JPRS ID: 10314 USSR REPORT LIFE SCIENCES AGROTECHNOLOGY AND FOOD RESOURCES

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JPRS L/ 10314
10 Fek~ruary 1982
- lJ SS R Re ort
p
_ LIFE SCIENCES
AGROTECHNOLOGY AND FOOD RESOURCES
CFOUO 1 /82)
~BIS FOREIGN BROA~CAST IN~ORMATION SERVIGE
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� JPRS L/10314
10 February 1982
USSR REPORT
LIFE $CIENCES
AGROTCCHNOLOGY AND FOOD RESOURCES
(FOUO 1/82)
CONTENTS
ECOLOGICAL PROBLEMS
Searching for Selectively Active Insect Acaricides 1
INUUSTRIAL TOXICOLOGY
prin~ipai Tasks Associated With Search for New Pesticides......... 10
- PESTICIDES
- Dimethyl Phosphite Puri�ication by Vacuum Distillation in F~lm
Rotor Evaporator 22
~
- a- [III - USSR - 21n S&T FOUO]
FnR (IFFTf�r+T I1SR nNT.Y
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' ECOLOGICAL PROBLEMS
SEARC~E?ING FOR SELF.CTIVELY ACTIVE INSECT ACARICIDES
Moscow INTENSIFIKATSIYA SEL'SKOKHOZYAYSTVENNOGO PROIZVODSTVA I PROBIEMY ZASI~HITY
OKRUZHAYUSHCI~Y SREDY in Russian 1980 (signed to press 31 Oct 80) pp 156-165
[Article by T.A. Mastryukova, Institute of '~etallo-organic Compounds, USSF',
Academy of Sciences: "Methods for Searching for New Selective Phosphorarganic
Insect Acaricides Which Do Not Leave Harmful Residues in the Environment," from
book "Intensification of Agricultural Production and Che Problems of Environmenta~l
Protection," edited by T. I. Lipatova, Izdatel'stvo "Nauka", 500]
[Text] Agricultural production during the second half of the 20th Century has
invariably been associated with the use of agents for protecting plants against
weeds, pests and agricultural plant diseases. This leads to a disruption in the
- existing ecological balance in a given region and it naturally and necessarily
serves to contaminate the surroundings [1].
Since we cannot cease aur efforts directed against harmful organisms, we must employ
preparations which, following th~ completion of their effective acti~n, wi11
disintegrate completely into non-toxic residues; on the other hand, the agents
employed must be highly selective, destroying the harmful populations but not
' disrupting other ecological balances in the region.
1
i
If we look at pesticides the principal means fo'r combating harmful organisms in
; agriculture, then it must be stated that first generation pesticides do not meat
~ these reguirements. They are nighly toxic with regard to warm blooded animals and
! they are characterized by a broad spectrum of action, a�fecting both harmful and
useful organisms and they are highly persistent, that is, they remain in the
~ atmosphere for a long period of time.
The toxicity of such well known �irst generation phosphororganic insecticides as
octamethyl, thiophos and aystox, for warm bloaded aniroals, was 1-7 mg/k~ (such as
~50~~ Which is�at the toxicity level for potassium cyanide (~100 2�5 mg/kg).
Exactly the same high toxicity was possessed by the chlororganic derivatives, with
the exception of ADT; their toxicity ranged from 7 to 40 mg/kg. It turned out later
that they were especially toxic for fish (SK5~ approximately 0.01 mg/kg). Their
high Fersistence was extremely unpleasant; they could remain in the environment for
_ years, circulating among the soil-water and food chains and evenCually entering the
human organism. At the pre::ent time, all of these pesticidea are either completely
prohibit~d hy~ law or their use is strictly limited.
1
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H'OR OFN'1(7A1. l~tiE ON1.1'
As a result of intenaive studir�, rai�i'ted out t~y firms anci sci~rltific iYisCitutus, ttic~
following pes[icides have baan obtaiiied during [he past few decades second and
third generation pesticides which to a considerable degree lack the above
shortcomings. Their toxicity for humans and animals has been lowered by tens and
hundreds of times. It is ;3ufficient to state that the average toxicity of
preparations in use at the present time is on the order of 900 mg/kg. These
preparations disintegrate rather rapidly in the environment. Thus, thiophos, a firsC
generation preparac:ion, disintegrates in the soil only 35 perc2nt over a period of
2 weeks. This means that 90 percent of the thiophos decomposes roughly over a
period of 3 months. Phosphamide decomposes in the soil.two and a half times more
rapidly. Many second and third generation phosphororganic preparations decompose by
90-95 percent in just 1-2 days.
~
_ Thus, considerable success has been achieved during the past decade in improva.ng the
chemical agents used for protecting plants. At the same time, the tasks for
protecting the environment continue to advance newer and more strict require;~ents,
which i:~ turn stimulate a search for new pesticides~ Here there are two principal
1 tasks: first of all, a pesticide must break down in the environmer.t and not leave
harmful residues and, secondly, a pesticide must have high selective action as it
affects definite harmful organisms. It must be non-toxic for othe~ac arthropods and
certainly for humans and domestic animals.
All successes achieved up until now in searching for second and third generation
pesticides have been obtained as a result of tremendous research work, carried out
using Ehrlich's "trial and error" method. Thf_s is a very laborious and costly
path and with the passage of time it is becoming more difffcult and more expensive.
~ It is sufi{cient to state that during the past few years only one substance of more
than 10,000 that have been synthesized and examined [2] has bean introduced into
agricultural practice.
Another method of specialized research is based upon a thorough study of the
mechanism of the effect and metabolism of pesti~cides in various types of organisms.
Some results obtained from the secon.3 research method are set forth below. This
method made it possible to find new pesticides which have a high level of
selective action and which do not leave harmful residues in the environment.
Our work is based upon the following consideratione. The absence of harmful residues
in the environment can best be achieved if the preparation breaks up into fragments
which are already present in abundance in the environment. The szarches for
selectivity are based upon differences in the metabolic changes of substances in
various types of organisms. The substance is toxic for a given type if the metabolic
activation "exreeds" the detoxication and conversely.
It was on this basis that we arrived at phosphororganic esters, which contain
, residues of acetylated amino acids in a side chain [3-5]
A ~ p~X p 0
B ~ ~ ~ _ R _ ~ ~
~y
= 2
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A~ B c R0~ CH3~ C3H~~ X a S~ 0~. Y� OR~ OH~ NHCH3~ R� CH2~ CH(CH3)~ CH(C3H7-iso
CH(C4H9-iso) CH(CH2C6H5 ) CH(CH2COOR) CH(CH CH2COOR) CH CH2 SCH3 and othere. For
these compQUnds, extensive variations were no~ed both in t~ie A and B aubatitutes in
the phosphorus part of the molecule and in the amino acid residues. A high
selective action was established for substances of this type for insects and mites
on the one hand and warm blooded animals and arthropods on the oth9r. Conaiderable
importance is also attached to the fa~t that theae compounds, upon decomposing in the
environment, give off biogenic and non-toxic reaidues: amino acide, glycolic or
thioglycolic acid and phosphoric acida. We studied the mataboliem, toxicodynamics,
anticholinesterase propertiea and the toxicity of the substances themselves and also
their more important metabolites [6-8]. It was on thia basis that we succeeded in
~ developing a picture of the selective toxicity of the substancea of this typ~.
_ By way of an example, let us examine the data obtained for certain dithiophosphates
which we studied. A description of their physiological activity is furnished in
Table 1.
TABLE 1
Physiological Activity of Certain Dithiophosphates Derivatives of Acetylated
Amino Acida and Their R~0 Metabolites, With the General Formula being
C2H50\ ~ X
~ \
C~i50 sCH2C02~4i-R-~OOC2H5
- ~ N~ X x Cx5~ ~xr ~(n.�MOnb-
~x"Z)
I 1~T~ (~t X3 T~ns AX3
- lU-I40 S-~H2CH2- 00075 qI9 2000
"a~ll-5 0-CH2CH2- C~0035 q0095 250 2, 3� I05 I~ 6� I03'
i
i ll!- I4I s-CH2~ C3H~-xso QI7 Qp027 90 - -
_ ~Ill-I56 0 C3fi~-aao QIO q0058 75 9,2�I03 3~6�I02
LU-I20 s -CH2- QOIS (~QIS 750
GI-I55 0-CH2- - Qp025 qp052 75 I,22,�I04 4;I3�I03
~ ~J-I22 s-L'~i2 (~pIB g004 I000 - -
I CH'3-
~ 3I'~3 0 CIi3- q025 qp023 290 7~ 5� I03 I~ 8� I03
xey :
1. Aphids 3. Lethal dose50 mg/kg (mice)
2. Mites 4. Acetylcholinesterase
Here ~-140 is the selective insecticide,f~-141 is the selective acaricide and W-120
is the insecticide and acaricide of identical strength. At first glance, the data
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run Vrr 1~.1~11. uJr. ulvLi
in the table present a rather complicated picture and yet can be understood
provided one takes inta account the simultaneous or consecutive flow of several
~ biochemical processes, ~he presence of which is confirmed both by the data in this
table and by special studies of the metabolism and toxicodynamics.
Precisely what changes are taking place in these substances?
First of all, there ;.s the process of biochemical activation. It consists of the
oxidation ox the P=S ;groups of our insect acaricides into the P= 0. Judging by the
results of the study, it is dependent to only a slight degree upon the nature of the
amino acid.
- Secondly, the inhibiting of the cholinesterase P~q by the metabolites. Generally
- speaking, these are inhibitors of average strength. With regard to the ACh~
[acetylcholinesterase] of mammals, their activity depends very little upon the nature
of the aroino acid: the changes do not exceed one order. With regard to the ChE of
aphids, to the contrary, an expregsed selectivity is observed. For ZhSh-5 ) Sh-155 >
- Sh-156 ~ EG-33, that is, th~ nature cf the amino acid affects the inhibiting of the
CYiE of the aphids and in a ma~ner such that the introduction of the t~=branchings
lowers the activity. Here we see an example ~f a different specificity fn the AChE
for mammals and the ChE for aphids.
Thirdly, there is carboxyesterase hydrolysis. This is the detoxication process.
According to our data, the carboxyesterases in the homogenates of mites are more
active than those in the homogenates of aphids.
With regard to the effect of the structur~e of an awino acid residue, it must be borne
in mind that the hydrolysis bf ethyl esters of carboxy acids slows down upon the
introduction of the branchings to the (X carbon atom of the acid, especially with the
entry of the isopropyl group., Thus, our substanceg can be arranged in a series
~ according to the speed of hydrolysis: derivatives j;-alanine ? glycine >a~anine >
valine. Moreover, in the,case�of mites the~-analine and glycine reaidues change in
some areas
Fourthly, there is the inhir'_~ing of carboxyesterase. As it turned out, the P=0
metabolites of our substances inhibit the carboxyesterases. The valine derivative
(Sh-156) shows the greateat inhibiting effect. It is obvious that the worse a
, substance with a carbalkoxy group is a s a substrate for carboxyesterases, the
stronger it will inhibit tilem.
Fifthly, there is carboxyamidase hydrolysis. This is also a process of detoxication
which we did not study in particular, but judging by the metabolites revealed, it is
taking place.
Let us examine che experimental data on toxicity. `i'he,~ alanine derivatives represent
the first pair of substances. Here, as already noted, Sh-140 is the selective
inaecticide. It hydrolyzes well in the liver of mice and in mites and thua its
detoxication takes place more rapidly than its activation: thus Sh-140 is 8 times
less toxic for mice than its Ps0 metabolite, 15 times for mites and only twofold for
aphids. Owing to the fact that carboxyesterase activity ia only weakly expresaed in
- aphids, a good half of the Sh-14~ is activated in the Po0 metabolite, ZhSh-5 is a
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- very strong anticholinesterase for aphids (105). It is precisely this which explains
the high selective action of Sh-140 for aphids.
The second pair of substances valine derivatives. Sh-141 is a selective acaricide.
Owing to the valtne grouping, not only does its carboxyesterase hydrolysis take place
in a slow manner, but the P�0 me~abolite (Sh-156) inhibits the carboxyesterases.
Thus, oxidizing activation with the formation of Sh-156 is preferred for Sh-141 and
once the Sh-156 forms it terminates further deactivation by inhibiting
- carboxyesterases. Hence the P=S compounds and th.eir P=d metabolite are cloae in
toxicity.
In a similar manner, it is possible to analyze the third pair of eubstances
glycin~ derivatives. Here Sh-12d is an insecticide and acaricide of equal strength;
in this, instance the detoxication processes are expressed in aphids to a greater
degree than with Sh-140 and in the case of mites to a lesser degree.
~ We are obviously aware that the interpretation cited above is sufficiently
a approximate and thus it can be utilized far pr.edicting the selectivity of action for
substances of related types and for planning further experiments.
If the substances or products of their activation are very strong anticholinesterases,
then their carboxyesterase detoxic~tion will not be very ef~ective. This corresponds
to the general rule o� Unterstenhofer, according to which high activity is
accompanied by a low sel~~ctivity. At the same tin~e, this rule can be disrupted by a
very high detoxication level.
Allow me to cite data for a number of thiophosphonates (see Tab~e 2), in which the
COOR group radicals vary; X-- sulphur or oxygen. Here the phosphoryl c anpounds ara
strong and highly toxic acaricides which surpass the standard thiophos in terms
of their action. With regard to the P:S compounda and with the exception of thiophos,
they are strong insect aclri_ctdes and rathe~ toxic for warm-blooded animals.
However, NSh-8, an isobutyl ester, is detoxicated to a conaiderabl~ sCronger degres
than lower homologs: its coefficients of detoxication for mfce 6.6, for aphids
5.3 and �or mites 5.7. Such strong detoxication is obviously associated with the
- ease xn alkyl-oxygen disruption o~ the ~ielimination. As a result, we have a rather
strong insect acaricide which is not inferior to thiophos, but which is at least 20
times less toxic than thiophos. This is an interesting observation and an e~ually
interesting substance.
The effect of isobutyl prot~ction is noted in other instancea, for exaraple, in the
derivatives of the ~-1lanine,in which the monothioanalogs are strong
ar~ticholineaterases (1Q5). Here the isobutyl derivative is the least toxic for mice.
The fact that in this effect we are dealing with hydrolytic detoxication based on
a carboxyl group is revealed by examples in which the detoxication encounters very
strong steric hindrance with the introduction of the isopropyl group (valine
derivatives). The oxygen analogs of these substances are also strong
anticholinesterases (105), but the substances themselves are not only poorly
hydxol.yzed by the carboxyesterases but in addition they are also strongly suppressed
by them. Fi~re there is no isobutyl effect whatsoever.
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t~Ul~ Ui~t~ Il:leU. Util~: t)NI~1'
TAB I.E 'L
- Physiological Activity of Certain Methyldithiophosphonates Derivatives of
Acetylated Glycine and Their Monothioanalogs, With the General Formula Being:
CH3\ ~X ~
P
C2H50/ \SCH2C01~iCH2C00x~
~ R~ x~'
i~g: tl~ ~K50
~ ~ e~
EDll-I CH3 ~i I25 0,0005 O,OOOIS
~3 CH3 0 I,7 0,0025 0,0003
3I'-20 C~ I40~0 0,0005 0,0003
3T-I3 C~ 0 3,3 O,OOI 0~0004
~_2 C3H.~-xso g 22~0 O~OOI2 O,OOOIS
~F~1-4 C3H~-x3o 0 I~5 0,0007 0~00035
- FM-8 C4H9-xao ~j 370~0 0~003 C,C~2
~p-9 C4H9-xso 0 5,6 0,00056 0,00035
K~~TOKCIdH3L~4d ~4 ) ~ 66 , 0 5, 3 5~ 7
T`gapoc~5~ 9-25 O,OOI- 0~003-
0~008 0,006
Key:
_ 1. Lethal dose50 mg/kg, mice 4� RDetoxication
2. Aphids 5. Thiophos
3. Mites
The same is o~served in a number of inethionine derivatives. And here the d branching
~ (introduct~on of the CHZCH2sCH3 group) lowers the poss~i~ility of effective
detoxication.
More complicated results ensue from the introduction--into the position alpha to the
carboxyl--ot groupings capable o~ carboxylesterase hydrolysis, for example, the COOR
groups, such as takes place in the derivatives of aspart3.c acid:
A \ p ~S CHZC00R
~
B / \ SGH~COI~ICHCOOR
Here, on the one hand, there is an a substitute which hinders carb4xylesterase
deCoxication but, on the other hand, a second c~:.rbzlkoxy group appeared whic.h
is capable of detoxication. The introduction of tl~e second carbalkoxy group
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lowers the toxicity for mice and leaves an overall strong insect acaricide effect.
- We obtained similar results from a series of derivatives containing residuss of
glutamic acid.
Subsequently, the effect of carboxylesterase detoxication was employed for loweriag
the toxicity of such well known first generatian insect acaricides as timet, M-74
and Niagara 1240. The introduction of carbalkoxy groups into the side chair
led to a reduction of 100-250 times in the toxicity of compounds for warm blooded
animals. Several dozer~s of substances were synthesized and tested in these series
of compounds and it turned out that many of them wera stronger than thiophos and
were considerably leas toxic for warm blooded animals. A number of preparations
from this series were tested in the field.
_ Thus the introduction into the molecule of a well known insect acaricide of
groupings which promote selective detoxicaCion but which do not inhibit their
interaction with the "target" among insects and mites, can serve as still another
' method for searching for new an~ highly selective preparations.
Nor were the above methods for searching for selectivity of a~tion the only ones
analyzed. We also studied stereochemical selectivity of action, using as an example
the derivatives of inethylphosphonic acid, which contain reaiduea of acetylated amino
~ acids. Examples were found in which the optical antipodes differ by one order or
mor~. ~
Other methods are possible when there are many metabolic changes in the phosphor-
organic substances in live organi~ms, for example the use of phoaphatase hydrolysis,
regroupings and a number of others.
These studies are the result of work carried out by a large inter-departmental �
collective, organized by Academician M.I. Kabachnik. The following individuals
participated in this work: A.E. Shipov, E.B. Gorbenko, M.S. Vaysberg, G.V. Zhdanova,
M.V. Markova, V.A. Sergeyev and Ye.M. Piskunova (INEOS [Order of Lenin Institute of
Metallo-organic Compounds] of the USSR Academy of Sciencea); M.Kh. Besrkhamov,
Z.K. Yemkuzheva and L.G. Grineva (KBGU [Kabardino-Balkarian State University));
A.P. Brestkin, I.L. Brik, Yu.Ye. Mandetl'shtam and A.N. Fedin (IEFB imeni
I.M. Sechenova of the USSR Academy of Sciences); M.P. ~'habanova, O.V. Sundukov,
K.N. Savchp:~ko, I.N. Sazonova, A.A. Rakitin and S.G. Zhukovskiy (VIZR [All-Union
Institute for the Protection of PlantsJ of VASKhNIL [All-Union Academy of
Agricultural Sciences imeni V.I. Lenin]); Yu.S. Kagan, Ye.A. Yershova and
M.A. Klisenko (~INIIGINTORS of the USSR Ministry of Public Health); S.A. Roslavtseva,
N.A. Guseva, T.N. Kaluzhina, N.G. Rozhkova and A.S. Sedykh (VNIIKhSZR [All-Union
Scientific Research Institute of Chemicals Used for P~ant Protection]);
S.A. Zhuravskaya (IZiP of the UzSSR Academy of Sciences).
, In conclusion, it should be mentioned that the developed system of views is making it
possible to carry out a purposeful synthesis uf insect acaricides. This ia not
meant to imply that it is possible to write a formula for an ideal preparation in
advance (this would be utopia). However, it does mean that it is possible to select
effectively classes of substances, among which there is a higher probability of
finding preparations which satis~y the high modern requirements.
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Summary
In the interest of finding selectively acting insect acaricides which are of low
toxicity with regard to wann blooded animaloseddac~ordingeto whi hf thermoleculesnof
the environment, a~asic principle was p p
A group
new pesticides must form from fragments disseminated naturally in nature.
of esters and methylamides of amino acids ~Qa~iAis~udy ofeanticholinesterasef
dithionic acids of phosphorus was synthe~oXicit for warm blooded animals and
properties, metabolism, toxicodynamics, Y
entomological properties has made it possiblittWgsnfound that~in theccasetof
the the
selective action of synthesized compounds.
leading anticholineaterase type of action, an important role is played by
carboxylesterase and carboxylamidase hydroly~is and by the ability of substances to
suppress carboxylesterases.
~ B IBLIOGRA PHY
1. Mel'nikov, N.N., Volkov, A.I., Korotkova, O.A. "Pestitsidy i okruzhayushchaya
sreda" [Pesticides and the Environmentj, Moscow, Khimiya, 1977:
2. Mel'nikov, N.N. "Khimiya i tekhnologiya pestitsidov'~ [Chemistry and the
Technology of Pesticides], Moscow, Khimiya, 1974.
Shi ov, A.E., Gorbenko, E.B., and others. "New Type of ~
3. Mastryukova, T.A., P ,
Selectively Acting Phosphororganic Insecticides and AcaricideNo"9,I 968TIYA AN
SSSR [News of the USSR Academy of Sciences],Chemical Series,
i
A.g., Gorbenko, E.B., Kagan, Yu.S., Yershova, Ye.A., ~
4. Mastryukova, T.A., Shipov, ;
Shabanova, M.P., Savchenko, R.N., KabachAcaricides.11NPartyll'ofIS~STIYAeAN ~
Acting Phosphororgaaic Ins~cticides and ~
SSSR. Chemical Series, No 9, 1971� i,
A.E., Gorbenko, E.B., Shabanova, M.P., Savchenko, K.N.,
5. Mastryukova, T.A., Shipov,
Kagan, Yu.S., Yermova~ Ye.A., Rabachnik, M.I. "New Type of Phosphororganic
Compounds Which Selectively Act Upan Harmful Insects and Mites." TRUDY VIZR
VASKhNIL [Works of All-Union Instinces imenihV.Ir~Lenin]n 1972,alssuef35he All-
Union Academy of Agricultural Scie
Yu.S. Klisenko, M.A., Mastryukova, T.S., Yershova, Ye.A.,
6. Kabachnik, M.I., RaBan, ' G.V. "Studies of the Metabolism
Snitkovskaya, T.M., Shipov, A.E. and Zhdanova,
of Certain Phosphqrorganic Insolo iCgriciP~~cologyeanddToxicology~~nA'loecow,
book: "Farmakologiya i toksik g y L
Zdorov'ye, 1973.
M.I, Mastr ukova, T.A., Shipov, A.E., Zhdanova, G.V., Kagan, Yu.S.
7. Kabachnik, , y yu.ye. Brestkin, A.P., Brik, I�L�,
Ye.A. Rlisenko, M.A., Mandel'shtam, ~
Fedin,aA.N., Sazonova, I.N., Savchenko, K.N. "Some Peculiaritiea in the
Metabolism of Phosphororganic Insecticides Which Contain Residues of Amino
Acids." Works of the All-Union Conference "Basic Directions for Scientific-
Research Work in the~~Sphere of Irgalzda elestvo1NIITEKhIM [ ScientificgResetarch
an~ Combating Weeds. Section
Institute of Technical and EconoCh ist arch1976the State Cou~ittee of the
Council of Ministers, USSR, for e ry~~
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- 8. BRIK, I.L., Mandel'shtam, Yu.Ye., Sundukov, O.V., and othera, "Some
Peculiarities in the Mechanism of Effect on Insects of the DerivatiWes of
Thiophosphoric acid, Which Contain Residues of Amino Acids." RHIMIYA V
6EL'SKOM KHOZYZYSTVE [Chemist:y in Agriculture], No 2, 1974.
COPYRIGHT: Izdatel'stvo "Nauka" 1980.
7026
CSO: 1340/534
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1~OK Oh'h'1CIA1, USI? (1NI~Y
INDUSTRIAL TOXICOLOGY
.�RINCIPAL TASKS ASSOCIATED WITH SEARCH FOR NEW PESTICIDES
rfoscow VESTNIK AICADEMII NAUK SSSK in Russian No 5, May 31 pp 44-53
~Article by N.N. Mel'nikov, corresponding member of USSk Academy of 5ciences:
~ "Principal Tasks in Fieid of Searching Eor New Pesticides"]
~Text] Pesticides usually include all chemical compounts us~d for combating various

~ harmful organisms in the environment. This ~ncludes substances for destroying
weeds, pests and the causative agents of diseases in useful plants, carriers, of
infectious diseases of ~nan and animals and animal ectaparasites and also fox�
combating biological damage to metallic and non-metallic materials and undeairable
harmful organisn~s in indus try (for example, mucous formation in the paper industry,
algae in water cooling s~~ste~ns and so forth), for prPVenting ships from becoming
fouled with barnacles a~id for many other similar purposes. In addition, pesticide~
include insect sterilizers, preparations of hormonal action and plant growth
regulators, which i~i low concentratiot~s are usually growth regulators and in high
conceatrations herbicides.
- The use of pesticides i� the national economy produces very great economic results.
It is sufficient to state that during the tenth five-year period the use of ineans
for protectin~ plants against pests, dieeases and weeds produced more than 7
billion rubles worth of additional output an~iually. These measures ensured an
additional increase of approximately 12 percent in overall farming output, against
expenditures of approxiu?ately 1.2-1.3 billion rubles annually.
The use of pesticides is also promoting improved labor productivity in agriculture
both in tending the pla~tings and in harvesting the crops, especially cotton.
It is appropriate to point out that the use of pesticides makes it possible to
reduce by almost f ourfold the energy expenditures required per ton of agricultural
output (taking into account the energy expended for producing the pesticides
them.se lves ) .
Great importance is attached to pesticidea for preventing damage to metallic and non-
- metallic materials and products, caused by various harmful organisms.
The data furnished below provides some insight into the scale to which pesticides
- are being produced throughout the world.
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In 197~, the average cost for 1 kilogram of pesticide was approxi~nafiely $3.49 and
this figure allows one to evaluate the overall tonnage of the preparations being
- produced. It is noted that from a cost standpoint t.he world production of
pesticides at the present time is commensurate with the production oi mineral
fertilizers and reflects a tendenc,y towards further growth.
World Production of Pesricides in 1978 and Fore~ast for 1984
(millions of dollars i~i 197~t prices)
Pesticide Groups 1978 19~34
Herbicides 3716.4 4792.3
Insecticides atld acaracides 3028.4 3821.7
Fungicides 153i3.8 1965.1
~ Fumigants 168.2 228�9
Defoliar~ts and clesiccants 96.8 146.9
Pesticides of othe~oups 120.5 155.9
Total 8669.1 11110.8
* See: FARM CHEMICAL5, No. 9, 1979, pp 61-64
Data on pesticide production in the USSR testifies to the fact that ov.er the past 20
years it has increased by a factor of more than 9(in a computation for 100 percent
active agent). However the rapidly increasing requireinents of agriculture for
these subatances are still not being satisfied fully. ,
Pesticide Production in the USSR From 1960 To 1970
(thousands of tons)
Method of Measurernent 1960 1965 1970 1975 1979
In standard units 61.4 197.8 289.7 438.3 474.7
In a computation for 100% active 30.6 108.3 163.8 264.08 284.3
agent ~
In connection with the fact that pesticides are physiologically active compounds
' and the scales of their use, as evident in the data cited above, are rather high,
~ a problem has arisen with regard to protecting the environment and ensuring their
, safe practical use. This problem is truly an urgent one, since the initial
pesticides used on a rather large scale (for example, compounds of arsenic, lead
and mercury) were stable and capable of being accumulated in surrounding ob,jects.
The second generation pesticides are also stable preparations; they include DDT and
a number of other chloroorganic compounds. Their accumulation is conditioned to a
considerable degree by the tremendous scales of their use, which is cocitinuing at
the present time in a nu~nber of countries (in particular, over the past 20 years
approximately 4.5 million tons of DDT were employed thro ughout the world).
The capabiliCy oF pesticides to accumulate has raised the need for increasing the
requirements for introducing ciew preparations into operational practice and for
studying their behavior in various surrounding objects. At the present tima, the
following principal requirements can be imposed with regar.d to new pesticides:
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...moderate persistence in surrounding objects within a given cliciatic zone;
...as low a toxicity as possible for man, animals and other useful organisms,
including hydrobionts;
...relatively rapid disintegration in soil, water, the atmosphere and in the
organisms of warm-blooded animals, with the formation of products deemed safe for
man, animals and cultivated plants;
...the absence of an accumulation of these preparations in the organism of man,
- animals, birds and hydrobionts;
...a maximum high effectiveness in combating harmful organisms, with reduced
expenditures of the preparation per unit of area treated;
...sufficiently high econo?uic effectiveness of use in agriculture and in other
~branches;
...absence of remote adverse consequences for man, animals acid other living
organisms, as a result of the systematic and extended use of the preparations;
...the possibility of alternating the pre4.arations from various classes of compounds
in order to avoid the harmful organisms from becoming accustomed to them and also
the accumulation of the preparations in surrounding objects;
- ...the absence of undesirable effects in the object being protected;
- ...adequate stability of the preparations during storage and low degree of
- aggressiveness with regard to the equipment used for employing the preparations;
...accessibility of the raw materials required for producing the preparation and the,
possibility of production on the scales required. ~
Constant increases in the requirements lowers the output from suitable preparations
when searching for them and raises the cost for developing one preparation. Based
upon the data cited here, it is apparent that over a period of 25 years the number
of compounds that had to be synthesized and studied, in order to obtain one
preparation of practical value, increased by a factor of almost 8.
Number of Compounds Subjected To Screening In Order To Find One Freparation
Suitable For Introduction Znto Practice
- 1956 1964 1967 19"/0 1973 1977 1980
Number of compounds, in thousands 1.8 3.6 5.8 7.4 10.2 12 14
We have estimated that there are presently 2U large firms in economically developed
countries which are annually spending approximately 500 million dollars for
scientific-research work in the field of pesticides. Some idea as to the atructure
of these expenses can be obt~ined from an analysis of the pertinent expenditures of
37 firms in the particular branch of the chemical industry of the U.S.A. during
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19i7, the total amount of which was 250 million dollars. Of thia amount, 41 percent
was expended for the synthesis and screening of chemical compounds and for
developing the forms for their use and the creation of a production technology
(usual items of expense for NIR [scientific research work] in the chemical industry)
and 42 percent was spent for determining the toxicity of the preparations, for field
_ testing them, for studyiag the metabolism and determining the residues, that is, the
entire complex of ecological studies. In the process, 65 percent of all funds was
spent searching for new pesticides and 35 percent for work associated with
preparations created earlier.
~ The creation and study of pesticides involves the participation of specialists
representing variQUS discit_ines, including chemist-syiithesie specialists, analysts
and technologists, biochemists, entomologists and phyto-toxicologists, toxicologists,
physicists, mathematicians, biologists of varioua specialties and many othera.
The principal method of..search is that of "trial and error" (screening), however
with a definite direction in mind. This matLer of direction is borne out by data on
the number of patents published during the 1916-1978 period for new pesticides by
classes of chemical compounds.
It is apparent from the data cited that organic compounds of phosphorus and
heterocyclic compounds of various ranks and also various derivatives of carboxylic
acids are being studied most intensively for pesticide activity. In recent years
the derivatives of cyclopropane carboxylic acid, which is close in structure ta
chrysantheminic acid, have been studied intensively as insecticides.
The intensive search for pesticides in the mentioned classes of compounds d::rives
from the fact that recent?y the greatest number of active preparations have been
found among these compounds. Attempts to predict pesticide activity for substances
through the analysis of physical-chemical and other properties in the new classea
of chemical compounds, using electronic computers, have still not produced
reassuring results. Success has been achieved in predicting the presence of
pesticide activity o~ily in those classes of compounds in which the bio~og~cal
properCies of at least two of the substances are known. However, in such instances
the predictions are purely qualitative in nat_ure. This is associated to a
considerable degree with the insufficient vo'~ume of studies of the manner in which
the various classes of chemical compounds act upon the harmful and useful organisms,
the metabolism and other changes in the chemical compounds in surrounding objects.
One of the most imQortac~t tasks is that of c~:eating the scientific principles for
the directed synthesis of pesticides having a given physiological activity,
persistence a~:d other pr.operties which satisfy the modern requirements. Towards
this end, a requiremenL exists for setting up all-round fundamental studies
involving the participation of specialists representir?g various fields of knowledge.
Only such an overall approach will make it possible to achieve a rapid solution for
the task of directed synt:7es?s of new pesticides having the given properties.
fiy way of an example of ~uch an approach, permit me to cite studies carried out on
the metabolism of DDT an~l some of its analogs (particularly mathoxychlor,
methylchlor and methylthiochlor) in various surroundirig objects.
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rvcc ~rri~ic+L u~~ u~vL~
PATENTS PUBLISHED DURING 1976-1978 PERIOD
Class of Compounds Number of Class of Compounds Number of
or Purpose Patents or Purpose Patents
Forms of use 202 Derivatives of urea and 216
Preparations based upon 126 thiourea
mixtures of several agents Mercaptans, sulfides, sulfones 50
- Hydrocarbons of various series 15 and related compounds
Halogen derivatives ot an 24 Derivatives of sulfo acids 136
aliphatic series Derivatives of hydrazine and 70
Halogen derivatives of au 20 azo compound
~ alicyclic series Organic compounds of inercury 3
Halogen derivatives of an 21 Organic compounds of tin, 44
aron~atic series lead, silicon, antimony
Nitro cou~pounds of various 26 and bismuth
series Organic compounds of 892
Amiues Slld their derivatives 165 phosphorus
Alcohols, phenols and simple 279 Organic compounds of arsenic 11
ethers Five-membered heterocycles 162
Aldehydes, ketones and quinones 114 with one heteroatom
Aliphatic carboxylic acids and 419 Six-membered heterocycles 201
their derivatives with one heteroatom
Alicyclic carboxylic acids and 208 Five-membered heterocycles 375
their derivatives with two heteroatoms
Derivatives of cyclopropane 173 Six-membered heterocycles 298
carboxyltc acid with two heteroatoms
Aromatic carboxylic acids and 158 Five-membered heterocycles 175
their derivatives with three or more
Aryloxyalkane carboxylic acids 95 heteroatoms
- and their derivatives Six-membered heterocycles 175
Derivatives of carbonic acid 31 with 3 or more heteroatoms
Derivatives of carbamic acid 246 Antibi~tics 73
Derivatives of thio atid dithio- 15~5 Inorganic compounds
carbamic acid Total 5365
_ The principal directious in the metaboiism of DDT are presented in Diagram 1 and
for its analog methoxychlor in Diagram 2.
It is apparent from Diagram 1 that the metabolism for DDT proceeds with the
formatio:i of hydrophobic compounds which accumulate in the lipoids. When a definite
level of DDT content is reached in an organism, undesirable consequences and even a
fatal outcome may ensue. Meanwhile, tne clcsest DDT analogs, particularly '
methoxychlor, form hydrophilic pr~ducts during metabolism, products which are
easily withdrawn from vertebrate organisms, do not accumulate and hence cannot cause
undesirable consequences. Actually, in studying the appearance of chlororganic
pesticides in the milk of cows, it turned out that even in the case of a large amount
of u~ethoxychlor in the feed, considered to be impossible for actual use conditions,
its relative content in the milk (with regard to the feed) was less by a factor of
100 than in the case of DDT, as can be seen in Table 1.
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DIAGRAM 1
r:i ~
\ ' ~ci~`=~ c~
~ . s,
~s � L
~ ~i ~ ~
- l/ / \ ci ci -~ii ~ ~ ci ci / \ ~H ~ ~ ci
- `..~J ~ ~ -~~-=J c~� ci,
CCIa (.UGH
~ ~
- c:i ~ ~ c / \ ~i ci / \ ~ / \ ci
~ I I i!� c?
o ~
c:i ~ ~ r.,t~, / \ 'c? � . ,
I / \ CH / \ c~
~�zc~
ci ~ ~ coo~~ ~ I
~ I 'Y
~ ~ ~ ~ ci
, CNz
Y �
c~ ~ ~ cuzcoox ci ~ \ cIrt ~ / \ ct
. CH3
The KBD's ~koeffitsiyent biodegradatsiya; coefficient of biodegradation] for DDT
(first line) and its analogs in a water ecological system, expressed in relative
units, are furnished in Table 2. The KBD is a value that is proportional to the
speed of disintegration of a preparation in a definite ecological system. The data
in the table reveals that even a~nong the closest analogs of.~DDT, compounds may be
found which disintegrate in the surroutiding environmeut 100 times more rapidly than
does DDT.
Such an approach to solving the task of searching for new pesticides and acaricides
is already being employed in the USSR Aca~emy of Sciences by a large group of
scie~itists under the direction of Academician M.I. Kabachnik. In additioi~ to the
institutes of the USSR Academy of Sciences, this work also involves participation by
the i~~~stitutes of VASKhNIL ~Al1-Union Academy ot Agricultural Sciences imer?i
V.I. Leriit~], VUZ's aad also by VNIIKhSZR [All-Union 5cientific Kesearch Institute of
Chemicals Used for Plant Protection].
The author of the present report made a suggestion regardir~g the high and diverse
physiological activity of organic compounds of phosphorus ha.ving an asymmetric atom
- of phosphorus:
R Y '
\II
P-Z,
' /
X
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P'UK Uh'1'11:LN1. UDts l1NLY
DIAGRAM 2
r - - - ~ - -�l ~ r - - - 1
~ i.ll~~l ~ ~ ~ ~ l:ll~' ~ ~ lu:ll~ i
L _ _ _ .J I I 1 ~ ' ~
~ I.l.i~l \ L _ _ - J .
~ ~--J Y
i~~~ ~ ~ ~I:ii ~ ~ ~~ii cii,c? ~ ~ ii r,cn,
r.ci, cc�~~
~ ~
uu / \ i~ / \ ~,ir .
. ~ ~:r.i: ~ ~
ii~~ ~ ~ ~.ii ~--~,ii ii� ~ / ~ c~ii
: ~ I. ~ ~ii~ -~~=f o -
i c
~ ~ , ~
~
11~~ ~ ~ t:ll: ~~II Il~~~tii) ~ ~ ii ~ ~ ntin~il
~ U
, II ~ti(~~, CU:, H~U
where R is the substituted or unsubstituted hydrocarbon radical, X: S or 0 and
Y and Z-- very different chemical groups.
As a result of having synChesized and studied a large~number of such compounds,
success was achieved i~i finding a number of practically valuable substauces such as
trichlormetaphos-3, isophos-~3, heterophos, etaphos aiid soine others. At the present
time, a nucnber, of compouads of the indicated structure have entered into practical
use both in the USSR and abroad.
The principal work concerned with the aynthesis of new pesticides is being carried
out in the USSIt at the following institutes of the USSR Academy of 5ciences: at the
Institute of Organic Chemistry imeni N.D. Zelinskiy, Institute of Hetero-Organic
Compounds imeni A.N. Nesmeyanov, Institute of Organic Chemistry of the Siberian
Branch of the USSR Academy of Sciences, Instieute of Physiolegically Active
Substances, Institute of Organic Chemistry of the ~SSR Academy of Sciences,
Institute of Organic Synthesis of the Latvian SSR Academy of Sciences, at
VNIIKhSZR and at a number of others. Interesting work on insect feromones and
~ hormones is being carried out at the Institute of Bioorganic Chemistry imenf
M.M. Shemyakin of the USSR Academy of Sciences and at certaiti other organizations.
At the present time, a number of new preparations are undergoing field testing in
various regions of the country.
For the successful development of the production of new pesticides, special
importance is attached to developing methods for obtaining the semi-finished
~ products and expanding their assortment. The development of studies in this area
- is of ~reat importance to other hraciches of fine organic synthesis.
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TA Bi.E 1
Passa~e of Certain Chlorine-Containing Insecticides into the Milk of Cows
Conte~~t of Insecticide, Ratio of Cottt~nt
Insecticide in milligrams per kilogram in Milk To
In Feed In Milk Contenit in Feed
- � Aldrin 40 16.1 0.4
10 3.42 0.34
1 0.41 0.41
Dildrin 10 1.78 0.1~
- 0.3 0.015 0.05
0.05 0.002 0.4
DDT 200 6 0.03
25 2.29 0.092 ~
10 0.63 0.063
0.3 0.007 0.023
Methoxychlor ~1000 2.14 0.00032
- � 1000 0.19 0.00019
aU0 0.13 0.00016
Extreme importance is also attached to the development of biochemical studies which
are of primary importance not only with regard to searching for new peaticides, but
also for introducing already developed preparations into agricultural practice, since
knowledge of their behavior in surrounding objects is the basia for their correct,
safe and effective use. Microbiological studies play a very important role in this
regard.
In view of the tremendous nu~nber of harmful organiems which are causing conaiderable
damage to agricultural production, the efforts of researchers rnust be directed
mainly to studying those harmful organiams which are inflicting the greatest amount ~
of economic damage. Studies must be launched on the biochemistry of both uaeful and
harmful orgaiiisms, particularly their fermentive systems, for the purpose of finding
the differences in their structures and creating the prerequisitea for the
directed syntheses of the pesticides. Considerable importance is also attached to
studies of the cometabolism of pesticides with soil microorganisms, which determine
to a considerable degree the .persistence of the pesticidea in the surrounding
- environinent. In addition, an important problem is that of studying the "ecology of
pesticides" in agrocei~osis, in conformity with the various climatic zones.
In order to accelerate thework of creating new pesticides and developing the scientific
- principles for the directed synthesis of compounda having a prescribed phyaiological
activity, it would be advisable to examine the question of creating inter-
departmental collectives which operate not on the basi.s of formal coordinated plans
but rather in close creative collaboration and under a common management, similar to
the collective headed by Academician M.I. Kabachnik. Thia collective needs to be
expanded. When efiort :s concentrated on solving definite problems under a common
n~anagement, inore complete and practically important results can ensue.
In conclusion, I would like to mention several problema the solutions for which would
promote improved 1Abor productivity and eciergy savings in agriculture.
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1 un va~ 1� L~, iiu. uJL vlvl~ ~
1.liB~ 2
Coefficients.of Biodegradation (KBD) for DDT and Its Analogs in a
Water Ecological SysCem
Co~non formula for compounds:
RI- ~~-CH- ~~-R~
I
R'
. R~ I R~ ( R~ ( HSi~
Cl Cl CCI, U,015
t;l Cl HCC12 0,054
CH,O CH,O CCI, 0,94
CH, CH, CCI, 7,14
CH,S CH,S CCI, 47,0
- Cl CH, CCI, 3,43
CH, CzH,O CCI, 1,2
CH,O CH,S CCI, 2,75
CH,O CH,O C(CH,),
Cl Cl HC(CH,)NOz 3,27
First of all, it will be necessary to supply agriculture with an optimum variety of
herbicides for such crops as corn, sunflowers, sugar beets, cotton, potatoes, soybeans,
grain crops and a number of others. DespiCe the fact that t.here are satisfactory
preparations for the mentioned craps in the international assortment, each one of
thern is marked by certain shortcor~ings.
The creation of effective and safe defoliants is required for the purpose of
mechanizing the laborious work of cotton harvesting and also ~;rowth regulators for
.accelerating the ripening of the cotton and some other crops. The latter i:s of
particular i.mportance for grain crops grown in northern regions where the growing
season is sliort. Great importance is attached to creating systemic fungicides for
combating cotton wilt and other similar diseases.
An important task in the area of insecticides and acaricides is that of combating
arthropods which possess a resistance to the usual preparations.
An attempt must also be made to reduce the amount of time between the synthesis of
a preparation and its introduction into operational practice. This is associated to
a considerable degree with rationalization of the processes for studying the effect
of new pzeparations on various biological objects.
* * *
During a.discussion of the scientific report dy N.N. Mel'nikov, a speech was
delivered by Academician G.R. Skryabin. He directed attention to the recent
appearance of a large amount of data testifyi~ig to the fact Chat quite often, as a
result of the effect of micreorganisms and also various physical-chemical
environmental factors on non-toxic or low toxicity pesticides in the soil or water,
- products of the disintegration of these substances are formed which are considerably
more dangerous to man and the biosphere than the initial pesticide. For example,
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studies ca~rried out on the herbicide Ordran at IBFM ~Institut biokhimii i fiziologii
mikroorganizmov AN SSSR; Institute of Biochemistry and the Physiology of
Microorganisms of the USSR Academy of Sciences] in Pushchino revealed that this
preparation disintegrates under natural conditions with the =ormation of partially
oxidized products, ~ihich are retained in water for a very long period of time 1nd
which are highly toxic.
Another example an entire series of pesticides, mentioned in particular in the
above report, which contain a molecule of nitrogen in their structure. Some of the
iiitrogen-containing pesticides disintegrate in the natural environment with the
formatioii of nitro compounds which even in insignificant quantities are highly
carcinogenic.
Thus a requirement exists for the study of and control over the toxicity and
mutagenic at~d carcinogenic activity not only of the pesticides themselves but also
of the intermediate products of their disintegration directly under natural
conditions. .
- Subsequently, G.K. Skryabin discussed one effective variety of chemical agents for
protecting plants feromones. Unfortunately, up ui~til now these compounds have
been extremely expensive and their production extremely complicated.
Recently a basically new and extremely effective and very cheap method for obtaining
reproductive feromones was developed at IBFM. At the present time, the institute
has four expeditionary detachments operating in different regions of the country.
Without losing any time and under field conditions, these detachments are carrying
= out checks on the biological activity of the feromocies obtained by this method.
Reports have already been received confirming the high quality of all of the
preparations tested.
In 1981; jointly witti G12:vmikrobioprom of the USSR Council of Ministers, the
institute intends to prepare a sufficient number of preparations uot only for
carry-ing out extensive field tests but also for employment as effective agents for
protecting plants in the Pconomic work of kolkhozes and sovkhozes.
In conclusion, G.K. Skryabin emphasized that the DDT problem continues to be an
extremely important one. Its,use is actually being continued in a large number of
countries and in those areas where iCs use is forbidden, its content in the soil in
many regions remains rather high aince this compound disintegrates extremely alowly.
Thus a requirement exists for developing studies aimeci at finding effective methods
for its disintegration.
Academician Ye.N. T�f.ishustin emphasized in his speech the tremendous importance
attached to expandin~ the variety of pesticides being produced in the USSR. At the
present timE, the number of types of pesticides being produced in our counCry is
several times less than the number ir~ such countries as the U.S.A. and Japan. It is
because of this fact that a number of preparations must be procured abroad.
Meanwhile, a situation is developing at the present time wherein, for failing to
treat the plantings with the required pesticides, the use of fertilizers is not on ly
- just slightly effective but i~; tact it may even lower the cropping power of some
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r~i< urri~.i~w u~n ULVLl
crops, for example soybeans, since fertilizers, especially nitrogen and phosphate
fertilizers, are actively utilized by weeds which subsequently choke out the
principal crop.
- In recent years, the Academy of Sciences has devoted a great amount of attention to
the problem of creating new pesticides. In particular, in the Committee on
Scientific Principles of Agriculture of the Presidium of ~he USSR Academy of
Sciences, a great amount of work was carried out in connection with composing an
overall plan for chemical and biological studies in the area of creating pesticides.
Coinputations were carried out on the capital investments required. In the absence
of capital investments being allocated, it would be very difticult to ensure the
required assortment of pesticides. However, this problem has still not been solved.
It is obvious that the program must include the most im~artant directions to be
followed in carrying out studies and such studies must be properly financed.
One of the main difficulties associated with the creation of new preparations
- the need for testing a treme~idous number of chemical compounds, as mentiotied by the
speaker. At the present time, our volume of such tests is completely inadequate.
But, in addition to intensifying the screening volume, a requirement also exists for
a more intensive search for a scientific approach for directed synthesis. Special
attention should be given to this problem.
Importance is also attached to taking into account the climatic condiLions under
which the pesticides are used, since the processes of pesticide disintegration in
the soil may be completely different depending upon these co~nditions. In a ciumber
of instances, an unforeseen formation of toxic and not easily disintegrated forms
rnay occur.
In particular, mention should be made of the Hungarian experience, where several
years ago, having established the norms adopted i~i the U.S.A., simasine was employed
on an extensive scale. However, owing to the differetit climatic conditions, this
preparati4n did not disintegrate in the Hungarian soils and the following year the
grain crop yield obtained from fields treated with simasine was considerably lower.
It is obvious that in the USSR, where the differences in natural conditions by
regions are tremendous, such problems are especially urgent and thus appropriate
- studies must be carried out on ati extensive scale. Such studies are being carried
out at the Institute of Agrochemistry and Soil Science of the USSR Academy of
Sciences in Pushchino, under the direction of M.S. Sokolov. Valuable results have
beeci obtained and yet this is oiily the beginning.
In conclusion, Ye.N. Mishustin directed attention to the t~eed for increasing
organizational support for work concerned with the creation and checking upon the
effectiveness of new pesticides in the USSR Academy of Sciences.
M.S. Sokolov (Institute of Agrochemistry and Soil Science of the USSR Academy of
Sciences~ discussed in his speech the ecological aspects of the use of pesticides
and the probleros concerned with evaluating and forecasting the consequences of their
use. This is extreinely important for those regions of thE country where pesticides
are employed more intensively, primarily in the regions of the Azov-Black Sea and
A ral-Caspian Sea basins in the Uzbek, Tajik, Azerbaijan and Moldavian SSR's.
Here their application dosages per hectare of arable land exceed the all-union
indicators by a factor of 10-15.
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Successful work is being carried out in this area jointly with the in.3titutes of the
republic academies of science and interesting results have been obtained within a
relatively brief period of time. For example, an inspection of the territory of
Azerbaijan revealed that for a generally high level of pesticide use, their content
in.the soil, even on plantings of the same crop, changes in the various regions by a
factor of 10 or more. The reason specific soil, hydrothermal and microbiological
conditions, as mentioned in particular duri~ig earlier speeches. Once again we are
_ able to take all of these factors into account to only a weak degree and, as a rule,
we pay no attentian to them when planning the use of certain preparationa.
If appropriate studies are not developed and if an ecological evaluatioc? of the
consequences of using the new preparations is not furnished, then we will be
- constantly forced into examining their assortment and introducing more strict
limitations upon their use. The development of a uniform method for conducting such
an evaluation is extremely necessary for our cout~try.
In summariZing the results of the discussion, the President of the USSR Academy of
- Sciences, A.P. Aleksandrov, comn~ented upon the need for preparing reconunendations
on the further development of studies concerned with the more urgent problems
touched upon in the scientific report by N.N. Mel'nikov.
COPYRIGHT: Izdatel'stvo "Nauka", "Vestnik Pkademii nauk SSSR", 1981
7026
~50: 1840/533
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P~;~TICIDES
l1DC: 66.048.5:[6b1.7:547.261.118.3]
DIMETHYL PHOSPHITE PURIFICATION BY VACUUM DISTILLATION IN FILM ROTOR EVAPORATOR
- Moscow KHIMICHESKAYA PROMYSHLENNOST' in Russian No 9, Sep 79
pl~ 33-34
~Arti_cl~: by V. V. I)e~;t_ya?-cv, M. Kukustikin, Yc~. A. Vinnikov, V. V. Klilynov and
L. G. Loskutov]
[Text] Among the organic phosphorus compounds with pesticidal praperties, chlorofos
and vinifos are of great practical importance, and the output thereof is constantly
increasing. Production of these agents is based on interaction of dimethyl phosphite
with chloral and acetophenone [1]. It has been determined [2] thdt at least 94%
concentration of dimethyl phosphite is required to obtain high-grade products.
Most methods of producing dimethyl phosphite that are described in the literature
[3-6] are purely preparative, and the main constituent in the.synthesized product
ranges from 80-90%. There are no data concerning production of dimethyl phosphite
in over 90% concentration.
Since the boiling point of impurities contained in dimethyl phosphite (mainly
monomethyl phosphite) is above its boiling point, one can remove the impurities
tliat subsequently contaminate chlorofos and vinifos by means of disi.illation. How-
ever, distillatiun of dimethyl phosphite under industrial conditions presents con-
siderable clifficulty because of its thermolability c~t temperatures close to the
boilin~; point (lo5s of product and contamination of heat-transmittin~; surtace).
Puril'ication ol` dimetltyl phosphite: in still-type circulating apparatus did not yield
good results wtien tested under industrial conditions. The proposed chemical methods
- of. neutralizing impurities (ammonia and soda) were found to be ineffective and
time consuming [3].
We have studied the possibility of using a thin-film rotor evaporator to purify
raw dimethyl phosphite. The diagram of the unit is illustrated in Figure 1.
TY~e original industrial dimethyl phosphite containing up to 85% of the
main constitu ent was loaded into tank 1, from which it ~aas delivered
by vacuum to the top part of the evaporator 2. A type V(~-2MG vacuum
pump was used to create vacuum in the system. Delivery of raw material
was dispensed by rotameter 3. The vapor of volatile cor,iponents was
condensed in a tubular condenser co~led by brine at a temperature of
-10�C. The condensate then drained into a collectinf; tank and the
unvaporized part passed into apparatus 7.
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cnv nr~ ~trt e i. I iCF nNl .Y '
~ casing was placed on tlic evaporator(Figure 2), wlilch had an area of
U.0628 m2, for heating by the steam. The flared top part of the apparatus
served to separate splashes from the vapor phase. There was a rotor with
- four hinged blades within the housin~. The rotor shaft turned in two ball
bearings installed in the licl of the apparatus and a sliding bearing in
the bottom part of the evaporator. An end gasket was placed in~o the unit
of the top bearing to se21 the place where the shaft exited into the
evaporator lid.
Vacuum in the evaporator was monitorec', by a U-shaped pressure gauge, and
vapor pressure was controlled by means of valves, with monitoring by
pressure gauge 8.
Dimethyl phosphite content in products of distillation of the industrial
product was determined by potentiometric titration with an alcohol solution
of alkali.
~4
' Q'gVapor Distillate
~
r--- �
Feed i
Vapor ,z
~3
~2 $rl S, .
N
. ~
b 4
N
~
~ '
~ ~Y 5 Con.densate
� 1 U _6 7
Figure 1. ~
Diagram of experimental apparatus
1) tank with initiai ~r.oduct Figure 2.
2) evaporator Di.agram of film rotor evaporator
3) rotameter 1) housing �
~ 4) vacuum pump 2) rotor
S) condenser 3) casing [jacket]
6,7) collectors for still residue and 4) tUp bearing
distillate, respectively 5) bottom bearing .
8) pressure gauge
Dimethyl phosphite breaks dow-n when heated, so that we used the maximum perinissible
, temperature of 143�C for the heatin~ agent. The mixture was delivered into the
evaporator starting with 19.1 kg/(m �h), which is the minimal amount with which
uniform distribution of film on the wall was obtained. With increase in delivery
there is increase in distillate output of the apparatus (Figure 3) due to agitation
of ~he draining film of fl.uid.
As can be seen in Figure 4, maximum extraction of dimethyl phosphite constitutes
97% with a load of about 200 kg/(m2�h). With further increase in load there is
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1~OR OH'I~1('IA1. Util~: ONf.Y
a decrease in extraction, apparent.ly due to an increase in share of heat-exchanbe
:~urface involved in heating the initial mixture to the boiling point.
_ 97 �
ZS
/
, 96
_ 200 - � o �
~ ~ y 95
� i50
N ~
v ~ 94
~ ~F00 I00 150 ?.OD 250 300
~ L~ kg/(m~�h)
� ,50
- Q ~ Figure 4. ~
o ~ ~ ~ ~ Degree of extraction of dimethyl
so ioo i.so zan zso ~oo phosphite as a function of load of
L, k�,/(m2�h) initial product at residual pressure
P'igure 3. of 100 mm Hg and excess pressure of
- Distillate yield as a Iunction of load heating steam of 2.8 kgf/cm2
of nitial product
The esults of the experiments revealed that, even with small loads and residual
pressure of 100-150 mm Hg one can recover distillate containing 90-94% dimethyl
phosphite. Let us mention that, in some of the experiments, there was an iiicrease
in dimethyl phosphite during distillation, which could be attributed ro dispropor-
tionate amounts of mononiethyl phosphite in dimethyl phosphite and phosphorous acid.
The results of potentiometric titration of fractions obtained with distillation of
raw dimetiiyl phosphite were indicative of presence of the latter. .
_ In~the course of the studies, we noticed that if the heat-carrier ~temperature
exceeded 145�C the a2~paraLus became less productive and the quality of the dis-
tilled product was poorer. Tiiese parameters are influenced by residual pressure also.
Oplimum resu.l ts are obt