SCIENTIFIC ABSTRACT RAZUVAYEV, G.A. - RAZUVAYEV, G.A.

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December 31, 1967
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SCIENTIFIC ABSTRACT
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Tiff, reaction of radical cleavage front completely stivni I fric derivatives cyf Ills I- A, Kipsivm , W f Im ki Stat'. I /k.,. I "It, 4,1 h h.- : I k hrm - 21. 111111 INHOW. I laf-Jr, --'t, I'mm. 15. 91(1919-; C.L. 43. 1571w N."t.. "t Fls,,Ph~ -illi CCI.. ClICT, I Nt.l )I I m Alca- pr-q-4-d 111T."ligh It-a'ag"d Ill.- I'llf...11ral Ifiril frar1% will) Iliv u)lvq-llf Vicifliflig. Ff.%p . MR1, C411.. (*,I[, Iffl- wrtf. i-h-tilifi"I dl~r iiitratimi,. Flw r,.., tm- -- rim 111) Ill b-. fit addiv t,, Ow A-v 1--in. 1,. the CIICI; Fe.41111118 Mill. al.) K.1%1' ttl ill.& VI-1111. -1111 .1 tlli\l J I:t,sli .11141 Ftvmcl.. ShiliUrIv. CO. al., K.,%. it. 111-1r lilid. %fillir Et,;fICI, itaf C,Cl.. aml a llttl,- I'll SA 1, Ill. fiW. MeMl Save -111, inrullir Sit. 01,0, Ilt,l j Ft'sli-Ph"ifiFl. Inixt.. as %VOI a, all ill.d. .40. 1N-1111%. 1:1 Slill )~ Rractioll of file lt\IK.X ff'.111 .4.5 It NIK ;.... I It I g I1IjCIf,CI with 20 11. Ph.,SisCl, rate 92,", I'll'sm Cl I -I'll , .1 vull- A. (1,': 1.:.'71. whi, If %,a, tjI.j,-vt,A to irradiati-, it. %.irmis- m)lvrnt, (or Of-1111, Itr% a% alwiv,-. [it CIICI. th,fr ,-r, b,irm"I C.114, and (PhClf-,~SuClt. sit It'W (All"; . Iml ,,,, hilwilryl "fuld fir isolalvd. In CCI, %%rrr forntrif C.11.. 'I'licilmit-sliclo, and imur tillmn't"I 'L"tilig I'murial It, till. WN; N,IV. 110 X.." 'm md 'jW'. 01hCII:,k-slICI" Ill. 10'. fluating Ph.'sill Cl I -I'll t2 X.; ith 0.02 It. mscinimid,- fit 1711* ga~r I$.-, it ""d "Itall att.1'. ,( (1-1101,14;nCl, .,fit llh.,;uCl. A.,th Aflt-r trratment M thr rr,idur, with ale IICI . %-I,r-t-4frciniTrli.Jc in thr t.1k)vr -actiors in CIICL fr- lluxt,l 11-5 fir. f flair Phllr and %uti-inimi4h . "hile the r-tiltir fifth a1c. IICI ga%t- mir I HiCII, G \I K USSR/Chemistry - Organomercury Compounds, Jun 51 Free Radicals "Free Radicals in the Decomposition Reaction of Benzene Azotriphenyl Methane, Nitroso Acetanilide, and Benzene Azotrinitromethane in Solutions," G. A. Razuvaev, E. I. Fedotova, Gorlkiy State U "Zhur Obshch nim" Vol XXIJ, No 6, pp 1118-1122 Proved formation of phenyl radicals in decompn of benzene azotriphenyl methane in CCI4 soln by fixa- tion on metallic Hg. Phenyl mercurichloride is sepd from reaction mixt. Phenyl radicals formed in decompn attach themselves tc diphenyl tin added to the mixt, forming heocaphenyl distannate., Upon 186T25 USSR/Chemistry - Organomercury ComDounds, Jun 51 Free Radicals (Contd) heating of CC14 soln of benzene azotrinitromethane in presence of diphenyl tin, the latter.is phenylized to tetraphenyl tin. In decompn of benzene azotrinitrometbame in various org solvents the usual products assocd with appearance of'the phenyl radical, viz. diphenyl in benzene-soln, benzene in ethyl cellosolve soln, chlorobenzene in CC14 soln, are not found. Nitrophenols are formed regardless of the solvent used. 186T25 RA71~!AE-7) ;AI USSR/Chemistry - Organomercury Compounds Jun 51 "Photoreactions of Oreanic Hg Compounds in Solu- tions," G. A. Razuvaev, Yu. A. 01'dekop, Gor'kiy State U "Zhur Obshch Khim" Vol XXI, No 6, pp 1122-1124 Photoreaction of diphenyl mercury with ethyl bromide isopropyl bromide, and chlorex (b1s+chloroethyl ether) forms benzene and phenyl mercuribromide or chloride. Diphenyl mercury and chlorobenzene upon exposure to light form calomel. In photoreaction of diphenyl mercux-j with bromobenzene, phenyl mercuribromide is obtained, and p-bromodiphenyl is found in reaction products. 186T26 jo - Tho PIMtorewelm Of MOUUodrpak cowp~ads ot mer. cury in sulatim. VIL The - 11, ad diphoullmorcury. 6- A. Raxuv~v and Vu. A. Oldektm. J.Geo. (A~, S.N. 23, 1225-WI931XFngl. trunalatkni). Sre C.A. 46. A Way. It. R. %0 Pi USSR/Chemistry - Organic Mercury Jul 51 Compounds "Interaction of Certain Organic Mercury Corpounds~ With Succinimide," G. A. Razuvayev, Ju. A. Oldek% N. S. Vyazankin "Zhur Obshch Khim" Vol XXI, No 7, pp 1283-12-87 Dipbenyl, o-didolyl, diethyl,+dinaphthyl, and 3-dinaphthyl Hg all reacted with succinimide to form RESN(COCH2)2 compds (prepd for 1st time),which are well-crystd colorless substances, sol in H209 interact with HC1 and KI to forri corresponding 191T26 USSR/Chemistry - Organic Mercury Jul 51 Compounds (Contd) Mig x Hal compds. With H2S phenyl- and 0-totylmer- curysuccinimide form diphenyl- anC 0-ditolyi-Hg, resp, while oL-naphthyl- and ethylmerc-urysuccinimide fom sulfides (RHg)2S. Dibenzyl HS with succinimide yields dibenzyl and Hg. 191T26 C A / J The reaction of some organomercury compounds with Succinimide. C,.A. HAzuw.i". Ytt A I WilAty..ind N S. I va.inkin .1 C-i. CA-, ) % N R 21. 1 013 ~ 1161 1 F"Cl 1--hiv.- S- ( 1 4r, P-7.4 It R USSR/qhezistry - Organic Ant Iimony and Nov 51 Mercury Com~ounds ,.ItPhotoreactions of loloorganic Compounds," G. A. Razuvayev, M. A. Shubenko, Gorlkiy State U "Zhur Obshch Khim" Vol XXI, No 11, pp 1974-1979 Conducted following photoreactions, Bz2ITg and Me2ffa with C6H61 and Bz2Hg with Mel in MeOH and CA solns; Et2Hg with C61~61, and Ph2Hg and Ph8_2 w'th BL-1 in Ke0H solas; Ph3Sb with C6H6I 'a C6H6, and CHCl 31 solas' Described respective reaction products. Proposes mechanism of all 194T45 USSR/Chemistry - Organic Antimony and Nov 51 Mercury Compounds (Contd) reactions, based on photolysis of org I compds into at I and free radical; studies their behav- ior further. 194T45 U~~/Chemjstry - Organic Mercury Dee 51 Compounds "Photapeactions- oi Mercury_0,j-g&-tjc.. Compounds in Solutions. VIII. Reactions In Mixtures of Sol- vents," G. A. Razuvayev, Yu. A.'011dekop, Gorlkiy State'U "Zhur Obshch Khim" Vol )=, No 12, pp 2197-2199 Investigated photoreactions of Ph2Hg with follow- ing mixts: CC14-MeOli, CC14-ethylcellosolve, CC'3-CC'3-MeOH, CC12CC12-MeOR, and EtBr-MeOH. Foulid-thAt radicals formed by -ohotolysis react in 194T67 USSR/Chemistry - Organic Mercury Dee 51 Compounds (Contd) follov;lng manner. PhHg radical takes halogen from halogen-contg component of mixt, forming PhEgHal, vhile Ph radical adds H. 194T67 Vm V) Gr' A 1"iteactiolls- of c-arbon tetracillocida With alcLiholi'O.- A. CCI, unit 17 cc.'IMOZI was stuntarly procesFednul t1u. proul-I 7 11 V fl e V a I ld N V 'U, i I L Staul ucts of rtaction were CII,CI, 11,0 nrid hji4O, IrgCI (0.K5 K Duklady Akad. Nauk S.S.S. M. 80, ,,,-72( R;iT.Mrin RULER~t ki CI 10 (2A4 g.), Of X I Sold IICI (0.2 g'. ot phol"reactioll-, of 111clalindrg. compt.15. in mixts. of 2 Later truit, indiciled that tile reactiolilietw(,clt MeOll alui- SoNtras, title of 1011ch C4111111iln. Iningen and tile ollict (I"es CUtprocteded %vidn-ut IthrcoujinN, 111, incrtly warming the Onot, in iutercsfisiK reactiun was diACAMed 10101 Tesillttd- ceitullonents, 2 CCI, +~ McOl-f -4 2 CIICl% + 2 IICI + in the follawin: each It )r RIlIg raCical reactud by split- .11C110, then NIWII + 110 --~ 11:0 + MeCl, and IICIIO ling offart atom of 11 front tile nonhalogen solvent, but the I Uct RFIL r!alical rmmted -.-;itli the halo&en-contg. solvent with + 2 MeOH ~ CfltOfkfe~ + H20. A scries of reactions c tile formatior of 11 llgX. -7 hua, IlgPhj in MeOH soln. with - also occurred in the preicnce of Ilg compds. llgCI realted CCI, 'ni exposure to ultraviolEt light gave PhHgCl, withCCltoformHgCItaudC~CJ.. Ales. (hie, Ht. PIICH,), 11CHO,audC20s. When IfgPhz in MeOlf was exposed to were dehydrated upon heating with 11 Cl, with the foruja- 1 9 ultraviolet light, C,V, and HCHO Avere formed. With tion of esters, and the reaction went more smoothly with ow CO,, HgPii, rcucted similarly oil exposure with formation of large amts. of HgCl:- and at increased temps. As sh i n~- PhHgCI, MCI, ard CCl. while upon heating tile reaction in the tests, ~ E-:tOH and PhCHIOH also gave esters. upon was not observed. It apprars probable that radicals are heating-mith HgCl-. PhCH-OR with CCll; nye PhCHLCl, formp.d in the thcrinal ritctiov of jIgphs will, Meoll W1,1ch dibenzyl ester, PhCHO, CHC13 Lind water, as well as con- can react with Mo. HjPh2 (2.0 g.) in 15 cc. MeOk were siderable quantities of resinous products. It is possible heat"Ll in as"ed tube ivi .th 15 cc. CC4Pt 200~10* for2i) brs. - that in the reactions with ales. the CCh radical was formed, vh1ch split off H from the a1c. A mixt. of MeOH (20 cc.) The reacOon mixt. Uter heating stpd. into 2 layers, watrr- v with CCh (20 cc.) on 14-day exposure to a Hg quartz lamp sol. combustion Kases which werf condensed to liquid upon co6ling, and 1.1 g. Hg ht bottutu of ube. The top HtO gave laminated mixts. The lower layer gradually enlarged layer contained IICIIO =d tile nortaq. layer contained and finally remained const.,(14 cc.). Thit,photoreaction: CLtC~1, --aiLd CCI,. A soln. of I g. H&Ch in 10 mi 7 _Gfv RIA-Z-1-)VAG, produced much HIM The reaction mixt. Was processed' Willi JIM, t1w tflosola. contained 0.32 g. HCHO and 2.10 g. i1cl; t lie imuml. layer consi3tcd fif a soln. of 2.4 g. CICI# in -CU,. fh~ thermal reaction aud plinjoreaction are sharply 9 lit the photoreaction tim pnxess also in- clude. I- reaction: Meoft + 2 Cl. - HCHO + 2 IICI. MeCl"_- not fi,ruscd, but laj ge Quantities of IICI are formed; the &-line diffmal;r. twvur.~ ill the behavior of the CCI, radi- cal ill the thermal process, is the rcaction procccds by re- moval of the H frout the a1c., but in the pbotoreaction di- nicrization takes place. The differenm lit the reactions with temp. change is marked for-other radicals such as Me ~~)r 13t. At lower temps. (lie dinterization reaction prevails but at higher lumps. (lie reaction of the radicals with other inols. aud roactious of disprop ,ortiouatiou prevail. , lit the thermal reaction the radical CCL partimlly~ ditnerizes tit C:C[&. which cau ill turn re-act with McOfl. ~ ClICh is not found ill the reaction products When NUOR is warinctl With C~Cl. ill a scaled tube at 200-20. IICI 10, AlcCl, and CCll,-CCl,l are obtained; therefore the reactiii is: C" + WWI (CI,C)2 + 2 IICI + 11010. F.. S. N-Pheny[mercurisucciniml le. G.A. Razuy -I'l N. S. Sq .~~ __F ~.". -7 % Akild. N' It', ( -~. Suedinrni.'. Sburnik 2. 136-7(195,I)-liltring :1.13 K. Pjljllc~ UFO :1 g. succillimide te, !:;5-40" with con- cvz~' tirluou, dktu. of Ul, Yidd, a residne of 90.4% PhFIgR r" c _(R = succininnido), m. 199-3' (Front 11.0). Similarly are l obtained: E., anal"". 8717, in~ 121 '; n-lolvl riwdq, 841-70, - In. l7s'; 1-napkilly! avvzh!'~' 63%, 111~ I'M'; 2-wipAtItyl ,,;:,.,,',,,,. .57~,~. tit, 221~ 2': sit. I.n.11,614YI alwh,.. 1'52 G. 'NI. Ko-lapoll USSR/Chemistry - Polymerization; Jul/Aug 52 Peroxides "New Polymerization Initiators," G. A. Razuvayev, Yu. A. Olldekop,.Ye. 1. Fedotova, Gorlkiy U "Uspekh Khim" Vol XXI, No 4, PP 379-421 Reviews foreign work on the siibject (101 refer- ences). Araon USSR contributions to this field wreferences~, mentions invest'igation which es- tablished that hydroperoxides of tertiary ales are extremely effective in promoting emulsion polymerization of 1,3 butadiene; comparison of rates of Aecompn of tertiary ale hydroperoxides at various- temps in alpha -methyls tyrene; study of the'effect of those peroxides on polymerization of Styrene In the liquid phase; initial work by A.A. 'Berl1n, A.A. Moiseyev, and F.Kh. Abel' on the use of azpnitril6a and azocarbo lic acid esters as polymerization initiators YthLe reference on this is apparently to a 1948 USSR patent applicatics-7. US=/Chemistry - Organic Mercury Mar 52 Coupounds "Photoreactions of Orysnic Mercury Coupounds in Solutions. X. Reactions of Dimethyl Mercury," G. A. Hazuvayev, Yu. A. 011dekop, Z. N. Manchinova, Gorl- kly State U '*Zbur Obahch Khim" Vol XXII, No 3, pp 48o-483 Dimetbyl mercury (1), in photolysis, splits into the radicals CR3' and CH3 Hg; the reaction proceeds as in the case of aryl mercury compds. When ex- posed to ultraviolet rays, I reacts with CH30H to form CH4, Hg, and CHCHO. In photoreaction with 209T45 USSR/Chemistry - Organic Mercury Mar 52 Compounds (Contd) CHC1 it yields methyl mercurichloride, CEE , and hex0h1loroethane. In soln of CH I when e)jsed to light, it forms methylmercuriio2L and CH4- In CC14, upon exposu:re to light, it reacts to form metbylmercurichloride, CH3C1 and hexachloroethane. C"I OH and CC141 it Dur,jng photoreaction in soln of CH3 f ~. .1 the radicals CH Eg. and CH3' which react with vaIr,ious components of3the soln. The former yields metliy1mercurichloride in reaction vith CC1 ) the latter forms CH4 in reaction with the CH304. 209T45 :4 USSR/Chemistry - organic Mercury Compounds A&r '52 "Reactlons of Diphenyl Mercury With Metal Chlor- ides, In Which No Stable Metalloorganic Oompounds ,Are Formed'" G. A. Razuvayev,. M. C. Fedotov, ICbair of Ora Chem. Gorlkiy State U "Zhur Obshch Khim" Vol XXII, No 3, pp 484-489 Diphenyl mercury in ethyl cellosolve or dioxane soln, when heated with cobalt chloride or iron chloride, yields phenyl mercurichloride and benzene as a result of the reaction between the phenyl radical and the solvent, With the saw solvents, 209T46 USSR/Chemistry - Organic Mercury Mar 52 Compounds (Contd) upon heating with cupric chloride, it forms phenyl- mercurichloride, chlorobenzene, and cuprous chloride. On heating in morpholine soln with FeC'31 CuC12, or CoC12, C6H6 is formed and metallic Hg separates. The reaction proceeds on account of reducing pro- cesses which take place upon heating of complex me- tallic chloride salts with morpholine. 209r46 USSR/Chemistry - Organic Mercury Compounds Apr 52 "The Reaction of Mercury-Organic Compounds With Fatty Acid Amines," G. A. Razuvayev, N. S. Vyazaakin "Zhurn Obshch Khim" Vol XXII, no 4, pp 640-643 The reaction of acetamide and diacetamide with mer- cury-organic compds was investigated. D iaryl mer- cury derivs react with acetamide and diacetamide, splitting off one radical in the form of a ~ydxrocar- bon and forming arylmercuriacetamide or arylmercuri- diacetamide. Diethyl mercury did not react with acetamide or diacetamid6 upon heating. 224T42 ND USSR/Cbenistry - Wrcury Organic 21 Jul 52 r_4 Compounds C14 "The Reaction Between Symmetrical Organo-Mercury Compounds and Iodirie," G.A. Razuvayev, A.B. Savitskiy, Gorlkiy State "Dok Ak Nauk SSSR" Vol 85~ No 3) PP 575-578 It order to learn the effect of neg charges at radicals attached to metals on the reactions vhicb the compda in question undergu, the reac- tion between sym organo-mercury compds and iodine was studied. The kinetics were worked out and ii was concluded that the reaction differs In 235Ti6 mature from that with hydrogen halide acids. Increasing the neg charge of the radical leads to a change in the mechanism of the reaction and a quant change in the kinetic parameters. Presented by Acad A.N. Nesmeyanov 16 May 52, 235T16 Cn USSR/Chemistry - Orvuiomiet.ELUic I Alig 5e r-oa" "o-'jn" Free Rtxdical Reactions of I',)W(c6H,47,'- G.A. Razuvayev, T.G. BriLkina, Goriki" 9~7a+c' -'r .f - .- , "Dok Ak NaWk SSSR" Vol 4, pp 8!r-" Reactions of co=lexes of the tYPe M-5(C6H~-:'4 where M = Be, Mg, Cd, Zn, Suli vxe -1nalo;7, those of oniu,.n. c--qirpds. Despite the praFcnce off phenyl radical-i at the anions in one case asqd at the cations in the other case., both. ~-_oups of compds react -under formation of fr,~!e mlicals. Presented by Acad G.G. Uraztx: 2 Jun fjzUVfjyEV, :1 1,17 c 7, '-photoreactious -of rVAMMAtAlHe m1Onj'nd&Of mercury in solutions. X111. Photoreactions of dlothylinercury. G. it. Razavaty and Vu, A. Ol'ifelco (.&Ite JIM ., (urki) -iFUbrWcl cf. CA. 49:' lii2e.-Ultravioletirr:LdLitiiiii ol2g. Etillgin2l) ml. NNO11 40 firs. gave 96% l1g, C111g, iml CH,O. in ko-Prilli tbe products were 4S% Rg and a little (CKWI)I. m. 113*. In CHU, th,: products were-41% fig, CIC11. 40% U-0190, in. IN', an I gims contg. 14%,Ctf.; W C41,14, 81% fig :uml gales contg. 33%-unsatel. hydro6djoin- in Uri IR1 184' cont m 67% Etil l l 1l l1 d . gascs g. , some g. an g , ,, g mmttd. hydrocarbons. The mults indicate radical ca~o age LJ~t~,Ffgin~oEt~12d]ZtH ad G. M. K. &L I _ -, . F " I~i F -( -~ ~t -1 RAZUVAYRV, G..,A.; MORYGINOV, B.N. Thermal decomposition of benzoyl peroxide in a mixture of solvents. Soob.o nauch.rab.chi.VKHO no.4:52-53 153. (MIRA 10:10) (Benzoyl peroxide) (Thermochemistry) -4 --Free-radical reactions of carbon tetrachloride. w' Bazu vaev ancillL kiva. UspekhsKh 22, 0 9w).-A revithVINVIN references on the properties and' reactions of the CCI, radical. G. M. Kosolapoff Ut- A L~;Reactlons of agimpm-ri, hyd G- R v d G k aFR OF A intion of PhHg radicals 10 ~ leads to decompn. via Ph2Hg. Photochein. decompit. of ArHgOH was studied in qtlartz tubes with the following re- sults. PhHgOH (3 g.) fit Ethyl Cellosolve (1) in 3 firs. of irradiation gave 0.13 g. Pirtlfg and 0.1 g. Hg; 20 hr. irr--t diation of a more dil. soln. gave the sanic products and a tittle Ph,. ~MeC.11,1 'igOll in I in LS firs. gave 82.670 MePh, 87% Jig, and sonic Ac1l; the p-analog in 22 firs. -gave 76.1% Mcph. 06.1% lig, rind sorne Acli. 2,4,6- MCIC4111119011 in IgaVein 10firs. 75.4%tricsitylenc, 92.1% 11g, and sonic Acll. I)-Nlc,NC&II,IlgOll lit I in 12 firs. gave 65% Nlc:Nl'li, 9".4% Jig, nud sonic Act[. o-Me- C,H,HgOtl in Coll, in 60 firs. gave (1570 o-MeCall.Ph, 01 4 Jig 11,0; the /,-;tii:tlog in 100 Jim gave : 4 !C 'I, , 80.2% fig, and SOHIC 11,0. 2.4,6- 8 o P_jJa ~? MCI sTI21fgOII in CIICI, itt 70 firs. gave 77.3% mesitylene, 23.4% HgC[,, 74.1% (IfgCl)-, and sonic CjCls; similar reaction in CO, in 60 firs. gave 32.8% mesitylenc, 14.2% HgCI2, 34.8% (IlgCl)z, and C20, along with an organo- mercury Compd. of unknown nattare. I'bl1gOFl irradiated 80 firs. in Ph[-CIII$ gavc 80.1% Philgl, sonic Phi, and HtO; in C4TI%-I the products %vere 111%. ffg.aud AcII, while Isubstitution of iso-PrOll for I gave NIICZCO itv;tead of AcH; .in C4HcCC14 the products were PlilfgC1, PhCC1j. 11gC12, 7(HgCl)j,andC2CI4. ltv:Ltitigillil[gOlliiiiNfcOH701i to ofrCS4H6 180-5* gave 73.6% fig. 24-9% Ph2fig. and traces .-and HICO; fit 24 firs, at 200' &S.2% fig, 12.4% PhjHg, and higher than above yields of Cal-I, and Il%CO were ob- tained G. Nf. Kosolapoff v J~, z relic Ong andnodhistillenzen in MI A. Itanivacy 7 redotava and hemical A~bst- in 25 vnL' CO. arid - 60 g~ fr~ PhCHsNHN. NPh Al) . ' 6 4a No . .5 -,&1 eircilution tk ) xave~ CCj tkrint-7 ~ his. (when _X ' . ~:` of -P ~1 d . . , 34. PbCHSNR, 5. -an ICHINTIph BzH M5 ic, Mar. 259, -1954 taffy msidue:3-lelded 151% PliHgCl.- fleating IS 1 ' ' anio Chemistry Cr HOCHICH3013ton :20 ml. a stenin bMif, finally oil a MCL-11 W th unill a 14 l d ti g t evo . on ce se u , 'but 10,'PhCffxNHPh 2 & and some AiH, -;io Cill,,w detected. ~ Hence 2 proemes occur siinultaiicnus;y~, a, I -an -6a1 -4mv* f0 *iw. pk: and PliOW MI- railicals, and ~;q T.:-Ko hzpqf~_. 01 Re& n of dlLfMh qlp-, ur~lth cn_rbqn tetrat ui mv, . . - '1, ----7 ---TZj t1tvacv rtriff L (I. A. 01 tIvNj)p,(.. .7sur. 7chet C, A 1~ r ar Khm. Z3, 597-9119,53); c . ittinurp and Thurritan, C.A. 23, 2955-Ph.-lig licated ho a scaled tufm with CCI, 24-42 IM-70* givp formatimi of PhlfgCl (max. yif!f;t hrs. to :. j8.,I% after --3 lim at 230'), llgCf (imix. vicid 51.20,10' after20hrs.at270*), HgOt(max. yicl(l73.l%aftcr27hrs.- at 26W), ind FhCCIj (i5olated as BzOll, max. yield being attained iii 421 firs, at 230*,', At 270' and ift prolonged rum, ahno,t complete dearx-lation of lfg takes place and JlgCI and llgCl.. sire forinzA, .ff RAZUVAYEV, G. A. Chemical Abstracts May 25, 1954 Organic Chemistry lor-Rwao-d- ar-Ag FIC -n=-- Q__ Wigan 1'. aff ~Tb.-; - M ZAur. ObskcW Khzm. 23, 580- -53)-_1d-e-n MAWR Goi- R aIlkyllradicals in the liquid phase was accomplished by fixa- Ition of Hg. In the thermal decompn. of Ac,02 in, C4Ho in the presence of metallic Hg there was obtained 64.7% McHgOAc. A similar reaction with Bx,02 gave 31.57c Ph- HgOBz. Thermal decompn. of AcAh in CClj in the pres- ence of Hg gave H I and HgOAc, along with prodiiets of ..chlorination of Hg tcy CM Initiated by the peroxide; C-Cle was the org. product isolated. Bz202 under these conditions gave If gOBz. G. Nf. KosolapQ", In a mixf thermal decomposition o"ONNO= Owl, solvent : benzene and nitro , M Itr zone and az carflort tetrachloride. -9- uvaev. B. ZrInwra"ov, and V A.Z", rVa ~~l .:!~njyj, ork% Tur. 'Jbl- ,rk?r - d 3 1. h 1951 e TIFermal ecompn. of DZ20~' the P11 radicali react With both C41f, and PhNOt. the formerbuing the preferred reaction. fn this system after reffitxing on ft %tram b-ath there ore formed 1.48 motes C02. 0.07 mole mi-;c,.f nitrobiphenyis (P-1somer isolated), an uppreciable itrot. of BzOlf~ some Ph2 (about 0.09 mole), atj appreciable aint. of tar. In Ph';Oi-CCI,, the preferred reaction is with the CC14, yielding CiCl., 0.31 mole PhCl, -0.06 male nitrobiphenyls, 0.81 mole BzOll. 0.07 mole w1d.0.88 mole C-0i. 0. INI. K -1-!P. 1 . ~ls - r -- - -- ---- - -- a olne reactions of 0, r A- and D it ~Ch 74 e Kh I M.2SEll.-TheWactions ~t t-NICHACIGIT~TI) "I'l, ClICIS (11) and N-bromoiticeinimide (M) were studied. 'nit "t reaction proceeded homolyfleally Upoll imfliation With ultrAviolet light, the naplithyl radical Wag split off. The- A radicals thus foringil reacted with 11 giving MeHgCl. (IV) and ClaH4 (V). "Symmetrizallon'!,of I takes place simul- tancously yielding I%Iclffg (VI) and (I-CjoHj)Jfg' (VIO., The reaLtion betveen I and III pr=cds by an ionic inech- UnIsm forming'bmmonaplithaterta -(VIII) anti (Ctl'co~-' NugiNfe(M), 1(2.5g.)and20tal. of 4 were irrndlated by'. til. 80% IV, in. 14-9*(27.0% yield), "dVI, m. 154', Wwas detd. by traWorming it into MeHil and VI into NleHgBr From the distn. residue was sepd. 06.0%VU, m.239'. To: 1.0 g. of III in 20 mI.of H was added 3.0 g. I in 10 ml. of II.; By steani distn. was septi. VM; picrate, m. 134*; After,` .b evapn. of residue wits obtained IX, m. - 128% yield 100%. jpd By.theact Ion of III It formed MCHKI. M. Hoseh,-' -'P for J RAZUVAY[dV, G.iL.; WIMP, Yu.A.; GRO-BOV, L.N. L : - -'- ...... --- New method of synthesis of organomercury comDounds. Doklady Akad. Nauk S.S.S.R. 88, 77-8 '53. NLRA 6:1) (CA 48 no.1:142 '54) 1. Gorki State Univ. t _H=VAi3V, G.A.; PRTUKHOV, G.P.; REKASREVA, A.F.; MIKLUKYIN, G.P.; VOLIYK-O- VICH, S.I., akademik. Use of deuterium in the study of photochemical reactions in the liquid phase of metalorganic compounds. Dokl.AN SSSR 90 no.U:569-572 Je 153. NTPA 6:5) 1. Akademlya Nauk SSSR (for Vollfkovich). 2. Institut fizicheskoy khimii im. L.V. Pisarzhevskogo Akademii nauk UkrainBkoy SSR (axe. Vollfkovich). 3. Gorlkovskiy'gosudarstyennyy universitat (for all axe. Vollfkovich). (Organometallic compounds) (Dquterium) The photo reactions of pheny-baercw-y and diphenyl-mercur"y do not proceed alike, al-though these comods are homologs. The reaCtiOrL of the first apparently takes place in a reaction "knot" consistiric of one molecule of the hydroydde and one molecule of the other reagent. Conversely, di-phenyl-me-rcl=j reacts by an open-radi- cal riecnanism. EX-ptl -)roo--F' of the transfer of the chain bv free radicals vit]h the reveneration of the reacting radical i-ras obtained. The above -..,,ork was done using ,T1 and etu-.yl alcs contain-inf: deuterium in the lhydro~-7[1 group. Presented by U Acad S.I.Vo-, lfkovich 9 T-~,r 53. 254T95 G. As Chemical Abet. vol. 48 No. 6 Mar. 25 1 1.954 Inorganic 'chemistry of -Complexes M(RPQ. and T. OL'Brilkina (Gorki State Univ.). Naul-9,777.71, MT=1aW7r---cr--C.A. 407k, 3M.-Readlon of LI(DP14).2LIBr with irg in CHCls ~el - `Tffff.M~ reacts with Rg. form- gT some PhH9CI free radical R. Addn. of an cqttiv. of I-QAtiLi with PhsB In RtjO gives LffBPhjCjX,j as a viscous oil: tmat-i ment with NHCI or KCI gives the NH4 or'the K analog, colorless solid. To eliminate the LiBr,- contamination the technique of prepn. of pure RM was employed for the neces- sary Intermediates (cf. Talalaeva and Kocheshkov, C.A. 45, 10191s). and the resulting pure Li derivs. were treated with the boranes in RIO to give cryst. LilBPAjCj1jMe-pj and Li[B(CaHr-1)Phj- Treatment of these with Hg In CHO, again gave free radicals &rived from the BR. frag- ment, with predominant cleavage of I-CIsH, rather than of Ph group, and predominant cleavage of p-MeCsH; rather than Ph. The mults parallel those obtained in thermal decompn. of NH4(BArj complexes; thus NH4fBPbjCtaFTT-1 I gives Coffs and NH,.BPh,; NH,jBPh,CJl,N1e-PJ given MePh and NH..BPh,; NH,jB(Cjaff~l),PhI gives 2 Claffs .and no Ulf, with probable intermediate formation of un- stable NHs.BM~H,),Pb. G. M. Kosolapoff_.~ V 1 ) EV 7' All TtW tk.6- bdtWj' I anlao-M&MIL.- G. -A. ZTEF, I an M 6; , -.717ama -Aatwv jj2!j4vqov~ I OM j A d lem tQ L e a i~i ~Q; 3453-4 i 4&onpll.:d BY4(3% (1) in a inixt. of cia ima ' ' iso-PrOH gives RCI, MejCOJa d CHC4 in qua~M16 ceeditiiSG-20titte5fhio~ional44a~tifyoff. Theyjedof_~ thqc prWucts iscreasm im-the'cQwm'*cf I deueas6. -It is SUg&Md that I t cibain maetivvk*tw~en CC14 aA4 iso-PrOH iii a6cordaiie '%vi , R + CC4 RCI + CCT Ith +'CC4- -4 U02C( OH)o:+-CHai. vf~~C(OH)q... 4 CC4_ XciC(OH)Cl + CC4- and Mc3C (OH)CI + MeXO.:'Wheri -R is priruiCry ridical fortmd-on: de-- corn-ow. of 1; - It is also ~ogsible~ that theradicalle2QOH); ' isf~ rniedbygi,~ingup4toPhCGOi.eidicah.: -j 3 'j. j 6,J) - USSR/Chemistry - Photoreaction Card 1/1 Pub,, 151 14/38 Authors Razuvaev., G. A.; 011dekop Yu. A.; and Latyaeva, V. N. Title Photoreaction of organometallic mercury compounds in solutions. Part 14.- Photoreaction of beta-mrcuribispropionic acid and its dimethyl ether Periodical : Zhur. ob. khim. 24/2, 260-262, Feb 1954 A s tract : The photoreaction (exposure to ultraviolet light) of beta:-mercuribispropionic acid in solutions of methanol and monoethyl ether of ethylene glycol was in vestigated. The rhotoreaction was concluded with the separation of the'mar-~_. cury and formation of propionic and adipic acids. The separation of the hydro" gen from the solvent by the carboxyethyl radicals was found to be instrLurLeatal:: in the formation of the propionic acid and the formation of adipic acid is due to the diinerization reaction of -above mentioned radicals. AldeKydes uere dis- covered in both cases. Four references: 3-USSR and 1-German (1907-1952). Institution State University, Gorkiy Submitted June 19, 1953 P U V USER/ Chemistry Reaction -orocesses (' ard 1/1 Pub. 151 15/38 Authors Razuvayev G. A.; Moryganov, B.N.; Dlin, E. P.; and 011dekop, Yu. A. Title Reaction of acyl peroxides with metals and metal chlorides.(Sn and Sb). Periodical Zhur. ob. khim. 24/2, 262-265, Fab 1954 Abstract t The reaction between benzoyl peroxide and SnC12, SbC13, metallic Sn as well as the reaction between acetyl peroxide and Sb were investigated. The reactions. were carried out in benzene, dichloroethane and acetic anhydride solutions. The products derived from these reactions are listed. Four references: 3- USSR and 1-USA (1927-1953). Institution State University, Gorkiy Submitted June 19, 1953 L1~(4%jPldx C610~4;nds of lyto MMAI!J~ ~Qp- ~A, and r. o. DO hia (State My, C, fir. 'Fly-, Ph grRup'(Col1j) 4hd ph,nmli, tn, W-14 141F-21(1054). cf. C.A. 48,3180f,m-Addn. o130 Khija.24 the aq, saln. contnincil 11110H. Refluking 3 1. KI Off , 1. OAN MeLl In M.0 under X2 to 1-4 of gave after evitpo, a cryst. residue Lit P, "I MOCHICH,011 2 CIN. and PhOH. Hed 11.0. gave Ft bask sofa. which Y!cldcd - (CMff1)PI4 I . - . I tiflir a g. with 75 NH47 decomposes on esposdri: to air; soln. In H20 yields mine Ph: and gives a basic 5oln-i fresh aq. 39ins. gave no ypts.. ML HLOC113cfflotl dild w. QA and 1.1 P , 95 0. Pro 8 irb. di faux gave U hAIM alonk *jflI Soule with K or NU, salts, but on prolonged standing ppt3. formed;, SIM111? rMCHCH 0 )CMACAM") kAVC 96 Meph: thus NffjBPh4J was obtained. %mmetrization of the' and some PhOR Stinitar reaction gave; complex accounts for formation of this substance. Simi In 4 his. a lossof2C,jl? groups as CtoU#, along with phenyl- r.. boricacid. To3-5g.XBPhJridrYMeOH8mI.1MJfB larly. 8.84 g. (1-CjiHj)~D.2Cj1s in Et3O and UBN EtU In C4111 (9 ml.) gav a prt hich fter vacuum drying yielded % w a l In MLOR was added; rilln. with 11.0 gave 1 .5 g-PhBr, I g. phenylboric acid Similar reaction of LiBpb~ g. Phi an air-unStlible it JOHI)jEt]. Aq. soln. of this treated . B . . C4H4Me-p voith Br, in aq. soln. gave p-ErcAme (809~1 with KCI or NH&CI gave n1ttr several hr3. a ppt. of the cor- responding K or N114 salt; only N)T4jB(CisffT)j was ana and dipheisylboric acid. Mumbiation of 3-5, g. KBP~ I . j lyzed. Heatlng 5 g. V-DPh with 80 nil. EtOCH&CM,01 in CKC4 100 furs. gave some COH4. Phi and PhOH. To 4 i dry #--C1, was added.- - The, KBM In dry hie c0 7.3 9 j and 20 ml- HtO 5-7 hrs., followed by steam distn- of CHa gave AcH and PhOH, along with crude diphenylboric acid. t - - . . s mbrt.. heated 0.5 hr. gave on dibi. 64% CJ-T* (based an loss Phi and phenytbork a6d; the sola of I Ph stoup 1.3 g Similar reaction of NH#BPh4.gave a loss of I Ph gioul, (W ined PhOH and di- d c t 2 l th Wl ) i . . ?, for errie and ferrous Ions. 0. M. Kowlarg'a e . ue a ,rs.; on n . , phenylboric acid. H g l4BPh4 with dry NleOH In; , 100- NH l 1 I ( l b ow o ~sca qd tu e 5 t & at pe t, n% -Z U Y USSR/C~jamistry Card 1/1 Pub. 151 41/42 Authors Razuvayev, G. A. Title : Remarks on the report by A. A. Bollshakova.entitled, "Reaction of Metbyl- Alpha-naphthyl Mercury and Methylphenyl, Mercury with Organic Acids". Periodical : Zhur. Ob. khim. 24/9, 1693-1694, Sep 1954 Abstract Brief discussion on the report by A. A. Bol'shakova regarding the mechanism of reaction of metbyl-alphbL-naphthyl mercury and methylphenyl mercury with-:.- organic acids, is presented. Six references: 3-1JSA; 2-USSR and I-Geri=*. (1943-1954). Institution 'tted S ubmi April 24, 1954 U V F4~ e USSR/Chemistry - Photo-decomposition Card 1/1 Pub. 151 - 13/37 Authors Razuvayev, G. A., and Osanova, N. A. Title Photo-decompositIon of pentachloroethane ft-riodical Zhur. ob. khIm. 24/10, 1771-1775, Oct 1954 Abstraot t The results obtained.by exposing pentachloroethans to the effects of violet ray radiation are described. The complete,reaction.schem., begir6inj,~.' with the separation of the'elementary Cl-atom from the pentachlorpethahs, anct'. the formation of tetrachloroethyl-radicals, which are finally.dimeriz6d into octachlorobutane, is explained. The separated dl chlorinatesthd basic pentachloroethane and the formed octachlorobutane up to the ion- and:decachlo-- robutane. Eleven references: 74JSA; 2-USSR and 2-German,(1940-1933). Institution State University., Gorkiy Submitted February 10, 1954 -WSR1 Chemistry - Physical chemistry Card 1/1 8 Pub. 22 - 28/49 Authors t Razuvaev, G. A.; 011dekop, Yu. A.; and Mayer, N. A. Title Decomposition of mercuric salts of oruanic acids initiated by free radicals Ferlodical Dok. AN SSSR 98/4, 613-616, oct. 1, 1954 A~strsct The reaction of acetyl peroxide with Hg was investigated to determine. the decomposition characteristics of mercuric salts of organic acids when promoted by free radicals.. It was found that the above peroxide reaction can be used as a suitable method for the synthesis of miethyl- mercury compounds and alkyl-mercury derivatives. Six references: 5- USA and 1-USSR (1921-1953). Graphs. Institution Presented by Academician N. N. Semenov, May 22, 1954 VR-actia I- radical in liquid phase. Readivity of L Of volychlotorneftl &ad h T*oV ;5111_~_ A Razuvacy, voprosy -KNI-17t. Kineliks, i S kad ' Nauk S.S.S.R.. VAL#'vOldel. KUM. Nauk I9TS55fO7lr7.-Thc radical reacition of Bz.02 in PhNO., CC4. WOH, Iso-FT011i Cilia-1-1g. CjI,: Cu. Cille-Sn, and their combinations was examd. In Ph-r NOrCtffs there are formed Plit, MANN and C%. In PhNOr-CCtA there formed PhCl, C(h, and CCI,C,114140~. In MeOH-C41`14 there formed BzOlf and CHA as well as PH, and BzOMe.. In Iso-PrOll,there forined.BzOH an# Me.CO. HCI and CHCI. are formed also In Iso-PrOll-CCI, ed (B.Hg),. R-' along with.CiCh. In CjIrHg there form HgOBz, and COi;. Ac,012 or Bz,O~ react with mercuric salts yielding products explainable by radical chain meclumi!m.: Reaction of BzA~with Cuor So also proceeds situttarly,.' yielding cuprous or statude benzoate~ Reaction with Hg in' CCI, gave no CO, and yielded CCI..and PhHg radicals, as y formation of PhHgCl. Thus the order of reac- shown b tivity with peroxides is descending: ales., Hgi Cu, Sal CC4, Calls, PhNOi. A convenient identification. of transient, radicals lies in th;ir fixation an Hg; thus:AcA in C,114 In contact with 14i gave a detectable odor of alkyl-lfg derivs.-~- (M-O.NCJI.CO~)s reacted with Ifg on heating without loss of C02, yieldlng-%H Ilydroqttinone or ales. suppress thi, reaction of acyl-peroxides with IIg..'Heatijtj*EtOFf with, CC14 to 210-20* does not produce CsC4, but y1elds Cs",~'~ HCI, and AcH. Irradiation of C,HC4 with ultraviolet gave ~ 3CI,, C401e. and butane derivs. Ac,% heated with AcOff C Vve C02, succinic acid, V~11,. and other products. G. M. Kowlavolf J ~!z CoUs 11 .5 his., evapn. of the org.- solm jind 9team ... ... ithe residue In the presence Of. 'a C&%~jlaveZ satd. -PhHgC], some Phi, and BzOH; Refluring 7 25 ml. I ( cohtg. 3.8 g. Act0j), And 70 ral.' 'from C6W# 0 sepz- -t~r, a little A with e Ro' Veil tl rmrtms for se o o o W! fio*m_xn1enufy salts of organic acids... U.; 0 e -Wb 4ree s owu with id IX, 4. MaTer (Sta IV. r ZhUr. t proportions of riactdnts kiW 25. en the reaction was rim in AcOH a 997 25. p yield ot-MeHit, 097-706; J. 666,- 55 (Engf.' n). tion of Hg salts of slat ~'L,r 7.7109 1JAW16.2ci Is In the prez-en Of (ides is used a's a new W-5 thesi!~,'.Of ali a unamercury cofnp&. be-ked niniiiech2n To 90 g. Ac2O and 2, vras nd the - 1_t'..~tjr;eNa0K, bedded with cooling 1840 g. 30% HA a 1 hr:-.with continued, cooling contained no nor, uure~ictid Hi0t; the conca. of Acz0x was 0.16- oin 0.18 pfml.'and the soln. (1) could be kept for several days. Heating 15 g; (AcOfte,. 18 mi. 1, and 150 mi. C4Hs 7.5 his. ~Rt reflux, filtering off and washing of the ppt. with H3(,),; and 1 L 1, m. irLiament nf the:acj.'ext. with KI imve-49% MeHg PLII;jxing~-S g. -(Aj;0Hg)j, 3., v-11Z20A., and .60 ml. was obtained and the reaction rate wrs 25 times greater 'it, C4Ra; the propagation coeff. of the chain reaction vras:: i at -near unity. In dil. AcOH only traces of Meftjr- -,e~ I ;were formed under similar conditions. Refluxing .15 . if. fHg(OAc):.'2.5 g. I-bYdroxycyclohexyl 1-hydroperbilde, sai .. - - 'a-cetate, and IGO ml. CU, 7 his. save 5.5 g. Pptd. Hg 4i and 40.4% MrHgI (after usual treataleuth'as well.",-~7 'Unidentified yellow oil. The res tion run in AcOH-AWt gave a little (AcOHg), Refl and 779.3% meHgci. . u3un 'Mg(0Ac)j with Bz2Os in C4Hj 12hrs. gave pptd. Hgsalt~-, 154% bicHgl (calcd. on , 41.7% PhUgCl (,=jcd -'J"' Hg) 0 jBzA), some Phi. and Bzotf. . Refluxing 7.2 gi.Hg(01lz).n;` .2 9. B402, and. 60 mi. C.Hj 12 hrs. gave 2.1 g. ~!Material with-some fir tvhilc'the filtrate, aft !treatment.with CaCl, aii. steam distu. gave 2.0 4nd some PhHgCl, along with Ph, and BzOH.-'~ CEt)% (15 g.), 2 g. bzj0j, and 60 MI. -1 . . . . . . . . . . gave a,PPt; Of 0.0 9. MM ;.wh the -fil with HC) and the ext. treated vrit , I i9rup H&C1, -and P 1; so tae hHgC z 7 RAZUVAYEV, G.A.; ETLIS, V.S. Condensation of benzene with certain symmetric chloreethers. Zhur.ob.khim. 25 no.9:1711-1713 S 155. (KIBA 9:2) l.Molotovskiy gosudarstvannyy universitet. (Benzene) (Ethers) d Ott W10sphorus by.mt I P 0 __UfEkDe -Daklady-Akad,lVall T"Asw n:th tudicals fri~sn A)hW itk It equtitorba kitiativils; thim 411:5 111L gn equally to-the, P`atom- in lspi pyramid., This icsolt i.5-dXcirek- fri rutes of d1frexcittly, lacked Cl a(bms and ljazilgmaf,~ C.A.:~49, 50(Ah~dnd, 48;,4001b). PlijPI,aud.C6D.U D,PI, 3-icilded D.Iab~kd PhiP.,--or PW,'l t6-OLTIO (iafitiii tit flit, Oi)lat locatib be labeled'ouly iii th6 jjo~ir location li~ "iid I -kiitli"is sfiould'ji,.4 LL-1: I tia. filibeliri'g, Af -the Ph- iijiioh~'add -4 avdi the- oilly_tfi wfiili~-'thti 2iid metliml should give 4A clel'vuvc,- oli l' 6v 2 Ph~ wlcnts ~ vy~. r lc I the- Ivan t etd.~ CIIC)j adlit w the a1c., by, resultinj Ph: radicdlsi~'yi bution inclicaiive-of ciiiial Mcifity. of 10 -6n With C.1i Un, Iv TII&P hi C'41D~-give initchl HO exclianp of Ph milkals-took place and reageitc. . rqual f(tdjitk,0f 10S'S Of iyus agairl ShOwri., 1) 7- U y 6 V) 9 idWO'C' Maims I"in therm&w and phot LAU out 9WOM ta omnounds. - ~~G. ,A.;'I;C G. 0. MCI z a.Wvaev, Fctukhov bl.'A -Shubenko antr1r. A., V5fWvm:h,(btate::: : t f ~ flowingivsults- were usslan lie A5 obtained f6i iiattions Involving -the H betlveeii~ the-Advent.."d Ahe- products of -the diecoinpn.: of orkaziomactallic compds. fevt '' no., s a., solmat, D 6oritent iu solvent L,.Q-. tatting comf fated pioduct, 'und. D conteni . -Oroduct~(-j) im]. '1F.1' Ju, Pbj14g(1),C4Di( L-38WI-P112, Phs 120- - 3 Ph&Pill, 3200, ' CAMe~ I&, . (Plitkii)t, 12i: 5j: PhC Hil, CjDjWfe. .781, '11~ 912, BzOff M8t- 7 1 Na, (PliCH6,167. -6, 1 + Na, + H * 320D; BiOll, 2608;4, (PhM' ,,Hg~+ Wa; C,l),h1e, 1218, ' 993j BzOH; 70; 10-- 4CH,CO.H, 424; . 9;-PhMkBr, 1r,, PhBr + . Na; -H, -3200, Plij,' k8; 11' PhBt* +. Na, 11, P11 fig. (PhCH.)~, W.. 2. 294, 12i ?hCJI;Br + Nq.,VDsN1e,, In expts. 1; 2.4i and 5, a sample (5-g.),af the staiting compd. i - test tube, was irradiated with in 15 ml. solient in a quartz -ultraviolet larnp (PRK-2).. Odmp1e'5,- in hddn., writaided -kept pptd. Cu.., In. expt.:3, 6eTeactants.*ere 19 ly - e OTh t l. xpts 'G, -(i-a-nd 8, earnh:d out in M &4-t M i em added to a ruaraplit (5 g* and later an e~%cez of Drjr. Ice iv _ - '-T6 of the o the-i Ek i ffi f lia t d 1 ip ~ . i a. r- rgarion c c co o o ., p g (expt. 9) in MO. CA ivsm dddW an ixcesibf ]Dry,ice.-: The mixt. ar PhBj(15 g.)1#8 g.'solveui (expt4lo) coatained:~ - ' - -C - 3~ N l D 3 x t 11 t t N W add d 8 c a.. . on e n ~ o as g. e a j~ j it. g. , p dropwis--16~.Phllriiiid.i6.th~.'atWoiousex0t.,12.1 9. 0 CoDIP every iustince a 2- Ila fir. re~cifon: thne was sufficivit to teach aneq". mu! av.~Crror A~~O ob USSR/Organic Chemistry Theoretical and General Questions on Organic Chemistry, E-1 Abst Journal: Referat Zhur - Khimiya, No 1, 1957, 769 Author:- Razuva Stupen, A. B., and Minsker, K. S. Institution: None Title: Oxidizing Action of Some Acyl Peroxides Original Periodical: Zh. obshch. khimii, 1956, Vol 26, No 2, 473-474 Abstract: The oxidizing action of benzoyl peroxide (1), acetyl benzoyl peroxide (II), and acetylated and benzoylated derivatives of type III and IV has been investigated with reference to the evolution of 12 from KI. A marked difference was found in the oxidation rate of I and 11 (3-5 minutes) and III and IV (20-100 hours). A mathematical expression is given for the oxidation rate of III and M V = X/(a-bx), where V is the milliliters of 0.1 N Na2S20, used in the titration, x is the time of titration from the start of the reaction in minutes, and a and b are constants which have different values for III and IV (for III at 220 a = 49.2.) b-= 0-0857). The rate of the initiating reaction is Card 1/2 Card 2/2 G-4), j amm ji. X.7 A-.. "'~j ow 4 oNegao ", " i -A -t3haking 4VU St. W _ p ' -Cli and _ 1104-Mli hi a6 4 ave,2 hm'at 35-4 5 4 ' 707,:.~Ield_ -wt is obtained 52R; m If Lraseotm NH, W~i Passed lni~ 6e -ahdiie reaction t., T., The firoduct is fairly stable itt. air-and c iinn6t.bedistd. ' _ '; I h fi l S0 e TRUo C _ Hydro ysis with 10.9% HI 4 kave, 78% c : NH , ( . 168 ivith NaOH guve',2 f ' s ae taf ALT , . , I)c haawne (11), bi 424', dig 1.002i nj?~ 11054, T t 'ment of the above PiWafe iAth 15%,NP-,014 jave MAT d' H dd un ist - - - "Ner ow _ (9: 'u ed i~ treat [able wt thout,6commi do I.IrM. -B) nj? 1 - ' oval,of *tl' struinz.-)UNH, 16 hrsi follavried-by' re WS I a ex- m ' cefts-Nff~ aad,refitriing 0.5 hr.'with eibugh F1,S0i to acidify ' form the MiXI., NHa in an aint; agreeing with ation Of 1. p -16 hrs. into'eycl6hexiwon v ~24% I assage of N% ga: e %Vb*te..U reacted with'gaseouSNH ed aq h-1 G~ -M analok tCLexmted *inoeycIohezyl , ..,, . 2- USSRi/Chemistry o-L High-Molecular Substances, F Abst Journal: Referat Zhur - kQ2imiya, No 1, 1957, 1146 Author: Minsker, K. S,Y Sheviyakov, A. S., and Razuvayev, G. A. Institution: None Title: The Part Played by Oxygen in the Initial Stage of the Polymerization of Vinyl Chloride Original Periodical: Zh. obshch. khimii, 1956, Vol 26, No 4, 1082-1087 Abstract: During the polymerization of vinyl chloride (I), both pure and in the presence of initiators (benzoyl peroxide (II), azoisobutyl cyanide, acetylbenzoy! peroxide, 21 2-azo-bis--n-isobutylpropyl cyanide, met-hylamino-bis-diazo-p-anisole, and methylamino-bis-diazolbenzene)) an induction period is observed, the duration of which depends on the amount of 02 present, as well as on the nature and concentration of the initiator. In pure I the induction period is considerably longer than in the presence of initiators. During the induction period the formation of Deroxides has been established iodometrically. Tn the Card 1/2 Y E- V/. (I - [J. USSR/Organic Chemistry - Synthetic Organic Chemistry E-2 Abs Jotir Referat Zhur - Khimiya, No 2, 1957, 4463 Author Razuvayev, G.A., D'yachkovskaya, O.S. Title ion of Tetrasubstituted Silanes with Carbon Tetrachloride-, Orig Pub Zh. obshch. khimii, 1956, 26, No 4, 1107-1110 Abstract Photoreaction of CC14 with (Cg )45' (160 hours, 35-4oO) proceeds over chlcrination w Kt removal of radical, ' and the formation of' CH CHClSi(c2"5)3' If in lieu of ir- radiation with ultraviolet lipbt the reaction is ini- tiated with acetyl peroxide at the temperature of boiling of CC141 there is formed a mixture of alpha- and beta- chlorethyl-triethylsilanes, HC1, I and CHC1,z Ben- zoyl peroxide does not initiate '2C16 -$ this reaction. Oil action of ultraviolet radiations on a mixture of alpha- and beta-chlorethyl-triethylsilanes, it is essentially the beta-isomer that undergees decomposi- tion. Card /2 - 99 - RAZUVAYEV, G.A.; OL'DIKOP, Yu.A.; IATYAYEVA, V.11. Reactions of asy=etric acyl peroxides with mercury. Zhur.ob. khim. 26 no.4:1110-1113 Ap '56. (HLR& 9:8) (Peroxides) (mercury organic compounds) 77 RAZUVAYEV, G.A.; OLIDEKOP, Yu.A.; SOROKIN, Yu.A.; TVERWVA, V.M. Free radical reactions of lead tetraacetate. Zhur.ob.khim. 26 no.6:1683-1685 Je '56. (MIRA 11:1) l.Gorlkovskiy gosudarstvennyy universitet. (Lead acetates) (Chemical reaction) RAZUVAYNV, G.A.; PETUKHOV, G.G.; KALININA, R.V. The catalytic decomposition of phenylmercury hydroxide in solvents. Zhiir.ob.khim. 26 no.6:1685-1687 Je 156. (MIRA 11:1) 1.Gortkovskiy gosudarstvennyy univerflitet. (Catalysis) (Mercury hydroxides) K ~ ev //-,k i/ 6 t1 9. '41, USSR/Organic Chemistry. Theoretical and General E-1 Questions of Organic Chemistry. Abs Jour Ref thur - Khimiya, No. 8, 1957, 2666o. Author Kolpowkaya G.A6;, Moryganov B.N,i- Razuvayev, U.i. Shushunov, ~.A. Inst Title Chain Reaction of Carbon Tetrachloride with Isopropyl Alcohol Initiated by Acetyiized and Benzoylated 1-Oxychclohexanone Hydroperoxides. Orig Pub Zh. obshch. Ichimii, 1956, 26, No. 7., 1981 - 1986. Abstract Acetylized (1) and benzoylated 1-oxycVulo- hexane hydroperoxide (II) starts a reaction between CC14 and isopropanol at 1+0 to 500. The basic resulting products are HC1, CHC13 and acetone (III). The influence of the concentration of I and II on the initiation Card 1/2 c,2 USSR/Organic Chemistry. Theoretical and General Questions of Organic Chemistry. Abs Jour : Ref Zhur - Khimiya, No. 87 1957, 26661. Author : Razuvayev, G.A.; Moryganov, B.N., Inst :--ICi~o6nman ~,. ~. Title Reaction B6tween Hexachloroethane and Iso- propyl Alcohol Initiated by Benzoyl Perox- ide. Orig Pub Zh. obshch. khimii, 1956) 269 No. 87' 2224 - 2228. E-1 Abstract When hexachloroethane 11) is boiled with isopropanol (II) in presence of benzoyl neroxide (III) the reaction proceeds accord- ing to the radical chain mechanism: initia- tion: III---)2C6H5CO00--4 C H'+ C02; beginning of the chain: C6H5COO-+ I~ 5 C6H5COOH + Card l/ USSR/Organic Chemistry. Theoretical and General E-1 Questions of Organic Chemistry. 1 1957~ 26661. Abs Jour Ref Zhur - Khimiya, ,To. 87 CH3C6(OH)CH (A); C6 He II ---~ C H + A- chain: A + 1 -4 (CH ~ 6 1 0 - ' C1 - ~C~2CC4 --+ CH-ACOCH2 * ~CY * CCrpCl!~; chain transmission: CCI 3~CM -* CC'?+',C 12 + Cl"CC13CC'2"+ II --+ A + CC13 C12H; C1 I--* A +HC1; break of chain: 2A _* CHVOCH 3+ 1,' C02 HC1, acetone, benzene, phthali and benzoic acids anid pentachloro- ethane were found among the reaction products. The circumstance indicating the chain mechanism of the reaction is that if it is carried out with 1 mol of Il and 0.125 mol of I in pre- sence of 0.0124 mol of 111, 24.1 mois of HC1 and 16.7 mols of CH COCH will be received per mol of III, wMe O.L21 mol. of III will produce 73.3 mols of HC1 and 37 mols of acetone under the same conditions. The length V of the Card 2/3 USSR/Organic Chemistry. Theoretical and General E-1 Questions of Organic Chemistry. Abs Jour Ref Zhur - Khimiya, No. 8, 1957t 26661. chain computed by the equation V-(,c~cVCl/'0't) ("' CIIIX &t), where &C I is the gain during the time Ha~ In HC1 At7 &Y-Tjj is the loss Of III during the time At, increases with the decrease of III concentration, because at the concentra- tion of III = 3. 6 x 16-2 m V 7, and at the c ' centration =1,2 x 10-2 M?,.,)--18. on- Card 3/3 lid Y4k V. Afag. 20; fAr uvM J4 -C psuv~kbfo'g.p. 4 JfiTs. PhDr with qn47t- , ' Q.64 K. i~ 4mci on tho folfowlp~ day with kc4fi5u, gave drio (1)',.d 0.38 g, mq.0 Ph.Crf-42CH" (W E. Refts'l 41., C.A. 1, j 0 to grCeg. = W-M wl)fi:b after stewn dista. a reactIon lei Similarly, th irmdiatkMal'11 30 brB' OVIZ.% pitik-violet,la colof (Iodiptc Id Clt d j a Vr " h eno thc~ptlf f - , C' -- - ~ us th, 6d er rgrth 478 AUTHCRS: Razuvayev, G. A., and Olldekop, Yu. A. TITLE: Reactions of Acyl Peroxides with Mercury (Reaktsii AtsillnyKh perekisey so rtutlyu) PERIODICAL: Zhurnal Obshchey Khimii, 1957, Vol. 27, No. 1, pp. 196-199 (U.S.S.R.) ABSTRACT: The investigation of the reaction of acyl peroxides with Hg in various media was expanded to include in addition to benzoyl and acetyl peroxides also chloroacetyl and m-nitrobenzoyl peroxides which during decomposition offer more stable RC02 radicals. The solvents used in che reactions and their properties are described. It was found that acetyl peroxide reacts with Hg in a benzene medium at normal temperature witholt separation of CO forming mercurous 2 acetate. Chloroacetyl peroxide reacts in a similar manner; the fixation of the chloroacetyoxy-radical on Hg was observed during the mixing of the benzene solution with the Hg at normal temperature. The reaction tendency in boiling benzene remained unchanged, only the rate of reaction increased sharply. The product of this reaction was identified as mercurous chloroacetate. It became evident that the introduction of C1 sharuly stabilizes the RCO 2 radical. The very same effect was demonstrated by a nitro-group on the stability Card 1/2 of the 02t'C6F4 CO 2 radical as compared with C6H5 CO 2 radicals. A Action by' 04 h 4 Val Mel*by. a ra4101-rowc-Thwil, 7 Thl TV aiiation 0cqIor 61 ~ho*ms. of PIuP Atoll -hi the Mel, CHC4, 6e~ ra2~4 0,N)AIAX 0 ir :The lonk f ee md1cal kiixtes)i PIUP with'AcOH was:c=fittned reaction wich CHC4 witiolml ' kinetic cunie is'shown. 'The r~Act Maid Intiatuake"my. i, I wai p a in 9 w1i pure CHCli wai zfi~~jj ' 411~- drY- NitSO4 I hi, Of . * h P* r e ft. of I phip, witif C114 in t L ica oix Froe:radicitt, f6rt -1 - 'd U ns - with -M~ VP a sthdi T U- A Ulu a nd .- ~ ~htp re6cts with trod 44z,g. 1-141 .. .... b u Od rm 3jddlUCA(tO1(j of. %4,i~OiN)s pwld~wlor 61 t he In,thc:'pmiwIci ar Th' ~drkaily_ a" AL ide a 51 to' m I- , ridd i T . _q nd 0.5 we Niol f a l d ju x e to x s y., is-46und i -pyl l 7 AUTHORS, Etlis, V. S., Razuvayev, G. A. 79-11-39/56 TITLE: Synthesis and Properties of Some Derivatives of Thioxanthene-5-Dioxide, With Indioator Character (Polucheniye i avoystya nekotorykh proizvodnykh tioksanten 5-dioksida, obladayushchikh indikatornymi svoystvami). PERIODICAL: Zhurnal Obshchey Khimii, 1957, Nr 11, pp, 3092"3097 (USSR) ABSTRACT- It was of interest to realize the synthesis of the other- wise little investigated derivatives of thioxanthene- 5-dioxide with a good yield, by means of sulfonation of some aromatic compounds. At first diphenylamine was treated with 66% fuming sulfuric acid. After neutralization of the excese acid the alkaline solution took on an intensive orange yellow color. This fact incited th.: authors to investigate the nature of the coloring matter with indicator character produced in sulfonation, By the action of fuming sulfuriv acid-upon diphenylamine and its derivatives during strong cooling the oxidation of the methylene group and simultaneously the sulfonation in the position 4,4'takes place. A coloring product in a small quantity already forms Card 1/2 on this occasion. When the resulting 4,4'-disulfonic acid Synthesis and Properties of Some Derivatives of 79-11-39/56 Thioxanthene-5-Dioxide, With Indicator Character of benzhydrol is treated with further quantities Of fuming sulfuric acid at 150-1600C a coloring matter with high yield is obtained. 1,1-diphenylethane, triphenylmethane and 2,2 diphenylpropane were treated in the same manner. Coloring matters were also found in the first two compounds. On the basis of these tests it must be assumed that at least one hydrogen atom at the methylene group, where the oxidation takes place on sulfonation, is necessary for the formation of coloring matter (see formula). The following compounds were synthesized and their properties investigated: 3,7-dichlorothioxanthenol-5-dioxide and 3,7-dichloro-10- ,netbylthioxantheiiol-5-dioxide. The indicator properties of the deriyatives of thioxanthenol-5-dioxide were determined and the structure of the coloring matter of these compounds was suggested. There are 2 figures, and 17 references, 2 of which are Slavic. SUBMITTED: October 20, 1956 AVAILABLE: Library of Congress Card 2/2 1. Thioxanthene-5-dioxide-Derivatives-Synthests- ev mAxtx= ilv E lit !CA vm . hq~ i.' pron: iW41CM idWtht n wem. "LW egftj'j Ok aiid Wilddi b. Mt. 0 t[it-MUK.-of -the, rtacting.114pus U'ym to epa r Aftera preded, time the mix pticid UA L 9 Mt" zel contg."HA'and the HCI hi tba o ' f di.: Su in thc u I whicli c6wLttid of iOulit.1 pper OL3rer.' U. sta cri 4etd.' The"reitetiou. and CCh was iabotit2O firries a fmt hi thiprqi~d Za X, - --10-8 to 7 xloz~l raot j4t ~Isfcrdeivtl trea~tlon 61 Bzt% decomps, he tbih- fit Sr IcAnfrole lii-thc:rimWon betwl CCU. 'HCI Bz I CiC14,04 iver of jrkht tbluic'steidweriloWidiatlic pvdittu--, land Oro A~ The a'v I~ng , ~ _ 'to,theitutlal BjjO2-con t in 'const. The. initial Bilot tkcoznp~.' %ih en pr~serl - .con&i. in the', iso.PrOH-CC4-jnlxt-.~. played no-S gut Ai . . . . . . . . . . . . . AUTHOR _~A~YF~.VG - A~_ , SOROKIN, YU A. , DOMRACHE V, G.. A. PETUKHOV, G.G., TSVETKOV, YU. D, MOLI~N, YU.N. TITLE On the structure of organochromic compounds. (0 Btroyenii khromorganioheakikh soyedineniy.- PERIODICAL Doklady Akademii Nauk SSSR 1957, Vol 113, Nr 6, (U.S.S.R.) 2o-6-3o/59 Russian) pp 1293-1294 ABSTRACT In a paper recently published by Fischer the synthesis of neutral dibenzolohromium and its salts is described and a report is made concerning some further aromatic derivatives of the chromium-(O). This author assumes that the latter compound has an A-structure analogous to ferrocaen. Recently a series of reports was published in which the separation from the reaction products of C6H414gBr and also of the dibenzolohromium with waterless chlorinechromium beside "pentaphanylehromhyclroxi- de" and "tetra" as well as "triphenylehromiodideall is descri- bed by Hein. According to a bold, but not precisely proved me- sumption of Zeiss, the polyphenyl derivatives of chromium have a common bis-aren-struoture. If it is assumed that in the chromium iodides (n-benzol, n-diphenTl) and di_(n-diphenyl)_ chromium the diphenylgroups are covalently connected, 10 % CARD 1/3 of D should be expected in the diphenyl separated after the On the structure of organochromio compounds. 2o-6-30/59 reaction with LiAlD4 . If, however they have a B-structure (illustration 1) diphenyl would contain no deuterium. The composition and the yield of the organic products of the light dispersion of the organochromic compounds in the chloroform agree well with the B-structures. It is known that the compounds of the B-series are paramagnetic and have the magne- tic moment = 1-7 of the Bohrs magneton. This corresponds to the. existence of a not coupled electron in their molecule. There- fore, the photographing of the spectra of the 'paramagnetic electron-resonance of such compounds was interesting' in order to obtain data about the localisation of the free electron. The absorption spectrum of the aqueous solution of one of these substances (III) is shown by illustration 2. The existence of a superfine structure and the qualitative analysis of the intensity distribution shows that the not coupled electron is in interaction with the hydrogen nuclei of the aromatic rings. (2 illustrations, 1 Slavic reference.) ASSOCIATION: Scientific Research Institute for Chemistry at the Gorkij State University "N.I. LOBACHEVSKIY". MOSCOff PHYSICALITSCHNICAL INSTITUTE. Institute for Chemical Physics of the Academy of Science of the CARD 2/3 U.S.S.R. 20-6-30/59 On the ntructurc of organochromlo compounds. PRESENTED BY: N.W. SZMENOV, Member of the Aoademy. SUBMITTED: 4-3- 1957 AVkILLBLE: Library of Congress. CARD 3/3 A U",,,'-. OR TSLTKOV YU,D-,VOY!MDSKIY V.V.,RAZUVAY_1-'V G.A., 20-1-32/54 SOROKIN 1u.V.,DO2,1HACF1_-'V G.A. T IT Lh Electron Spin Resonance in Some Sandwich Type Chro=aronatic Co_"pounds. -lektrcr,.,Vy- paraLagnitnyy rezonans v nekotorykh khromarromatiches- L ( soyedineniyakh sandvichevogo stro,;,fenija -Russian) PERIODICAL Doklady kkad.11auk S'"SR,1957,Vol 115, Nr 1, pp 118- 121 (U.S.S.i.) ABSTRACT In recc:rit t-i::.es increased interest was devoted to the study of the uentioned co.:,pounds of the ferrocene type,(Fe(C5H5)2),the ferrocene ion arid analogous molecules with aro;,-Latic addenda.In spite of -a great nu..-iber of' papers on this subject,there hitherto exists no general theory which mi~5ht explain the present data on the "sandwich"struc- ture o'l these molecules.Their fori:iation and steadipess cannot be ful.- ly explained by the ~;enerally accepted conception of valence.The da- ta obtained indicate that in the majority of compounds of this type the lina,.7e of addenda with the complex-forming atoms is of a cova- lent character.This is especially indicated by magnetic measurements. Accordin.- to the latter these materials are either diaz-Tiagnetic or they possess a magnetic momentum which correspond s to ont~,two cr at -..o5t three ron-paired electrons.The ion salts of these metals of such coi:ipounds by the L~ietiiod of electronic paramaZoMetic resonance (called EPR in the followincO have hitherto been desc-ribed in neu- blications.The presiant paper chives .-:,~_asurements of the _*-'PR spectra of the folioz-in8 cGii-.Dounds: CrtC6H6)2J (I),Cr(C6H5)2J (II) and Cr Card 1/-, V 0 ). The static oa,~;netlc susceptibility 1 ("(1115 - C05- C6H5)2 C6H 5 (111 Electron Spin Resonance in Some Sandwich Type Chromaro- 20w1-'12/54 Matic Compounds. of these materials correspondsto a single- non-coupled electron.The presence of a hydro,--en-overrefined structure of the absorption line in solutions of the materials II and III can be explained in two ;q,ys. -coupled electron and the positive charge of the 1.The non coi:q)lex are located onthe chromium atom. The estimation made or. the basis of this assumption shows that the density of the non-coupled 3(!-electron on the positions of the hydrogen atoms of the aromatic rings is sufficient to effect an "overrefined" cleavage of the EP11 s-Dectrum.2.The non-coupled electron and the positive charje are loca- ted on the aromatic addenda of the complex.The overrefined structu- re is in this case due to the interaction of the non-paired x,elec- tron of the aromatic rihg with the hydrogen atoms of this rinS.The extent of cleavage, the number of com-ponents and the ratio of their intensities are in this case dependent on the distribution of elec- tron density on the addenda molecule.The followinS facts speak in favor of the first assumption: a) presence of the anisotropy of the Z-factor in the materials I and II, b) the value of the g-factor is less than that of a free electron.The true picture of density di- stribution of the non-coupled electron is probably a superposition of the two extemum cases mentioned above. Card 2/3 (2 illustrations, 2 Slavic references.) 20-1-32/54 Electron Spin Resonance in Some Sandwich Type Chromaromatic Compounds. ASSMIATION: Institut khimicheskoy fiziki Akademid. nauk SSSR, Gorlkovskiy gosudarstve=yy universitet PRESENM BY NESMEYANOV, A. N., Academician, April 19, 1957 SUBMITTED 13.4-1957 AVAILABLE Library of Congress Card 3/3 T o o SOV/81-59-5-15249 J ? O'D (9) Translation from- Referativnyy zhurnal, Khimiya, 1959, Nr 5, p 167 (USSR) AUTHORS, Razuva~%rev, G-,A,, Brilkina, T-G, TITLE~ An Investigation of Free-RadioailResc-TIone of the MEER41 Complexes PERIODICAL .-- Uch, zaD, Gor'kovsk, un-ta 1958, pp 169 - 173 ABSTRAOT-~, It i!~ _--hown that when Li[B(C6H ats with Hg in 5)412LiBr (I) intera, CHCI C H HgC1 is formed, which proves that the M[B( -type J;x'605 C6H',)41 5-;~ds are capable of reacting with Fg with the comp C mpol formation of only one free radical from the elementorganic anion. NH4[B(C6H ) C10H ] (H) and K[B(C6H )3c,OH7] (III), when reacting 5 &C, 7 with Hg in , 3 form 01--dinaphthyl mercury, which, in addition -to the absence of phenyl derivatives of mercury, points to the Primary break of the naphthyl radicals from -the complex anions st-idied, The thermal decomposition of I! at 120 - 1300C causes the formation of naphthalene and tripher-,yl boron ammon:Late, i.e., the mechanism of the thermal decomposition of the anion also Card 1/2 takes place with the separation of ons naphthyl radical from the ill 6 Z5 sov/81-59-5- An, In"'astigation of Free-Radloal Reactions of the M[BR41 Complexes --omDlex, II and III are obtained by their precipitation from the aqueous rK Solullion of Li[B(CO-5503C.10H 7]9 which is synthesized similarly to I (G. Wittig .hers~ Liebigs Ann addition of and ot ~h -m., 1949, vol 563, p 110), with the ~TNC' or 011, respectively V,,A, Card 2/2 660CXt 30V/81 ~501-8 - 2 642 L' I-TY-anslation from.- Re--'I-Zr-atIv-n-yy zhurr-.-L--,. -Khimiya, !9,1z.9, '-q:i- AUT-MORS Razuv~qev, G. A , 012 dakop, Yu. A TIME: The Den-arboxylizing RP-ac-.t-Icr- of Orgsx-ic Mer SeLts -L EERIODICAL. T-r.- po IftUmii I khIm. tekhn.-,Iog., 1958, Nr 1, p& 178 - 181 AMTRACT--, The'possibility has been st;udied cf inItACtimg a c-haLll r-Saction of de- carboxylizing maroury sal's ,%-f' organic ac�ds with R3024, radicals forin.~d in the thermal deccmposIt'lon of peroxides or ~4-4 -:;he photolysis of mercu2:7 salts. In the heatirg of' a solution o--:' 0.047 mole of Hiz acetate (T) in glaelouls CH3COOH with 0.01 mole of /U, -n,'.'.robsn-zovl p6rojuds (Ti) the separattion. o-~ 3Fgo'o^-F- C02- and the formation of 0.032 mole of CH was obsez-vad. The reaction, proceeded In the-following (CH 3C 2)2~~ + 0,2='-q-61-OT~C00- ---5' -0- 1 (CH3CO2) 21;-9021"~%HO021 -0 + C-L--- C~02* 41 3H9Oe'-O"T3 + + C02 + Gli CC) ** II. was takA--n Dr~eventliig -th~ dee -11--loxylizing oft the II-COO* r2c2s, the stability of w"hq-A-b- increass-z along the series R C6H , The n-itrobenzoatte grvu:~ ^t d N02C6H4- s r-, -am the st proca-eds wi-,h diff-"~IIwvlt,,jr cz2oxyllzed. Tn a ~76f% m,-d:i on I a-r, Card 1/2 and the yield of M is -7C A 6-hcun Irradiation of a C 66o(x Tn~: Dei~.axboxyllzfng ssa:~ts ISOT/81-59-8-28-424 bclling solution of 0.01 moie of v -Y~- *0 .,Hg I-zads to the -fonmation of (C :at d! a Z: y 1q, .- P- H COOH and C:02, During A-rr lat'on of :,;' ~x.~ 0"i .Irv.F~d In bol!Lng ~,r!30H, Cje,=,-- d~l ~a:, 27. a.~ c-ni-vW a ' 2 equation. I.Ir + Ch-30H -- W T4 --0 0 f I A--,:- anei- -D" a ma-d-lum of boil.!-ng lz -ii,jugatQ:l C6.e*5CO2---rad'L(-!al "formation. of C~6B6) 0. Card 2/2 85372 1 3/081/60/'000/0 17/004/0 16 A006/P.00 I ReferaL- '_vnTy zhurnal, leiim' a, 119E0, MC - 17, p, 63, # 68688 -Y 77:,t1n,wa, L.M., E-,1ILS. V~S~ C.-m-, -n d s as ca~aiy~~tstf Oleftn FclymerlzatioO in'icrma- T% k~,t.,_rn.i i kh1m, tekk"nC.-_,,, 1958, No~ 0 _3, pp. 6.59-663 -ha-~,-,he TiCI TI H7)4 s7stEm is an effective ':.! ra e m ar - of TIC14 to Ti(iso-OC31~)4 -a !quid pclymer is f,:rrr..eJ consisting of wnsaturated hydroca bons :-ain. The f -Ilowing titan-D-organic c-_mpounds~are synthesized: cy~lo_%"Ijanci 1~ is established that these se--C4 Y :1,:, torage resulting in 'r:he formation of titanium, nLZ 6 is an ac_-Ilv~ catalyst in the 1-clymerizaticn of olefins (propy- s-yrene), The authors' summary I --1 Thz i_Q -he full tlxansla-ic_,n _-,fL 'he _-_riginal Ru3slan abs-!;ract. 307/8.2-59-8-27394 Tranz-1ation from. Relferatllvnyy zhuma-- YhImIya, .1959,, 'Nr- 8, p 213 (USSOR) AUTHORB, Razuvayev, G-A... VaZ:Lleyskaya, N.3- TITLE~ The Reaction of' Ca~bcn TE~trac.WlorldlWlth Cyclobexanol PERIODNAL~ Uch. zaD. Gorlkovsk, un-tal, 1958, Nr 32, rc, 17.r, - 178 AMAIRACT. The heating of cyclohexan--l-, with an- equal alnount of CC14 :L-~ a saal~d ampoule (30 - 35 holairs at 200 -' 210ol") Is al~lt,:=janled by debydrogenat-1-:Ln, leading to CHCl and ovo-Ighs~xan-=-a.01 83'~multaneo-asly wit-h the dehyd-r-o- 2 genatIon. the delydration of I to cyclohex.:--s tak~-z plac-5~ As a r--s-jzl* of secor-dar7 pro.,,ea--*,,:yczlohe-k:y-I c1-0c:-ide and a mixture, of dicyoloher-vl chloride isomers are formed, Th-z is poll-Ited apparantly by a small quantity of --yolohsxw_y-'Icyolohaxyl chlor-Ide. L, Khayfits Card 1/1 'UTHORS _-.azuvayeL._~~ ?Jinsker. K, S. -3C/~o T I'1=" iolymeric. C,,lorovinvlneroxide (Polimernaya pere:~is' khlor- istoa-,o Vinila) FE-7ilODICAL: 4':hurnal Obsh.-,hey 1'11imii,10.58~.Vol.28,Nr 4,PP.983-95`1(US3R) A'T. In the present Paper the authors have separated the :~-.eri(~ c",lorovinylperoxide compourds and their structure, !',croovor they have invecti,-ated th.31'r "ro,-Ier- ties-. t',eir reactivity as well as their influence on the quality and -,"ro _' ei-ties of the polymer. Because of the irotability cf those comz)cunds and because of the diffi- cii1ty of cbtaininC a suffic-.ent Quantity (all 0-~erations carried ou~ with some dozens of milliGrams separate- ly produced for each ex~leriment) it was not possible to senarate the precipitated chlorovinylperoxide. it c~n be _,.-.sumed th~Lt dur~n,-, t*ae oxidation of chlorovinyl the development of th 'e polymeric peroxide takes place all, the ex-,ense of the co'clyMer-lZation nrocess of' the chloro~ vinyl with oxy-en. '-'he formula for the idleal 1 : I co- Card ~)olymer of the oxy,,,7en an,' of the chlorovinyl ;-iniOt be C1 Cil !."!T tj 7 1" 20 -- 1: ... 3 0., f" 0 it i,; euny '~o ;ompu 'f,,~ that ir. th.~! .%re.4,3lied portLon of the poly,jeroxidle 33,86 'If of oxyj~En 37:59 of c1ilorine Cl = C.,,-105. As t.~-Ie Poly- 1-le con-La-lneo, C r c, V -1 r. Y-p e r, a. e s ne ither Durified nor re-- cry E; -.,a I I i z ed , i t n be ar,::,umed -th --, t the -respec t ive com, -jound --obob-!-, hL-s stru-:ture v.,rith, rojular alter-- n.--. 'Lion o~~' the --,.onds I --CH-CT1Cl00--)', The infrared spectrum inif the ---arbon totrac'-loride soli, tinn an iiitens-~~ ~wl ,-;ide adsor-tiop. band at F333 cm cf u.ie in-dispensable C-0. bond. vihic",-, is characterized -For conT;l ound--, as as a strong cdoorpticn at 1060 cm- ': which can have devel oned b.-- cause of LAO presence of -b 0 0.- ~;roups. The extraordinary robi4li-- ty of tl,.e chlorinel atoms ir, -`11orovinylperoxide -ust be c.-:phusized. Dur,L'n,,-, the lhydrGlyois C~ lor4re --!ready a' low atures splits off from the -17,oly-eric molecule '-.Fi7ore ','-reri~ents aith tl~e initiLtion cf the -.-oly- a r G~ dif-rerent -oroners wilth L Polymeric Chlorovinylperoxide 7 9 - 26 vinylperoxide hive shown that they cause the polymerization of styrene, vinylidene chloride, chlorovinyl, butylacrylate and methacrylic acid. The facts that were obtained durin- the investigation of the properties of the polyvinylic chloride in the initiation by polymeric chlorovinylper- oxide imply the presence of a peculiar block polymer. One p---Lrt of the latter has a polyperoxide structure and the other has the structure of a real polymer. Thus during the polymerization of the chlorovinyl, the molecular oxygen hasq)art from an intense inhibiting effect also -- negati,.e effect on the quality of thedeveloping polymer. This polL,7-er has a lower decomposition temperature and a lower molecular wei~;Iit than -- polymer produced by ordinary initiators. The ~iiminution of pi-I in the reaction medium during the suspended polymerization of the chlorovinyl can be col,ditioned by the presence of the molecular oxygen-oyiin~ to the hydrolysis of the pol-,Y:eric peroxides, rlevelopin,'- durin,-~,- tie inIaction ueriod. Card 3/4 1 olymeric, Ch'Lorcv-ir..yli;cruxide 79-26 -4--30/60 aut'icj-= -:-odit, A.I. Rirlellshteyri withhav:Lag made the zpectroE;co~)ic analysis of 1;k-- polym-ric percxicti~-. Tin-ere are 1, z; 2 e_~ -- ~ Les, aad 23 refexer-ces-, 11 of which --re Soviet. SUBMITTED. D-acembex 15, 19~37 Card 4/4 AUTHORS: Etlis, V. S. , R~azuy ffv,~.J;.. A. 79-28-5-2o/69 TITLE: Synthesis and Properties of Some Aryl Derivatives of Thioxanthenol-5-Dioxide Having Indicator Properties (Polucheniye i svoystva nekotorykh arillnykh proizvodnykh tioksantenol-5-dioksida, obladayushchikh indikatornymi svoystvami) PERIODICAL: Zhurnal Ob--hchey Kh-imii, 1958, Vol,, 28, Nr 5, pp,,~ 1225 - 1227 (USSR) ABSTRACT: As was already reported b,, r the authors (Reference 1) they obtained in the sulfonation of some aromatic compounds of the Ar2CH - RI -type (where RI = H, alkyl or aryl),,on certain condition~,derivatives of thioxanthenol-5-dioxide.7 which have indicator pro-perties. It was of interest to investi.-ate the influence of various aryl aibstituents on the color of the comDounds obtained in sulfonation as well as to investi,-ate t1heir applicability as indicators in acidimetric determinations. For this purpose the sulfonation process of 4-benzyl diphenyl., a-tenzyl nalhthalene -ind a, ct I. dinspi~thyl methane was investi,~ated. Card 113 This process was carried out -.,,rith 2j - 1'o~o oleum at hiE;h t 79-26-5-2o/69 Synthesis and Properties of Some Aryl Derivatives of Thioxanthenol-5-Dioxide Having Indicator Properties temperature. The final products were sulfoacids ahich have indicator properties similar to those described earlier (Refer- ence 1). In neutral and acidous media these compounds remained colorless and only colored intensely 3n the addition of alkali. Also the color of the one or the other compound depends on the nature of the substituent, which can be seen from the absorption curves in the visible spectrum of alkaline solutions of the mentioned compounds in the picture. The synthetized compounds are easely oxidized by potassiun permanganate and on this occasion lose their capability of changing the color in alka- line media.. They can be used in the filtration as indicators. The absolute error in the titration of various organic compounds on the avera.-e amounts to * cl,3,~S. Starting from their properties and from the analysis their structure can be given by the formulae (I - III). A simple synthesis of a,al -dinaphthyl methane Card 2/3 of naphthalene, and of the a,a"-dichlorodinethyl ether 79-28-5-2o/69 Synthesis and Properties of Some Aryl Derivatives of Thioxanthenol-5-Dioxide Having Indicator Properties nitrobenzene in the presence of AlCl were elaborated. There are 1 figure and 5 references, 3 of hich are Soviet. SUBMITTED: June 8, 1957 Card 3/3 .1UTHORS: Razuynyev, G_ A,,_,__Bobinova, L. M,, SOV/ 79-28-6-43/63 Etlis, V~ S. TITLE: Orzanozinc Com,.)ounds,Catalysts for the Polymerization of Propylene (Tsinkorcaniclieskiye soyedineniya-katalizatory poli- merizatsii propilena) PERIODICAL: Zhurnal obshchey 1-himii, 1958, Vol. 28, Nr 6, pD, 1623 - 1626 (USSR) ABSTH"ICT: The authors regarded it necessary to investieate the catalytic activity of organozinc compounds (diethyl-, dipropyl- and di- phenyl zinc) for the polymerization of propylene, Diethylzinc with an addition of titanium chloride proved to be an active catalyst. In the presence of diethylzinc and tin tetrachloride (or sodium isopropylate) propylene does not polymerize. The in- fluence of the reaction temperature on the polymerization of propylene, of the reaction duration, the composition of the cata- lyst (molar ratio between Zn(C2H 5)2 and TiCl 4(furtheron denoted by C) and of the solvent were investigated-, It was found that the best yield of polypropylene was obtained at llo-12oO(Tab 1). Card 1/3 After a lonjer duration of the polymerization (from 3 to 5 hours) Oreanozine Compounds/Catalysts for the Polymerization SOV/79-28-6-43/63 of Pro;)ylerle the yield incrc:ased only little (Tab 1). The composition of the catalyst has a strong effect on the yield and the quality of the polymer. The best yield was obtained at the equiimolecular ratio between Zn(c2H 5)2 and TiCl,,, hovieveri, in this care the polymer was obtained as an oil of varyini.; viscosity. At C=3 a solid0 propylene was obtained (yield - 30A, melting point. 150-158 , Mo- lecular -,-.,eijlit = loooo--18ooo). On a further increase of C its yield decreased considerably (Tab 2). Reptane and isooctane %vere used as solvents for the polymerization, the first mentioned supplyin.- somewhat smaller yields (Tab 3). The substitution of zincdiethyl by zinc dipropyl and zincdiphenyl chanCed only little the activity of the catalyst in -bile polYmerization of propylene. Thus the character of the radial exerts only little influence on the catalytic activity of the orranozinc com-pound. The authors investigated the influence of the component molecular ratio on the yield and qu~:-lity of the polymer in the case of the catalysts Card 2/3 Zn(C3H7)2 + TiCl 4 and Zll(C6H5)2 + TiCI 4* There are 5 tables and Organozinc Compounds,,Catalysts for the Polymerization SGV/79-28-6-43/63 of Propylene 7 references, 4 of which are Soviet. SUBMITTED: May 23, 1957 1. Propeaes-Polymerization Card 3/3 AUTHORS: Razuvayev, SOV/7-1-28-6-40/66 Latyayeva, V. 11. TITLE: Reactions of the Acyl Peroxides lvlith Metals (Reaktsii atsillnykh perekisey s metallami) PERIODICAL: Zhurnal obshchey khimii, 1958, Vol. 28, Nr 8, pp. 2233 - 2239 (USSR) ABSTRACT': The authors were interested in investigating more closely the influence of different metals on the decomposition of symmetrical and unsymmetrical acyl peroxides in solutions. Special attention was paid to the reactions of the radioactive hydrogen atom which gives up its electron pair in alcohols. For this purpose decomposition reactions of benzoyl peroxide were carried out in methyl, ethyl, and isopropyl alcohols, and in chloroform, M and C 6H6 in the presence of metallic Na, Zn, Cu, Fe, Ni, Ag and Pt and at room temperature. A few reactio--s with phenacyli phenacylbenzoyl, and p-nitroben7oyl neroxide ware also carried out. The experiments with benzoyl peroxide showed that in benzene and alcoholsolutions and in tile presence of Ila (e. amalgam) and Zn, salts of benzoic Card 1/3 acid form quantitatively, but no salts form from the mercury Reactions of the Acyl Peroxides With Metals SOV/79-28-8-48/66 in the sodium amalgam. In tile presence of Ni and Fe in alcohol only some of the benzoyl radicals become anions. Free benzoic acid and aldchydes were found 4n the reaction products in addition to the salts. The inechanism of tile described reaction are probably thus: in one case the peroxide accepts two electrons from the metal and forms ben;%oaLe anions: (C 6H5CO 2)2 +Zn ---)2 C6H5COO-+Zn2+. In the otlier case the electron transfer occurs with the fOrl:L-atiOn of a benzoate anion and a benzoyl-oxy radical (see the second reaction diagram). The latter reacts with the solvent, the alcohol. In the case of acetylbenzoyl peroxide similar results were obtained, i.e.) acetate and benzoate in the presence of Ila, HC, and Zn r,.:acted in benzene in the same manner as in the alcohol solution; in the presence of Ni, Cu, and Ag acetates of tile metals and free benzoic acid were lound. In cl-,loro-or,~,-anic solvents chlorides of the mc-tals we--e observed to form initially. In the presence of platinum a hydros.-enation of the peroxide with the alcohol llydro~--en occtirred. The table indicates the reactions of the acyl peroxides Card 2/13 'with th-- r.-ietals. There are I figure, 1 table, and 11 re--'er- Reactions of the Acyl Peroxides With Metals SOV/79-28-8-48/66 ences, 7 of which are Soviet. ASSOCIATION: Gorlkovskiy gosudarstvennyy universitet (Gorlidy State Uni- - versity) SUBMITTED: JulY 8, 1957 Card 3/3 AUTHORS: Spasskaya, 1. F., Etlis, V. S., SOY/79-28-7-21/64 Razuvayev* G. A. TITLE: The-Chlorination of Ethylene Glycol (Khlorirovaniye etilengli- kolya) PERIODICAL: Zhurnal obshohey khimii, Vol 28, Nr 7, pp 1827 -- 1851 (USSR) ABSTRACT: Contrary -to-the chl-orination of monovalent alcohols only few pub,ld-cat,ions, are- known -on that -of -bivalent and especially of ethylene- glyaols.- -The anthors -were -interested in a detailed this--reacti-on. The chlorination of ethylene glycal- takes -plaxye- sufficiently rapid only in ultraviolet light .~at,room-t~emperat-ure,--~with-a great amount of heat being developed (maximum-up-t-o,12T0-)-with a-pronounced absorption of chlorine, -and the in-it-ial- we-ight inc-reasing- by 70 - 80%. The final product conaist-s- o-f- 27% P-ahlaro-ethyldichloro acetate, of 15% of a -cycl-ic- acetal- not. d-esor-ibed -in papers (A), 12% H20, 11% of dichloro aeeta-ldehyde, 11 % chloroethylene hydrine, 6% dichloro- methyl-1,3-dioxolane and of an admixture of oxalic and dichloro- Card 113 acetic acids. The cyclic acetal corresponds to the formula The Chlorination of Ethylene Glycol SOV/79-28-7-21/64 CHC1 2- CHO-CH 2- CH 2- OCHCHC12 L 0_-CH2-~CH20J (A). This structure was proved by cleavage with concentrated hydro- chloric acid under-the formation of dichloro acetaldehyde and chloroethylene hydrine. The chlorination only with a previous addition of SbC1 yielded about the same composition of the 3 mixture, however, witho'utthe acetal of the ethylene glycol and without the CHC1 2CHO. Prior to the separation of the mixture it had to be liberated from the-Aisturbing hydrogen chloride. In order to explain the nature of-the high-boiling products it was of interest to subject the maim product of the ultraviolet treatment, t.he-p-ehloro-ethyl dichloro acetate, to the conversion with..chlorine::T.he,ohlor-inat-ion experiments in the ultraviolet range_yielded~a.,_(~, 0~, 511-tetrachlaro-ethyl ester of trichloro acetic acid--Thus-,-i-n the-case of the above mentioned chlorination reaction in the ultraviolet range, or with a catalyst, the oxidation and chlorination processes, i. e.jthe formation of Card 2/3 ester and acetal, take place at the same time. The Chlorination of Ethylene Glycol SOV/79-28-7-21/64 There are I table and 10 references, I of which is Soviet~ SUBMITTED: May 31, 1957 1. Ethylene glycol-Chlorination 2. Ultraviolet waves-Chem.-i-cal effects Card 3/3 AUTHORS: S;Dasskaya, I. F., Etlis, V. S., SOV/79-2a-11-22/55 ?-azuvayev, G. A_~, TITLE., Chlorination of Olefin Chlorohydrins (Kilorirovaniye k1ilorgidrinov olefinov) PERIODICAL: Zhurnal obchcl-.Iey 1himii, 1',-i58, Vol 28, Nr 11, PP 3o04 - 3008 (USSR) A 1)'S T R A C TThe reaction of chlorine -with olefin c*lalorohydrins is little investi,~ated. T`,ere --re no re-oorts or, 'he chlorin-Auion of the propylene chloroh,,drin. The aim of thic paper was th-c --~t ion o--F' the and nro,~---,---ne chlorohydrin. The chdori-nation of et'iyle-lie c*-1-oro'id---1,--i,- w--s carrier-' out ui-.der ultr~- ---'Uion nt 30-4o0 0, 90-1000: It violet i:: --dJ , 60-70 30-400 in the precence of 1"'7 ;,iater, at 50-6o0 in the presence of marble, and a170-800 in the presence of 0*5';~'., acetyl cyclohexane su, fonyl perox-ide. The and (V) -.,;e~e separated fr,D,2 t-.,P- -.~rodi-cts of the chlorin-tion. The d2at- on tne compo2ition of tile forr-ed zi-iX-.ures a-"e Card 1/2 mei-.tio-ned in t---'L~le 1. As the P-chloro-et'a7l dichloro Chlorination of Olefin Chlorohydrins SOV/79-28-11-22/55 acetate was found in all experiments in the company of dichloro acetalOehyde of dichloro acetyl chlori0e, it muct be a~'sumed Vi-t an the action of c,,lorine on (Can oxidction and chlorination take plLce easily, accom.-,)~-.n-lod 'Q,-- secon~larY for~--,LLions of '1'-e acetal and, e'U'-..er. T,-.c free --I,iloro acetalde'-Yde could not be sencrated, izo f'ormat.ion is, be,.,ond any doubt, di,,.e to tle acet-al (V) separated in most ex.-~eri7e-nts. the r-2action of clllo,,ine with -3t!-.ylc--~.e -.-.ydrin could be by :ne--.ls of t':le r--,~-ctiors -ncntioned in the sche-,.e. In the c1lori-ation of propyl---,-c- chiji-oh.-drin u,~r]e-- ultraviolet irraz'1-4'~tion at ~o-1000 a mixture of chlGri-e 'Ketones is formn-d, from -.-,'hic"- tl--~c 1,1,3-tri-chlaro acetone is senarated - and was also identified as suc'---. There are 2 tables and 12 referc%--.ces, 4 of which are Soviet. SU2=-1T-ED: September 30, 1`57 Card 212 AUTHORS: Razuvayev,_ G. A., Petukhov, G. G. , Artemlyev, A. G- 20-118-5-31/59 TITLE: Reactions of the Exchange of Radicals in Presence of AM 3 (Reaktsii obmena radikalov v prisutstvii AM 3 ) PERIODICAL: Doklady Akademii Nauk SSSR, 1958, Vol. 118, Nr 5, PP. 96o-963 (USSR) ABSTRACT: The authors proved that the exchange of radicals of organo- metallic compounds with the "solvent" takes place in reactions of the radical as well as in ionic reactions (reference 1). In the present paper the authors wanted to examine the possibility of the progress of the exchange of cations R+ + R*D < ~"R*+ + RD (1), by using deuterium-containing "solvents" and AM The use of this last catalyst was chiefly investigated iA*reactions of one acid type (reference 3). Exchange reactions which take place with the participation of carbonium ions we.re investigated by means of deuterium in reactions between aliphatic hydro- Card 1/4 carbons and H2 s04 (references 4, 5). For the investigation Reactions of the Exchange of Radicals in Presence of AM 3 20-.118-5-31/59 of the exchange of cations haloid and aromatic hydrocarbons were used. The chosen substances show as exchange systems a double interaction with AM - the haloid compounds show carbonium ions in presence o~'AlCl3 , as is well known (references 6, 7). Here the exchange can take place according to the equation (1). Aromatic hydrocarbons form a n-complex with AlC13 in which they are subjected to a strong protonization (reference 8). The exchange can take place according to the reaction of the acid type. Table 1 shows that chlorobenzene-deuteriobenzene as well as cyclohexyl- deuteriocyclohexanechloride carry through the exchange in presence of AM 3 until the state of equilibrium. The exchange takes place in these systems according to the equation (1) with the participation of the phenylcarbo-cation and the cyclohexylcarbo-cation. It is possible that the deuterolysis of the deuteriobenzene favors the reaction of the hydrogen exchange. This condition, however, is not necessary. Contrary to these systems the hydrogen exchange between toluene and deuteriobenzene (table 1, experiments number lo, 11) only takes place according to the equation Card 2,14 (2) (acid type). The particles that take part in the exchange Reactions of the Exchan~~e of Radicals in Presence of AlCl_ 20-118-5-31/519 are a proton and a deuteron. The exchange Drocess can also be represented as a reaction of electrophilic substitution. By 2 isotopic markings (deuteriotoluene and radiobenzene 1-6 C14.)it was proved that besides the exchange of hydrogen there is also an intramolecular migration of the CH group of toluene towards the benzene nucleus. There is practically no exchange between deuteriobenzene and cyclohexane and between cyclohexane and deuteriocyclohexane (table 1, ex- periments number 12-15). This partly confirms the correctness of the conclusions drawn above. There is no exchange of hydrogen if one of the components forms no n-complex with AM (cyclohexane) or if the formation of such a complex is not accompanied by a protonization. In chloronitrobenzene and bromoanisole the influence of the substituents on the exchange was to be investigated. In spite of the expectations it was proved here that only a limited exchange occurs between p-chloranitrobenzene and deuterionitrobenzene, and between o-bromoanisole and deuterioanisole (table 1, experiments 6-9). These results do not quite agree with the Card 3/4 fact as stated above that the radicals located at the oxygen Reactions of the Exchange of Radicals in Presence of AlCl 3 20-118-5-3,1/59 atom are stable (reference 11). Finally the experimental methodology is given. The results of the analysis are included in the tables 1 and 2. There are 2 tables and 11 references, all of which are Soviet. ASSOCIATION: Gorlkovskiy gosudarstvenny-j universitet (Gorlkiy State University) PRESENTED: October 23, 1957, by V. 11. Kondratlyev, Member, Academy of Sciences USSR SUBMITTED: July 17, 1957 Card 4/4 AUTHORS: e 9 pond, ng SOY/'20-122-4-22/5! Member, A,-.ademy of S---J en.-.es j USSR, Bob-inova, L. M, , Et-.Iip, V. 13. TITLE: Producl-fon and Properrt.ies of Several Tri~.hloro-.TJtane-Alkoxy Compounds With Sez,:indary and Tertiary Alkyl Groups (Poluchr-niye i svoystva nekotorykh trikhlortitaualkoks-i- soyed.;neni.y ,j vtorichnymi. i trptichrtyml- alki.1,nymi gruppami) PERIODICAL: Dok-*Lady Akadem-i-i nauk SSSR, 1958, Vol 1102, NT 4, pp 618 - 620 (USSR) ABSTRACT. Some authors believe the 'titars :Drgarn.-, compounds to be the Initiators of 'the po-lymer~ 'zat2on of the alefines, therefore, lvhe,,,r hatra been caxefull,,- Sansidered recently as possible intermediate products of the reaction of trialkylaluminum with titarle -retrachloride (Refs I - 3)- In the present paper some t-it-ane --ompounde of the type TiCl OR were syn- thetized. and irvrestigated. in tnis cinne- ti 3n R denotes 5he secondary or tertiary grour. Sin--e in the synthesis, according to relf-arence 6 an -isuffic-ant, puz7P compound was obtained, the authors used lw~:;propyl s.3cohol and an excess Card 1/4 of T4-Cl- 4 *-in a oetxoleum point, 60 - Production and nf 6,everal '11 ,, hz 3OV/9(,':--!-22-d-22/57 Titane-Alkoxy Cowp~,-t:.n,~s W.-th 3~--.cmndary and Alkyl Groups 70') for the sy.,,chea-'s of J -"C ff,OTiC! at approximately 0. Crysta-s of the p'0-27k-i were pre,iipitat~d from the fil-trate after a paxt, :)f sh-a had bee~n dizit-illed off ani :~noled doRri, Se~;oridary C4HOOT4C;. 3 and 1QTirl %rh.i~therto not dpscribed) were In a 9A,41'r Pa I "I ~- - - y - b u ~ by d i s t i I I i L. g on d e r ,wa-,~uum In -.Drde~ rs~-duc~p the deooMD,,-)s4.ti-on of the said ,-,mpn - -- Th~ ti-t;,~7 qr~, howavex -unstable 4n limdo (Tab7--- o P ~,~ r a z- -T,!.) ~~:Lmilar ---Ompo~-,.nds Uri-1h primary groups~ In the c;asa of gase-Dus p-r*du:~ts cs.-,ape and titane oxyc~hlo~:-Jde ic. p:-odu~eI. The following compounds were fu-rthe.7*m,):7;-- J,dentj--f.Led in tha :base of isclation of liquid products -under hydrogen chloride, alkylehloride, i--C Ti,C)- from the secondazy C H OTiC1 and C H OTit^,l f A 6,11. Fur~he:rmore, polymer'-zation pvogui~ts ~f the 01~3:lnes ;ere closely adscrbed 0" Lhe surface of the oxychloride. Table 2 c;hnwg a balan~;,~ cl this de--ompos-itAion. Table 3 gives the phy-ica1-c;hemP---Ca-', DT,Dperties of the decomposition products. Card 2/4 From the isolal.nd Tjr;iducts it may be assumed that the Production and Properties of Several Trichloro- SOV/20-122-4-22/5'1 Titane-Alkoxy Compounds With Secondary and Tertiary Alkyl Groups primary decomposition process of the mentioned compounds is the formation of the titane oxychloride and of the radicals. The latter might then yield one olefine and HCl or an alkylchloride. Finally the authors were able to prove that the titans oxychloride effectively catalyzes the reaction of the hydrochlorination of propylene, iso- butylene, and cjc1ohexene. Alkylchlorides with good yields are formed in this case. No inverse reaction (dehydro- chlorination of alkylchlor-ides) takes place in the case of decomposition of the titane organic initial compounds. On the strength of the above-mentioned results a decomposition scheme is suggested. Further ranges of application are finally given along with exemplifications. There are 3 tables, and 7 references, 2 of which are Soviet. 6UbbliTTED june 17, 1958 Card 3/4 Preduction and Pxoperties of Several Trichloro- SOV/20-122-4-22/57 Titane-Alkoxy Compounds With Secondary and Tertiary Alkyl Groups Card 4/4