos is 8'7-88 percent. It contains a rather large amount of acidic impurities, as well as 0-methyl-2,2,2-trichloro-l-oxyethylphosphonic acid and the reaction product of chloral and phosphoric acid. The di.methylphosphite required for synthesis of chlorofos is obtained by reacting phosphorus trichloride with methanol: . PCIy 3CtI,Utl (CII,O);{~IIU '~FICI Ct1,Cl , Usually the process is performed in an organic solvent at low temperature. Methyl- chloride is a convenient solvent. It boils at -24�C,~and as it evaporates it cools the reaction mixture w~ile simultaneously removinq the hydrogen chloride formed. - Dimethylphosphite is usually obtained in a continuous process. After the reaction ends, the solvent is distilled away, and the liqht fractions are evaporated in a column. Dimethylphosphite is purified by distilli~ng it in a film evaporator at a temperature on the order of 120�C ati 5-8 aan Hg. TY~e dimethylphosphite yield in this method exceeds 90 percent, if we count phosphorus trichloride. Obtai.ning dimethylphosphite in the presence of water has been proposed as a way of avoidinq formation of inethylchloride (549): PCI~ -I- 2CH,OH 1i,0 (C[-I~U),PHO 3HC1 212 FOR OFFIC[AL USE ONLY ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY ~ . However, no information on industrial use of this method has been published. - Monomethylphosphite and phosphoric acid are fozmed in small quantities as byproducts of the dimethylphosphite acquisition process: (CH,O)1NH0 HCI CH,U~(Oli), CH~CI (CH~O)zPFfO ? 2l~ICI -r Fi~PO~ 2CFI~C1 At high temperature phosphoric acid is capable of undergoing disproportionation, _ releasing phosphine: 4H~P0~ 3H3P0~ ? Pt{~ When the process of obtaining dimethylphosphite is performed incorrectly, liberation of phosphine may be a cause of spontaneous combustion. ~ ~ In the second method the reaction of forming dimethylphosphite and its reaction - with chloral are combined into a sinqle stage. The process is performed in organic solvent, with the heat beinq extracted: 3CH~OH PCI~ -1- CCI,CHU (CIi~O),P-CHCCI~ CH~CI 2HCl ~ b bH . - The chlorofos yield in this'combined method is more than 80-85 percent. � Chlorofos is purified by recrystallizing it out of water or organic solvent. The mother liquor from chlorofos recrystallization is usually "used to p'roduce DDVP, which is enjoying increasingly greater application in agriculture and at h~me. There are many modifications of the second method of obtaining chlorofv~: tiatious solvents can be used (carbon tetrachloride, methylchloride, chlorobenzene etc.); the process can be performed in a broad interval of temperatures. Chlorofos may be obtained by both the first and the second method in periodic arid continuous processes (543,544). Chlorofos obtained by the methods described above can be purified by washing away - the acidic impurities in chloroform solution; when the latter is evaporated away, the resultinq chlorofos contains more than 90 percent principal ingredient and a minimum quantity of impurities. Wettable powders are easily produced from such chloxofos. Surfactants and solid carriers performing the role of crystallization centers are added to technical-grade chlorofos to hasten its crystallization (545). A large number of arialogues and homologues of chlorofos has been synthesized, but - their insecticidal properties are siqnificantly weaker than those of chlorofos. Thus for example, 0,0-diethyl-(lioxy-2,Z,2-trichloroethyl)-phosphonate is almost 15 times less active against flies than chlorofos, and it is more toxic to homeo- thermic animals. Among the derivatives of chlorofos, some of its esters with various acids have.attracted in}erest in their use as insecticides. . 213 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 - FOR OFFICIAL USE ONLY , ~ N6ention should also be made of 0,0-dimethyl-(2,3,6-trichloro-a-oxybenzyl)-phosphonate, ' - obtained by condensation of dimethylphosphite with 2,3,6-trichlorobenzaldehyde, which exhibits herbicidal action (546). 0,0-Dimethyl-(1-butyroxy-2,2,2-trichloroethyl)-phosphonate (butonate) is a colorless = liquid with almost no odor; d4~ 1.3998; n$ 1.4740. Hutonate is moderately soluble - iri water and freely soluble in most organic solvents (see also Table 48). Its LDSp in rats is 700 mg/kg. ~ Butonate has strong contact action, and it is used mainly against ectoparasites in domesti.cated animals. It is marketed as an emulsion concentrate. - The preparation is more resistant to hydroly~is than chlorofos. Its hydrolysis pro- ceeds quickly in an alkaline medium. The end products of hydrolysis ~re phosphoric, hydrochloric and butyric acids. Butonate is obtained by reacting~chlorofos with the anhydride or acid chloride of butyric acid: _ (CH,O), i HCCI, {K-C~H~CO)~0 O OH ---r (CH~O)tP-CHCCI~ N-Ca~ivC00H ~ bcoc,H,-K Phosphonium Salts Besides phosphoric acid esters and amides, some salts of substituted phosphonium, - which have varied pesticidal activity, have been studied as pesticides. One of thE~ first to be used aqainst moths was 3,4-dichlorobenzyltriphenylphosphonium chloride, which was an ingredient of eylan, with which furs and wool were impregnated to prevent destruction by moths. Tetraalkylphosphonium salts have almost the same bactericidal and fungicidal action as do ammonium salts with identical hydrocarbon radicals (547). ' . The preparation fosfon-D--tributyl-2,4-trichlarobenzylphosphoniumchloride enjoyed some Systematic study of the bialogical activity of phosphonium salts established that the activity of a compound depends not only on the structure of the cation but also on the structure of the anion. Substances have been found among phosphonium salts that exhibit not onl~� microbiological and insecticidal activity but also herbicidal properties (548). However, they have not as yet found practical applications. Some practical applications as a fungicide have been found for the binary salt of tripheny~decylphosphonium cri h se beents gqestedlashanragentmagainst phyt phthora and ~50 ~00-1,010 mg/kg), cercosporosis as a 50 percent we~table~powder. 214 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2047/02/09: CIA-RDP82-00850R000504040001-1 FOR OFFICIAL USE ONLY _ BIBLIOGRAPHY 1. Kabachnik, M. I., VESTN. 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FRG Patent 1278172 (1962). 404. Osborne, G. 0., and Page, G., J. CHEM. SOC., 1967, pp 1192. ~ 405. FRG Patent 1245206 (1958). 406. U.~S. Patent 3551562 (1971); RZHKHIM, 21N696 (1971). ~407. U.S. Patent 3502670 (1970); RZHI~iIM, 12N536 (1971). 408. Japanese Patent 12145 (1969); RZHKFiIM, 13N698 (1970). 409. English Patent 1167785 (1969); RZI~KHIM, 11N888 (1970). 410. French Patnet 94008 (1970); RZHKHIM, 20N544 (1970). 411. U.S. Patent 3428655 (1969); RZHICHIM, 12N1005 (1970). 412. U.S. Patent 3564013 (1971); RZHICHIM, 20N633 (1971). 232 FOR OFFICIAL USE ONLY ~ APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFF[CIAL USE ONLY 413. USSR Patent 284257 (1970) ; RZHKHIM, 12N1000 (1970) . 414. Author's Certificate No 192692j IZOBR., PROM. OBRAZTSY. TOVARN. ZNAKI, No 33 (1969) . 415. CSSR Patent 132856 (1970); RZHICHIM, 5N642 (1971). , 416. U.S. Patent 3403201 (1969); RZHKHIM, 1N654 (1970). 417. 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N.,.et al., Author's Certificate No 245111; IZOBR., PRDM. OBRAZTSY. TOVARN. ZNAKI, No i9 (1969). ~ 434. USSR Patent 146719 (1960). 435. Japanese Patent 11877 (1969); RZHKFiIM, 15N665 (1970). 436. GDR Patent 77211 (1969). 437. FRG Patent 1300932 (1965). . 233 , FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY 438. USSR Patent 196654 (1967); IZOBR., PROM. OBFtA2TSY. TOVARN..ZNAKI, No 11 (1967). 439. Lieske, C. N., Hovanee, J. W., et al., J. AGR. FOOD CHEM., Vol 17, 1969, p 355. 440. Szabo, K., and Menn, J. J., J. AGR. FOOD CHEM., Vol 17; 1�69, p 863. _ 441. Shaw, J. G., J. ECON. ENTOM., Vol 63, 1970, p 1590. _ 442. Menn, J. J., and Szabo, K., J. ECON. ENTOM., Vol 58, 1965, p 734. 443. Fearing, R. B., Walsh, E. N., et al., J. AGR. FOOD CHEM., V.ol 17, 1969, p 1261. 444. U.S. Patent 3476836 (19'10); S.A., Vol 72, 1970, p 32017. 445. Bliznyuk, N. K.,. et al., Author's Certificate No 232971; IZOBR., PROM. OBRAZTSY. TOVARN. ZNAKI, No 2(1969); RZHICHIM, 7N689 (1970). 446. Peag, W. E., Beards, G. W., and Swenson, A. A., J. ECON. ENTOM., Vol 62, 1969, p 1083. - 447. Japanese Patent 10800 (1969); RZHI~iIM, 12N997 (1970). 448. U.S. Patent 352?~yS (1970); RZHKHIM, 18N627 (1971). 449. USSR Pa~ent 280368 (1970); OTKRYTIYA. IZOBR. PROM. OBRAZTSY. TOVARN. ZNAKI, " No 27 (1970). , _ 450. Brestkin, A. P., et al., IZV. AN SSSR, OKHN, 1969, p 814. 451. Swiss Patent 497127 (1970); RZHKFiIM, 11N531 (1971). 452. U.S. Pat~nt 3426021 (1969); RZHI~iIM, 7N685 (1970). 453. Mistis, W. J., and Smith, F. D., J. EGON. E'riTOM., Vol 62, 1969, p 712. - 454. U.S. Patent 34209918 (1969); RZHKHIM, 6N860 (1970). 455. U.S. Patent 3351679 (1968); 3401220 (1969); RZHKHIM, 2N717 (1970}. 456. ~Kondratyuk, V. I., Slyusarenko, Ye. I., and Derkach, G. I., "Fiziologicheski aktivnyye veshchestva" [Physioloqically Active Substances], Collection 2, Kiev, "Naukova dumka", 1969, p 37. 457. USSR Patent 304727 (1971). . ~ 458. ~Thornton, J. S., and Stanly, C. W., J. AGR. FOOD CHEM., Vol 19, 1971, p 73. 459. U.S. Patent 3413381 (1969); RZHKHIM, 3N650 (1970). 460. FRG Patent 1924083 (1970); S.A., Vol 72, 90621 (1970). ~ 234 ~ FOR OFFiCIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02109: CIA-RDP82-00850R040500040001-1 FOR OFFICIAL USE ONLY 461. U.S. Patent 3560596 (1971); RZHKHIM, 22N590 (1971). = 4~2. Prokof'~eva, A. Melnikov, N. N., and Vladimirova,~I. L., ZHOKH, Vol 41,~ 1971, p 1702. . ~ 463. Mel'nikov, N. N., Grapov, A. F., et al., KHIMIYA V SEL'SKOM KHOZYAYSTVE, Vol 7, 1969, p 55. 464. Grapov, A. F., Lebedeva, N. V., et al., AGROIQ3IMIYA, No 1, 1972, p 96. 465. U.S. Patent 3499964 (1970); RZHKHIM, 6N671 (1971). = 466. Unterberger, V. K., et al., Author's Certificate No 249399; IZOBR., PRrJM. OBRAZTSY. TOV~RN. ZNAKI, No 25 (1969); RZHKHIM, 18N625 (1970). 467. Bliznyuk, N. K., et al., Author's Certificate No 239946; IZOBR., PRfJM. OBRAZTSY. TOVARN. ZNAKI, No 27 (196g); RZHIQiIM, 21N559 (1970). 468. English Patent 1175220 (1969); R~HKHIM, ].SN349 (1970). 469. GDR Patent 77712 (1968). 470. Englin, M. A., et al.~ ZHOKH, Vol 38, 1968, p 869. ` 471. Unterberger, V. K., et al., Author's Certificate No 246957; IZOBR., PROM. OBRAZTY. TOVARN. ZNAKI, No 21 (1969); RZHIQ~IM, 17N595 (1970). 472. USSR Patent 298093 (1972); OTKRYTIYA. IZOBR. PROM. OBRAZTSY. TOVARAI. ZNAKI, ~ No 10 (1972~. - 473. Ferte, L., and Pecheur, J. PHYTIATR. PHYTOPHARM., Vol 19, No 3, 1970, p 113. _ 474. Morgan, P. W., et al., WEED SCI., Vol 17 (1969, p 353. 475. Martin,. G., J. AM. SOC. HORTIC. SCI., Vol 96, 1971, p 434. 476. Edgerton, L. L., and Greenhalgh, W., J. AM. SOC. HORTICC. SCI., Vol 94, 1969, ~ _ p 11. 477. U.S. Patent 3513233 (1970); RZHI~iIM, 6N672 (1971). 478. U.S. Patent 3467736 (1970);.S.A., Vol 72, 32027 (1970). 479. Danish Patent 118858 (1971); RZHKHIM, 24N650 (1971). 480. French Patent 2032006 (1972); RZHKHIM, 22N562 (1971). . 481. U.S. Patent 3481731 (1970); S.A., Vol 72., 32022 (1970). - 482.. Swiss Patent 499963 (1970); RZHI~iIM, 15N808 (1971). 235 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USF ONLY ' 483. U.S. Patent 3529041 (1970); RZHI~iIM, 11N653 (1971?. 484. English Patent 1183130 (1970); RZHKHIM, 22N710 (1570). 485. U.S. Patent 3416912 (I969); RZHKFiIM~ 9N683 (1970). 486. French Patent 1577278 (1970); RZHKHIM, 16N681 (1970). 487. U.S. Patent 3455765 (1969); S.A., Vol 71, 91654 (1969). ~ _ 488. USSR Patent 212179 (1966). 489. U.S. Patent 3511636 (1970); RZHICHIM, 7N725 (1971). 490. II.S. Patent 3553233 (1971); RZHKHIM, 18N626 (1971). 491. GDR Patent 71771 (1967). 492. GDR Patent 79180 (1969). ~ 493. USS R Patent 304725 (1971). 494. U.S. Patent 3462439 (1970); RZHICFiIM, 19N637 (1970). 495. FRG Patent 1924260 (1970); S.A., Vol 72, 90622 (1970). 496. FRG Patent 1925653 (1970); S.A., Vol 72, 79223 (1970). 497. Bliznyuk, N. K., et al., ?~uthor's Certificate No 239328; IZOBR., PROM� OBRAZTSY. TOVARN� ZNAKI, No 11 (1969); RZHICHIM? 4N713 (1970). 4g8. Bliznyuk, N. K., et al., Author's Certificate No4N715641970)BR~~ P~M. OBRAZTSY. TOVARN. ZNAKI, No 3(1969); RZHKHIM. 499. Bliznyuk, N. K., et al., Author's Certificate ~O 232972; IZOBR., PROM. OBRAZTSY. TOVARN. ZNAKI, No 2(1969); RZHKHIM. SN821 (19 ) SUO. U.S. Patent 3479418 (1970); RZHKHIM, 22N633 (1970). ' 501. Australian Patent 403186 (1970); RZHKHIM, 17N639 (1971). 502. Gladshteyn, B. M., et al., Author's Certificate No 230814; IZOBR., PROM� OBRAZTSY. TOVARN ZNAKI, No 35 (1968); RZHICHIM, 4N712 (1970). 503. Vliznyuk, N. K., et al., Author's Certificate No 222384; IZOBR., PROM. OBRAZTSY. TOVARN. ZNAKI, No 24 (1969); RZHKHZM, 17N594 (1970). 504. Bliznyuk, N. K., et al., Author's Certif~a~IM~ 19N578~(1970).' P~M� OBRAZTSY. TOVARN. ZNAKI, No 28 (1969); 236 FOR OFF'ICIAL U5E ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R000540040001-1 FOR OFFICIAL USE ONLY 505. Shj.tov, L. N., and Gladshteyn, B. M., Author's Certificate No 239953; _ IZOBR., PROM. OBRAZTSY. TOVARN. ZNAKI, No 12 (1969); RZHICHIM, 6N859 (1970). 506. Dutch Patent 130909 (1971)~; RZHKHIM, 19N735 (1971). 507. U.S. Patent 3442985 (1969); S.A., Vol 71, 22184 (1969). 508. Kabachnik, M. I., et al., Author's Certificate No 253063; IZOBR. PRpM. OBRAZTSY. TOVARN. ZNAKI, No 30 (1969); RZHICHIM, 22N650 (1970). 509. Japanese Patent 29497 (1970); RZHI~iIM, 16N678,i1971). 510. Grapov. A. F., et al., P;uthor's Cez'tificate No 274111; OTKRYTIYA. IZOBR. , PRfJM. OBRAZTSY. TOVARN. ZNAKI, No 21 (1970) ; RZF~iIM, 9N613 (1971) . 511. Arbuzov, B. A., in "Reaktsi'i i taetody issledovaniya organicheskikh soyedineniy," Book 3, Moscow, Goskhimizdat, 1954; pp 5-72. . 512. Grapov, A. F., in "Reaktsii i metody issledovaniya orqanicheskikh soyedineniy," BOOk 15~~MoSCOW~ "Khimiya"~ 1966~ pp 41-231. 513. Bliznyuk, N. K., Kvasha, Z. N., and Kolomiyets, A. F., Author's Certificate No 179316; IZOBR., PROM. OBRAZTSY. TOVARN. ZNAKI, No 5(1966); ZHOKH, Vol 37, 1967, p 890. 514. Baranov, N. K., Filippov, 0. F., et al., DAN SSSR, Vol 182, 1968, p 337; Author's Certificate No 209455; IZOBR., PRpM. OBAZTSY. TOVARN. ZNAKI, No 5 (1968). ~ ' 515. Bliznyuk, N. K., et al., Author's Certificate No ~37890; IZOBR.., PROM. OBRAZTSY. TOVARN. ZNAKI, No 9(1969); RZFIKHIM, 3N652 (1970). 516. Bliznyuk, N. K., et al., Author's Certificate No 255267; IZOBR., PROM. OBRAZTSY. TOVARN. ZNAKI, No 33 (1969); RZHI~iIM, 21N662 (1970). 517. Zinov'yev, Yu. M., and Soborovskiy, L. Z., in "Reaktsii i metody issledovaniya ~ organicheskikh soyedineniy," Book 21, Moscow, "Khimiya", 1970, pp 6-40. 518. GDR Patent 77712 (1970); RZHKHIM, 17N645 (1971). 519. U.S. Patent 3457303 (1960); RZHKHIM, 14N136 (1970); U.S. Patent 3457305 (1969}; RZHKHIM, 15N168 (1970). 520. Japanese Patent 4518 (1969); RZHKHIM, 4N750 (1971). 521. U.S. Patent 3472932 (1969); RZHIQiIM, 20N589 (1970). 522. French Patent 1558607 (1970); S.A., Vol 72, 90620 (1970). ~ 523. Prokof'yeva, A. F., Mel'nikov, N. N., et al.,~ ZHOKH, Vol 41, 1971, p 1702. . 23? . FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY 524. Japanese Patent 16202 (1970); RZHKFIIM, 15N672 (1971). 525, U.S. Patent 3459836 (1969); S.A., Vol 71, 81519 (1969). . ~ - 526. French Patent 1570485 (1969); RZHIQiIM, 11N892 (1970). . 527. U.S. Patent 3551563 (1971);.RZHKHIM, 21N652 (1971). 528. Japanese Patent 27098 (1970); RZHKHIM, 16N635 (1971). 529. English Patent 1197111 (1970); RZHKHIM, 7N670 (1971). . 530. Swiss Patent 495112 (197.0) ; RZHI~iIM, 1ON563 (1971) . 531. U.S. Patent 3577482 (1971); RZHKHIM, 23N583 (1971). - 532. USSR Patent 51739 (1970); RZHI~iIM, 17N593 ~1370). 533. Japanese Patent 12760 (1969); RZHKHIM, 1ON656 (1970). - 534. U.S. Patent 3555153 (1970); RZHKHIM, 20N634 (1971). ~ ~ 535. Japansse Patent 9316 (1969); RZHKHIM, 11N887 (1970). 536. r^RG Patent 1925763 (1970); C.A., Vol 72, 79221 (1970). ~ 537. Shcheglov, Yu. V., Gilyarov, V. A., Kabachnik, M. I., et al., Author's . Certificate No 298317; OTKRYTIYA. IZOBR. PROM. OBRAZTSY. TOVARN� ZNAKI, No 11 (1971); RZHICHIM, 24N747 (1971). . 538. Sotnikova, Ye. V., and Markova, N. P., KHIM. PROM., No 10, 1969, p 738. . 539. Bull, D. L., and Ridway, R. L., J. AGR. FOOD CHEM., Vol 17, 1969, p 837. 540. McBain, J. B., Hoffman, L. J., and Menn, J. J., J. AGR. FOOD CHEM., Vol 18, 1970, p 1139. 541. Schulz, K. R., and Lichtenstein, E. P., J. ECON. ENTOM., Vol 64, 1971, p 283. 542. Browmann, M. C., and Heroza, M., J. AGR. FOOD CHEM., Vol 17, 1969, p 1054. 543. Mel'nikov, N. ~N., Mil'shteyn, I. M., and Shvetsova-Shilovskaya, K. D., in "Khimicheskiye sredstva zashchity rasteniy," Moscow, Goskhimizdat, 1961, p 15. 544. Nagy, B., and Nadasy, M., NEHEZVEGYIPARI KUT. INTEZ. KOZ., Vol 3, No 3-4, 1970, p 185. 545. Yukhtin, N. N., Mel'nikov, N. N., et al., Author's Certificate No 239713; IZOBR., PROM. OBRAZTSY. TOVARN. ZNAKI, No 11 (1969); RZHKHIM, SN824 (1970). 238 - ~ FOR OFFICIAL USE.ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 . FOR OF'FICIAL USE ONLY 546. U.S. Patent 3515537 (1970); S.A., Vol 73, 35509 (1970). 547. Mel'IlikOV~ N. N., Khaskin. B� P?�~ et al.~ KHIM. FARM. ZHURN.i NO 5~ 1968~ p 8. ; 548. Khaskin, B. A., in "Novyye gerbitsidy" [New Herbicides], Moscow,."Mir", 1970, PP 189-237. ~ ~ . 549. Fest, C., and Schmidt, K. J., "Chemistry of Organophosphorus Pesticides," Berling, Springer Verlaq, 1973, 339 pp. ; ~ ; } i - ~ 239 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY CHApTER 29 HETERaCYCLIC CON~'OUNDS WITH TFIREE 1~ND MORE HETERpCYCI'IC ATOMS PER RING Derivatives of Six-Membered Heterocycles - ~ 8-Triazine Derivatives Despite the fact that research on the pesticidal properties of s-triazine derivatives � began relatively recently, there have been siqnificant successes in this area, and a large number of preparations' have found practical applicatia:~s in agriculture and industry. Triazines of the followinq types (XII-XVIII) are used aS pesticides (61): CI i~ ~ NIN N~N � Nl`^)N RN11," " \CI R'NH~ `N~~NHR R~N~ N' ~NfIR N xyi . xiti x~v - , OR" iR~ . N1N N^N ' I R'NH~ N~Nf~R R'NH' 'N NHR xv xvi ~ ~ I R' . N^N N~N . � . R~Nf~�.~ J~NIiR ~ RNH~~ l~N~ N ~ xv~i xv~u Compounds with qeneral forcaula XII containinq an aliphatic radical at ~he noncyclic nitrogen atom are inadequately stable, and t~~ey do not enjoy practical use, though they do have herbicidal properties. When this aliphatic radical is replaced by an aranatic radical the phytoc~.dal properties decrease, and the compound's funqicidal activity rises. The most active compound used aqainst plant diseases is 2,4-di- chloro-6-(2'-chlorophenylamino)-a-triazine (diren). Its isomers with halogen in other positions are less active. 240 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY Compounds with general ~or~nula XIII exhibit high herbicidal activity in the event that the hydrocarbon radicals at the� noncyclic nitrogen atom contain not more than four carbon atoms. When the length of the carbon chain of the radicals at the nitro- gen atom increases (>C4), the compound's herbicidal activity decreases. A similar 1gW iS observed with the series of compounds with general formula XIV. When a halogen atom is substituted by a hydroxyl group the compound loses its herbi- cidal properties completely, while substitution by an alkoxyl group (compounds with formula XV) or an alkylmercapto group (compounds with formula XVI), the compound's selectivity changes while herbicidal properties are retained. Compounds of this series exhibit optimum activity when the alkoxyl or alkylmercapto group contains - one carbon atom, though there are indications in the literature that compounds con- taining a carbomethylmercapto group (62,63) and some other groups (64) do have herbi- cidal properties as well. Substitution of the halogen atom by a 2-chlorallylmercapto (65,66), benzylmercapto (61) or benzyloxy group (68) causes fungicidal properties to appear. ~ 2-Fluoro, 2-azido (70-73), 2-cyano (75-77), 2-dialkylaminooxy (78) and 2-dialkylamino- mercapto (79) 4-alkylamino-6-alkylamino-8-triazines also have herbicidal properties. Herbicidal properties are possessed by 2-azido-4-methylmercapto-6-alky.lamino-s-tri- azines (69,74) and trialkoxy-s-triazines (80) as well. ~ Herbicidal properties are exhibited by diamino-s-triazines containing hydrocarbon radicals at the noncyclic nitro.qen of the most diverse structure, to include secondary (61,82) and tertiary (61,83,84) alkyl groups, unsaturated groupings (85-89) such as allyl (87), acetylene hydrocarbon residues (86,89) and polyfluoroalkyl groups (90,91) obtained in.the reaction between 2-chloro-4-alkylamino-6-aminotriazine and polyfluoro- chloracetones: : ~ CI CI ~ ~ CF~COCX,F ( N ~ \ \i \NF J\ /CF, t H N i, RNH N NHC OH . ~CFXz X = CI, [ir, F, SCN A large number of 2-chloro-4-amino-6-cyclopropyl-s-triazines and their 2-methoxy- and 2-methylmercapto- analogues (92-100) as well as 2-chloro-, 2-methoxy and 2-methxl- mercapto-4-alkylamino-6-alkoxyalkyl-s-triazines (101-104) and -6-alkylmercaptoalkyl- triazines (105) have been patented for use as herbicides. s~-Triazines containing heterocyclic radicals at the nitrogen atom have also been described (106,107). 2-Chloro-, 2-methoxy- and 2-methylmercapto-4-a~kylamino-6-(N-alkyl-N-acylamino)-s- -triazi.xies (109-112), cantaining (as the acyl group) carboxylic and sulfonic acid residues as well as residues of various derivatives of the acids of phosphorus, have been patented as herbicides. ~ A large number of s-triazines containing a nitrile group in the hydrocarbon radical at the noncyclic nitrogen atom have been described (113-118); some compounds of this _ class have enjoyed practical use (an example is the herbicide bladeks (121)). In 241 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 NUK UhMt(;IA1, u,~ UNLY � addition 2-chloro-4-hydrazino-6-alkylamino-s-triazines have been described in the literature'(119,1'?0), but they have not yet achieved practical use. Substitution of ane of the hydrocarbon radicals at the noncyclic nitrogen atom in diamirio-s-triaz:nes,by an alkoxyl group reduces the compound's stability and decrease~ its life, w,:ich may be af great practical interest in relation to some compounds f81). In~~oduction of imine nitrogen into the hydrocarbon radical at the noncyclic nitrogen atom of 2-chloro-, 2-methoxy- or 2-methylmercapto-4-alkylamino-6-alkylamino-s-triazines produces herbicidal compounds (108). . Compounds with general formula XIX have also been proposed as herbicides (122-124); compounds with general forn?ula XX possess fungicidal propert.ies (125-127). CCI~ NHAr ' ~ N^N N^N . R~%N/~ J~ R a/ Nl\CCI, N NCCH~C~I; xix xx R ~ R' = Alk Fungicides have been found among the N-oxyamino derivatives of aminotriazines also (128)� . In addition insecticides.(129) and insect sterilizers (130,131) have been found among derivatives of s-triazine.~ ~ 2,4-Dimethoxy-6-pentachlorophenylmercapto-s-tri.azine (melting point 162�C) has herbicidal action (132). ~ Derivatives of 8-triazine that have come into use as pesticides are shown in Ta.ble 49. ' 2-Chloro-4,6-bis-(alkylamino)-s=triazines may exist in three tautomeric forms; however, in most cases the equilibrium is shifted in the direction of the amine form XIII (133): CI I' l~H HN~~N _ N l~ ~ 'NH~ ' `NR ~ R~N~NH 'NR R'Nf1~N NfIR R NH xci xxt~ x~ii , . 242 ~ , FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 ' FOR OFFICiAL USE ONLY ~ Table 49. Derviatives of � Chemical NFUne Formula Synonyms 2-Chloro-4,6-bis-(ethylamino)- ~ CI ' Simazine, primatol-S, , -s-triazine I gesatop, G-27692 . N^N~ ~ ' )I ' C~HsNti~ `N ~NF1C?H` ; 2-Chloro~4-ethylamino-6-iso- i~ Atrazine, primatol-A, propylamino-e-triazine N ^N izapri.m, aatrex, ~ G-30027 ~ C=EieNFI~ `~j `NHCH(CH31~ I C~ . 2-Chloro-4,6-bis-(isopropyl- I Propazin, qesamil, amina)-s-triazine N^ N milogard, primatol-P, . ~ ~ Cr30028 (CH,),C}INH N NHCH(CH,~ . CI 2-Chloro-4-ethylamino-6- N~N Primatol-M, -tert-butylamino-s-triazine ~ GS-13529 C~HeNH~~,j ~NHC(CH,)i . CI . 2-Chloro-4-ethylamino-6~-di- ~ Gesafloc, trietazine, ethylamino-8-triazine Ni N~ ~ G-27901 JI~ ' ~ C,H,NH~ `N/ `N(C,Nf), ; ~ . 2-Chloro-4-ethylamino-6-(2'- CI -cyanopropyl-2'-amino)- Bladeks, tsianazin, N I N CN VL-19805, SD-15418 _ -s-triaiine ~ I ' C,HeNH~ `N ~NHC(CN~)= . SCH~ 2-Methylmercapto-4,6-bis- I Gi-bon, G-32911 - (ethylamino)-s-triazine N^N ~ C,tl~Nl�i~ N' ~NHC,N~ . _ ~ 2~+3 FOR OFFICIAG USE ONLY . APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFF'[CiAL USE ONLY - s-Triazines Used as Pesticides Solubil- ity in LDSp _ Melting Water, Vapor in Rats ~ Point, mg/ Pressure, (Orally)- �C /liter mm Hg mg/kg Use. Forms of Applicatiort and Consumption Norms 225-227 5 6,1 � 10'' S000 Herbicide controlling weeds in corn. 50,80$ ~ w.p.; 0.2-3 kg/ha. A total herbicide at 5-20 ~ kg/ha. Also used mixed with other herbicides. 173-115 33 3� 10-' 3080 Herbicide contralling weeds in corn, sorghum, sugar cane etc. 50,80$ w.p.; 0.75-3 kg/ha. 212-219 8;6 2,9 � 10-' S000 Herbicide controlling weeds in sorghum and carrots. 50 and S0~ w.p.; 0.5-2 kg/ha. ~ 177-119 8,5 1,12� 10-� 2160 Tctal herbicide; additionally used to control weeds in vegetables, corri, potatoes. 50$ ~ ~ w.p.; 1-3 kg/ha. ~ 102-104 ~ _ ~qgp Herbicide controlling weeds in potatoes and chrysanthemums. W.p.; 1-2 kg/ha. ~67,b-169 i71 1,6� 10-a 149-334 ~ Herbici3e controlling weeds in corn, potatoes, l~�~) soy. W.p.; 0.5-3 kg/ha. ? Fierbicide controlling weeds in rice; 0.5-1 81-82,6 4b0 7,1 � 10- ~.kg/ha. ACSp in fish, about 26 mg/liter. ~ . 244 ' FOR OI~'FICIAL U3E ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 FOR OFFICIAL USE ONLY Chemical Name " Formula, ~ . Synonyms 2-Methylmercapto-4-methylamino-~ SCH, � Semeron, desmetrin, ~ -6-isopropylamino-s-triazine I ~ G-34360 N^N ' - CI~i,NH~' N~NHCFI(CH~)~ 2-Methoxy-4-ethylamin~-6-iso- OCH~ Atraton, gezatamin, propylamino-s-triazine � Cf 32293 Ni N ~ . CzEIsNH~ `~j ~NHCH(CH~}~ � iCH~ ezapaks, . 2-Methylmercapto-4-ethylaaiino- Ametryne, g -6-isopropyiama.no-t3-triazine N ^N . G-39162 )I ' C~HbNf~l~N ~NHCH(CH,)z . OCH; 2-Methoxy-4,6-bis-(isopropyl- ~ ~ Prometon, primatol-0, amino)-s-triazine . N ^N primatol, G-31435 (CH,).Cf~INt~I~ `N ~NHCH(CH~), _ ~ ~ i CH, 2-Methylmercapto-4~,6-bis- Prometryne, gezapaks, -(isopropylamino)-s-triazine N ^ N caparol, G-34161 (CH~hC!-iNN~ `N/ `NHCH(CH~)z . . SCH, Terbutrin, igran, 2-Methylmercapto-4-ethylamino- preban, GS-14260 -6-tert-butylamino-s-triazine . N ^N JI~ . C~HaNH~ `~j `NHC(Cfl~), SCH~ 2-Methylmercapto-4-isopropyl- ~ Metoprotrin, metotrin, amino-6-(3'-methoxypropyl- ~ N~ N gezaran, G-36393 amino) -s-triazine (CFt,)1CHCH~ N/ ~NH(CH,),OCFI, " 245 FOR OH'FICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2047/02/09: CIA-RDP82-00850R000504040001-1 FOR OFFICIAL USE ONLY ~ Solubil- ~ ~ ~ ity in LD50 ~ Melting Water, Vapor in Rats Point, mg/ Pressure (Or.ally) . �C ,(liter naa Hg mg/kq_ Use Forms of Application and Consumption Norms &1-8~ 580 1,0�10'� 650 Herbicide control.ling weeds in cabbage. W.p.; . 0.5-1.5 kg/ha. . � , � r 9~t-96 1654 2,9� 10-~ l466 HeL~bicide controlling weeds in coffee, pineapple . and sugar cane. W.p.; 1-2 kg/ha. Total herbicide at 5-10 kg/ha. 84-86 193 8,4 � 10-' 1110 Herbicide controlling weeds in suqar cane, . carrots, pineapple. ~50~ w.p., 25~ e.c.; . 1-5 kg/ha. ~ 91-92 750 2,3� 10-' ' 2980 Herbicide controlling weeds in sugar cane. W.p.; 1-1.5 kg/ha. _ ! IS-120 48 � 10 � 10-~ 3750 Hexbicide controlling weeds in cotton, carrots, r.ice, vegetables. W.p.; 0.5-2.5 kc~/ha. AC50 in fish, above 23.6 mg/liter. 10�l-106 58 9,6� l0-' 2400 Herbicide controlling weeds in cereal grain - ~rops. W.p.; 1-2 kg/ha. ' 68-70 320 50pp Herbicide controlling weeds i.n cereal qrains and corn. W.p.; 0.5-2 kg/ha. ~ 246 " ' ' FOR OF'F[CIAL US~ ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 ~ ' ~ FOR OFFICIAL USE ONLY C~emical Name ~ Formula ~ ~ Synonyms , 2-Azido-4-ethylamino-6-tert- . . N~ VL-9385 -butylami.no-s-triazine ~ Ni N C,HaMH~ \N \NHC(CH,), , . N~ ' 2-Azido-4-methylmercapto-6- I Aziprotrin, mezoranil, -isopropylamino-S-triazine Ni~N brasoran, Ts-7019 )I CIi~S~ `~j ~NIICFi(Cf~~)s CI 2,4-Dichloro-6-(2~-chloro- ~ Diren . phenylamino)-s-triazine N ^ N ~ , CI/ `N \NHC61l~C1-2' ~ ; Utfoks, prefok, 2-Chloro-4-isopropylamino- ~ -6-cyclopropylamino-s-triazin N i N I tsiprazin JI / (CH~):CHNtI~ N/ \NH-{ I . . \ 2=Ethylmercapto-4,6-bis- iC'H, Sankap, kotofor ~ (isopropylamino) s triazine N~N (CII,),CHNH~ N~~NHCti(CH,), - SCH~ _ 2-M~ethylmercapto-4-ethyl- ~ ~ 5-18898 amino-6-,sec-isoamylamino- ~ N ^N -s-triazine ~~~.~6N f~/ N/~NIiCbEi~~-u3o ~ 247 ~ . FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 FOR OFFICIAL USE ONLY Solubil- . , ity in LDS~ M~elting Water, Vapor in Rats Point, mg/ Pressure, (Orally) �C /liter mm Hg mg/kg Use. Forms of Application and Consumption Norms IUI-10~1 72 7,4 � 10-' 460 Herbicide controlling monocotyledonous annual weeds in cereal grain. W.p.; 1-3 kg/ha. 91--93 75 - 5833 Herbicide controlling weeds in cabbage. ~ W.p. ; , 1.25-3 kg/ha. - 155-157 - - 2710 Fungicide controlling potato and tomato diseases. 50~ w.p. Liquid _ _ a10_12~ ~Selective herbicide. E.c.; O.C-2 kg/ha. I~~1- IINi 16 5000 Selective herbicide W.p. ; 1-2 kg/ha. 151-153 50 - 500p Selective herbicide. Usedmixed with 5-19490 - � (O,US) in rice crops. 22 3uK. tl:l: . 248 ~ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 ' FOR OFFICIAL USE ONLY ~ Only two tautomeric forms.XXIII and XXIV are possi.ble for 2-chloro-4-dialkylamino-6- -alkylamino-s-triazines, while only one amine form XXV is possible for 2-chloro-4,6- -bis-(dialkylamino)-s-triazines.: ' . CI CI i~ N I N N/`NH N^N l` ~ ~ l` ~J R,N~ N~~NHR R,N~ ~NR R,N~ N/ ~NR, xxiii xxtv xxv These groups of compounds also differ in physical properties. 2-Chloro-4,6-bis- . -(alkylamino)-s-triazines are predominantly solid crystalline substances with high melting points and.poorly soluble in water and in organic solvents, while 2-chloro-4, -4,6-bis-(dialkylamino)-8-triazines have a low melting point and are soluble in many organic solvents. 2-Chloro-4,6-bis-(alkylamino)-8-triazines are stable when stored at room temperature, and they can be stored~~practically indefinitely without change. When heated with water, especially in the presence of organic or inorganic bases, they hydrolyze to inactive oxy compounds: CI . OII ~ Ni N N^N - RNFt~ \NHR + H20 RNH~ N/ \N1~IR + HCI The halogen atom may also be substituted by other groups; thus when these compounds react with metal alcoholates,.the appropriate 2-alkoxy-4,6-bis-(.alkylamino)-3-triazines form, and when they react with mercaptamides, 2-alkylthio-4,6-bis-(alkya~tino)-s- -triazines form: . . ~ ~ - XR' . ^ . N: I N Ni V J R'XNa _NaCI ~ ~ RNIi' l N ~NIIR I~~II~~I N~~NH(t ~ X = O, S ,Both of the groups of compounds formed as a result are valuable herbicides. , 2-Chloro-4,6-bis-(alkylamino)-s-triazines are obtained with good yields by reacting cyanurochloride with amines. If both amine groups contain identical hydrocarbon radicals, the reaction is performed in a single stage: = 249 FOR OFF[CIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2047/02/09: CIA-RDP82-00850R000504040001-1 FOR OFI~'[CIAL USE ONLY � cl . ~ cl ~ N I N ~ N~N CI~N' ~CI + 2RNF(z _sf~C~T RNH~ \NI-IR But when the radicals in the amino groups are different, a two-stage process would be suitable. In the first stage one of the amine molecules is made to react, forming 2,4-dichloro-6-alkylamino-8-triazines; one molecule of the secondary amine is then attached to the latter. Both inorganic and organic bases or excess amine can be used as the hydrogen chloride acceptor. This reaction is at the basis of industrial acquisition of 2-chloro-4,6-bis-(alkyl-~ amino)-s-triazines (134-137). In this case if the target compound is symmetrical 2-chloro-4,6-bis-(alkylamino)-8-triazine, the reaction may be performed in a single stage, using sodium nydroxide or some.other inorganic base, including ammonium, as the hydrogen chloride acceptor (136). , ~ The cyanurochlor~de required for synthesis of substituted triazines is obtained by ~ . polymerization of cyanogen chloride: . ~ � N^N ~ ' � 3CICN ~ ~ _ J~~, . The reaction is performed in the presence of activated charcoal at 350-400�C, or in a liquid phase under pressure in various organic solvents using, as the catalyst, anhydrous alumintun chloride, boron fluoride, hydroqen chloride and so on. The basic flowchart for production of cyanurochloride is shown in Figure 20 (138). 7 ~6 5 _ . j,, 2 4. ' . HCN ~ g CIZ 3 9. Fiqure 20. Basic Flowchart for Production of Cyanurochloride: 1--column for acquisition of cyanogen chloride; 2--column for regeneration of ~ FiCN; 3--cyanoger. chlaride dryinq column; 4--reactor for acquisi- - ~ tion of cyanurochloride; 5--cyanurochloride collector; 6,7,8,9-- devices allowinq for :atalyst (activated charcoal) replacement ~ 250 � FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 FOR OFFICiAL USE ONLY C~anurochloride may also be obtained by the action of phosphorus pentachloride on cyanuric acid (the yield is 55-59 percent, while when cyanogen chloride is subjected to polymerization, the cyanurochloride yield is more than 90 percent of theoretical): a OH CI ~ ~ N^N rci, N^N oH~ J~oF~ ~ ~~~N~~~~ When methylrhodanide is chlorinated, the cyanurochloride .yield is 85 percent, but it is difficui~ to remove other chlorination products from the target compound. Pure cyanurochloride is a white crystalline substance with a melting point of 146-147�~ 146-147�C, it is practically insoluble in water, and it is.freely soluble in most _ organic solvents. It is readily hydrolyzed by water, transforming into cyanuric . - acid. Hydrolysis proceeds especially quickly at high temperature and in the presence of bases. This must be considersd when using cyanurochloride to synthesize substi- tuted triazines in an aqueous medium. In the presence of bases, cyanurochloride reacts with many cor,pounds containing active hydrogen. Gaseous cyanurochJ_~~.i.de formed out of cyanogen chloride upon trimerization in - charcoal cataly~~t ~~ay be used to obtain symmetrical chlorotriazines; cyanuro- - chloride is passt~', through an aqueaus solution of amine and sodium hydroxide (134). The formed chloroaminotriazine is filtered, washed with water and dried. This method can be used to obtain simazine (Figure 21) and propazin. Other triazines . obtain~d by this method are low in quality because they contain a large quantity of related compounds. This process can al~o be employed to obtain symmetrical fluoro- triazines, using four moles of amine to every mole of cyanuroct~loride (134). In this case the process is carried out without adding sodium hydroxide, and the amine is regenerated iz~ the next stage. ~ Acquisition of asymmetrical triazines may be demonstrated with the example of ' atrazine: CI I c,Fi6Nti~ I ~2so C ~~,Nn, N~~V 2. Na0lI N~~N t. N~~~~ ~ ~ ci 1.~~~~ ~,:-L J~.rv~ic,i~i, N (:I ' ~ . - N~~N ~ - ZSO-C,FI,NI1~~~ ~~NfiCtt(b ~ . . 251 FOR O~FICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-04850R000500040001-1 FOR OFFICiAL USE ONLY _ ' g 9 - ~ Z � (1) 6 (L~yx JZ IJ u~aNyp- .znopud � ~ ~ (3) aoNo- 3 ~m~c~aMUN ~ ~4 ' . . _ S ~ (2) Boda 7 � Figure 21. Flowchart for Production of Simazine Out of Gaseous C~ianuro- chloride: 1--ethylamine gaging tank; 2--sodium hydroxide solu- � tion gaging tank; 3--reactor; 4--centrifuge; 5--vat for dis- , tillation of ethylamine from mother liquor; 6--cooler; � 7--container for~acquisition of simazine pulp; 8--calorifier; 9--spray dryer; 10--spray disk; 11--cyclone; 12--dust filter Key: - ~ 1. Cyanurochloride 3. Monoethylamine � 2. Air . These reactions are easily performed even in the same apparatus, since the second reaction proceeds at a higher temperature than the first. It has been sugqested that in some cases the reaction of abtaining asymmetrical - chloroaminotriazine should be carried out in a mixture of water and an organic solvent that is immiscible with water. In this case the 2,4-dichloro-6-alkylamino- triazine formed in the first stage moves into the organic solvent, which reduces - the possibility of its hydrolysis by water and its interaction with the second amine molecule. Chlorobenzene, dichloroethane and a number of others have been recommended as organic solvents. The reaction with the second araine as a rule results in a product poorly soluble in organic solvents and readily filtered out. A flowchart for acquisition of atrazine is shown in Figure 22. It should be noted that owing to high persistence, production of symmetrical - fluorothiaZines such as simazine and propazin is continually decreasing. These compounds are being substituted by less-persistent preparations--primarily various 2-methylmercapto-4,6-bis-alkylamino-s-triazines as well as the corresponding azides. The latter can be obtained either'by an exchange reaction between the appropriate _ chloride derivatives and soelium azide (139) 252 ~ ~ FOR OFF[CIAL USE ONLY ' APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2047/02/09: CIA-RDP82-00850R000504040001-1 - ~ FOR OFFICIAL USE ONLY . ~c,N,ci, ~ 1 Z ~ 3 ' ~ ~ Z � . 4 7 5 6 . Figure ~2. Flowchart for Acquisition of Triazine: 1--amine gaging tanks; 2--sodium hydroxide qaqing tanks; 3--reactor for obtaininq 2,4-dichloro-6-ethylamino-s-triazines; 4--reactor for atrazine acquisition; 5--filter; 8--dryer; 7--atrazine collector CI Na . ~ N I~N NaN~ N^N l /J -----a ~ ' R'NH~ Ni ~NFtR -NaCI R~NH~~ ~ ~NfiR or by reacting the appropriate hydrazides with nitrous acid at 0-5�C (140): . . NI�INt(~ , N~ ~ _ � ~ i N r,.NO,; H� N^N , J~ ~ R H}( N NtIR R'Nfl~ N/ ~Nf1R - 2-Methylmercapto-4,6-bis-(alkylamino)-s-triazines may be obtained~ as.was indicated earlier, by reacting methylmercaptide with 2-chloro-4,6-bis-(alkylamino)-s-triazines _ (141). This reaction proceeds both in an aqueous medium and in organic solvents. According to the patent literature, when isopropyl or see-butyl alcohol is used as the solvent, the y~.eld of the end product may climb as high as 98 percent. The reaction proceeds at 70-75�C (141,142). In another interesting method, 2-methylmercapto-4,6-bis-(alkylamino)-s-triazines are obtained as follows (14~): 253 . _ FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00854R004500040001-1 FOR OFF[CIAL USE ONLY - NH � C~ SCNIiz � tlCl . _ N I~N INHz1aC5 N I N F~s�_ I ~ R'NH~ u~~NIiR ~ ~ % ~ ~NtIR ~ ~ nti~ ~ J . sti � sci t, ~ ~ ` N~~ ~at,?:so~ N^N ~ ~ , 'NI1~ ` ' \NFIR R NH N N}la R N The merit of this method is that it does not require acquisition of inethylmercaptan. However, the process consists of many stages, and it requires the use of toxic . dimethylsulfate and rather expensive thiourea. A si.mpler method of obtaining 2-methylmercapto-4,6-bis-(alkylamino)-8-triazines is to react 2-chloro-4,6-bis-(alkylamino)-s-triazines with a mixture of sodium sulfide and sodium polysulfide: ' . . . ~ . a N^N 6NazS + 9S GNaOH ( ~ R'NI1~ ~~Nt1R . SNa~ I g N~N 8NaC1 Na~S~O, 3fi20 ~ R'NIi~N NHR � The reaction proceeds relatively easily in an aqueous solu~:ion at high temperature. The resulting sodium salt of 2-mercapto-4,6-bis-(alkylamino)-s-triazine is easily transformed, without separation, into 2-methylmercapto-4,6-bis-(alkyalmino)-s-triazine in response to the action of dimethylsulfate. The yield of the sought triazine - exceeds 90 percent of theoretical. However, intermediate 2-mercapto-4,6-bis-(alkylamino)-s-triazine can also be obtained by oxidation~with mineral acids; in this case the final 2-methylmercapto product is completely free of initial chlorotriazine impuzities. This method requires simple apparatus, and it provides a sufficiently pure 2-metYiylmercapto compound (148). Moreover 2-methylmercapto-4,6-bis-(alkylamino)-s-triazine can also be obtained by ' the followinq pathway (144-147): 254 FOR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 - FOR OFF[CIAL USE ONLY C~ SCFI~ N I N cH,sii N I N HNiis: Nat)tl II - C'~N~~C` (base) .T Cl~~ J\CI SCf~~ i Cli~ N ,~N e�tVt1~: NaoF~ N~~N . ~ CI~ `N/ ~NHR R�N!i/ N' \NFIR . The process may be carried.out in both an aqueous medium and in a mixture of water and an immiscible organic solvent; either alkali or organic bases can be used as the hydrogen chloride acceptor. There are indications that the entire series o~ the transforniations described here may be carried out within a single reactor, in which individual stages of the reaction are perfozmed in succession (146). - As was noted earlier, 2-alkoxy-4,6-bis-(alkylamino)-s-triazines may be obtained by the action of alkali metal alcoholates upon the appropriate chlorotriazines. The reaction proceeds most readily in organic solvents at high temperature. Most substituted s-triazines are sufficiently stable at room temperature, but when heated to 240-250�C, they undergo dealkylation to form olefins (149). It has been established that the principal pathways of inetabolic transformation of triazines are: hydrolysis (in whieh halogen atoms and alkoxyl and methylmercapto qroups are Y split off), dealkylation at the noncyclic nitrogen atom, and splitting of the ~riazine ring; these reactions proceed at different rates in dif�erent media. It is believed that hydrolysis is catalyzed in plants resistant to chlorotriazines by 2,4-dioxy-7-~ethoxybenzo-l,4-oxazinone-3 (151,156). , CI1,0 /OH . ~o . ~ ~ bf~ . ~ ~ ~ ~ The metabolism of prometryne is an example of this (see diagram on p 252). In addition to the s-triazines described above, a large number of other compounds of - this series with pesticidal properties have been synthesized, particularly 2-chloro- -4-dialkylamino-6-dialkylthioamido-s-triazines, which have fungicidal properties (157). ~ Among the hydr~ted derivatives of s-triazine, mention should be made of the deriva- tives of tetrahydro-8-triazine (158,159) and 1-ary1-4,6-diisopropyl-3,5-dimethyl- hexahydro-s-triazine (160), which have herbicidal properties, and a nu~nber of - other derivatives of.hexahydro-8=triazine possessing insecticidal and fungicidal properties (161), though they have not as yet achieved practical applications in this direction. Various products of cyanuric acid that are easily obtained by thermal cyclization of urea should be included among the derivatives of hexahydro-s- - -triazine: 255 ~OR OFFICIAL USE ONLY APPROVED FOR RELEASE: 2007/02/09: CIA-RDP82-00850R000500040001-1 APPROVED FOR RELEASE: 2407/42/09: CIA-RDP82-40850R000500440001-1 FOR OFFICIAL USE ONLY � z ~ ? z z_~ = z=~ . o~~~Z ~ o-~ ~ z ~ z z z z � Z T~. T z � , - z o u z~ ~ _ ~ ~n . ~ z ~ v ~ w ~ z ~ y . ~ q h ~ / z Z ~ o--'~~ ~~z a~'i z z~ ~z \ a _ ~ ~ i O-Z ~ Z c~i N . T . Z 'd ^ ~ Z N'-~~'~ ~ z~ z ~ U Z ~ x U ~ z . u ~ z=~ . ~ ~ \ //z ~ I z ~ . ~ ~ V , : z = U Z ~ ~ ~ Z Z V V -Z~ - ~ ~ ~ � p-
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