STUDIES IN THE FIELD OR ORGANOPHOSPHORUS INSECTICIDES

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80T00246A003900400002-3
• Release Decision: RIPPUB
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• Document Page Count: 15
• Document Creation Date: December 22, 2016
• Document Release Date: July 9, 2009
• Sequence Number: 2
• Publication Date: June 13, 1958
• Content Type: REPORT

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 Approved For Release 2009/07/09: CIA-RDP80T00246A003900400002-3 leskikh
Soedinenii, pp. 148-163
Studies in the Field of Organophosphorus Insecticides
T. A. Mastryukova
(Institute for Hetero-Organic Compounds, Moscow)
The present study was carried out in the laboratory of organo-
phosphorus compounds under the direction of the Corresponding Member
of the Academy M.I.Kabachnik. The studies in the field of insecticides
were begun in 1952 and at first had a nonsystematic character, but
from 1953 And especially from 1954 numerous ftanophosphorus compounds
were synthesized in our laboratory with the purpose of obtaining new
insecticides. _?
In 1953 there was established a constant contact with V.I.Z.R.
of V.A.S.Kh.N.I.L, where the tests of insecticidal properties of ours~
compounds were made. This contact was expressed not only by the trab' for
of substances for tests but also, and this was very important, in a
systemltic discussion with the workers of V.I.Z.R. - D.M.Paikin,
M.P.Shabanova and N.M.Gamper - of the results of the tests and means
of preparing new active compounds. A similarly friendly contact we
were able to establish with the representatives of the Chemical
industry. S.L.Varshavakii and S.V.Preobrashenskaya aided in many ways
the successful completion of the present work. Part of the work was
carried out in the laboratory of vinyl compounds of the Institute of
Organic Chemistry of the Academy of Sciences (M.P.Shostakovskii,
E.N.Prilezhatva) and in the laboratory for organic synthesis of V.N.I.I.V.
M.P.T.Sh.P. (V.N.Odnoralova).
In order to have a possibility of selection among the uncountable
number of esisting and possible organic substances of a definite and
necessarily limited number of objects for the testa, it is necessary
to be guided by some working hypothesis which permits one to carry
out such a selection consciously and with aim.
In our studies we used the rather well accepted. working hypothesis
concerning the inhibition of cholinesterase as the cause of the toxic
action of organophosphorus insecticides and concerning the acylating
action of organophosphorus insecticides on the cholinesterase of insects
as the chemical mechanism of this inhibition.
Insofar ae at this time it is probhble (1) that the object of phos-
phorylatlon in this enzyme is the hydroxyl group of "rise which enters
the polypeptide chain of its molecules, the working hypothesis was
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refined in that the oelectida was made asoag orgenphespherus compounds
which are capable of phespherylating the alcoholic hydroxyl group having
some noticeable but weak acidic properties. Such orgaaphosphorss compounds
may be the anhydrides of acid esters of phosphorus acids, acid halides,
substances similar to acid halides but containing, is the molecule, some
pseudohaloid groups instaed of the halogens, and, finally, neutral eaters
of acids of phosphorus is which one of the alkyl groups would correspond
sufficiently well to'am acidic alcohol. Since the acid halide and the
anhydride derivatives of acids of phosphorus, as well as phosphorus
eaters of phenols, to which one ^ay assign, without stretching the point,
some functions of sized anhydrides, have been already. studied in detail
and are being intensively studied in other laboratories, we concentrated
our attention on the derivatives of acids of phosphorus which have
residues of sufficiently acidic alcohols or mercaptaas.
Further, we refined our working hypothesis is the sense that we
realised the necessary prose"* in the molecule of as effective insect-
icide of a certain ptiatlm mount of the phosphorylatiag properties.
Organophosphorus compounds with sharply. displayed phoaphorylatiag action
as for instance dialkyl chlorphosphates, naturally cannot be sufficiently
selective agents since they would show their phosphorylating action with
any substrate of the organisms unspecific proteins, carbohydrates and,
finally, water. Such substances would be very rapidly detoxified in the
organism and would not reach those vitally iyertant cotters, the phosphor-
yletion of which would be the consequence following tease effect. On
the other hand substances having but feeble phospherylatiag properties
such as neutral esters of phosphoric or thiophaspboric acids, although
able to reach the necessary receptors without large lassos, would be
able to react then with the latter so slowly, it at all, that no action
would result.
Therefore in the process of synthetic searches, when we found a
poorly physiologically active substance, as an insecticide, with weak
phosphorylating properties (slow hydrolysis, reactions with alcohols,
amines), we along along the path of such a change in the structure of
the ^oleuule as to strengthen these properties. Conversely, if an
insufficiently active (as an insecticide) substance turns out to be
a good phosphorylating agent, we went along the route of such a change
of its structure which would yield an analog which would be less active.
The above shown principles wore naturally not adhered to very firmly.
The chemical distinction between the true cholinesterase, the inactiv-
ation of which assures the poisoning of wars blooded animals, and the
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pseudo-choliaestorese or the insect choliaosterase is atilil not clear.
We know too little about the mechanism of toxic action to dspsad with
complete confidence on the accepted working hypothesis. Newever, by
being guided by these principles we built in general lines the plans
for our syntheses and same positive results ndniob we obtained were too
ry etematic to be purely the work of chance.
Many literature data permit us to conclude that.tbore to **am* in
searches in the area of thiophosphate compounds. The latter are dis-
tinguished from their oxygen analogs by lower toxicity to warm blooded
animals with preservation of the effective properties in respect to
the insects.
In orde' to run the syntheses of substascos with various structures
it was necessary first of all to develop reasonable methods of prep-
aration of the starting materials.
The majority of the known methods of synthesis of tkie-orgaaephosphorus
compounds are mainly based on the chloride derivatives of phosphorus.
The latter are often incea eaiout is handling and during the work with
than it is necessary as a role to conduct out of the some of the reaction,
by some neass,the hydrogen chloride which tones in the reactiea.
Thio-orgaaophosphorus eempounds can be prepared also from the sulfides
of phosphorus. Salfidss are sheep, simple in handling and their prod-
uction is well in head* Therefore we stepped with the sulfides of phos-
phorus as the initial starting base for the syntheses of thisserganophos-
phorus compounds.
back in 1950 we explored the reactions of phosphorus sulfides x485.
P486 and P487 with alcohols (_)
r4aw It" (RO)=r(8)R Z (RO)=r(S)SR
P4 S
P487 S0? (RO)=r(a)w ? (RO)=r(8)U ? (R0.)=r(a)
It had been established that lower sulfides of phis P 4 a S and P 4 2 S
react with alcohols forming "alkyl thiephosphites and trialkyl dithio-
phosphates. The phosphorus sulfide P437 terms in i`s reaction a mixture
of three substances which may be separated in a nasal tractional dist-
illation into dialkyl thiephosphites, dialkyl dithiophesphates and tri-
alkyl dithiophosphates. The only exception is the reaction of this
sulfide with methyl alcohol as the result of which there are formed but
two compounds' dimothyl thiephosphite and trimethyl dithiephesphate.
As to the mechanism of the reaction of the lower sulfides of phosphorus
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with alcohols, this appears to be a complex is.. we examined the reaction
of the sulfide P4$7 with ethyl alcohol, along with the three products
indicated above, there are also formed hydrogen sulfide, pbosphise and
phosphorus. It is very probable that all these presets form as the result
of not a single reacties but of several which row is parallel. The hydr-
olysis of T427 is similarly 00ple2 is its eeuarse.
we also studied (4) the prsvieasly knows, (5) s of the reaction
of phosphorus dooasnltide t4210 with alcobolst
t4a10 ? SRO1 4 (**)=r(a)U + 21 11111280
In this way there were developed the preparatively accessible methods
of synthesis starting with phosphorus sulfides of dialkyl thiophosphites,
derivative! of trivalent phosphorus which were ebtaiwe in this work for
the first vise, dialkyl dithiepbosphates wed trialkyl dithiephosphates.
Here were prepared for the first tine :is were state Um tree dialkyl
dithiophosphates.
The constants of the eospsesds prepared by an is these three classes
of substances were used by as for the ealculaties it atemie retractions
of sulfur boned to the phopberas is the tries and the thiol. type of
linkage (6#7). The knowledge At the atests eefraotiis of sslfsr was
later of eossiderable help Ss the synthesis of ee-d$ of predetermined
structures.
These three elasssi of eel+MSds were the firat objeets tested for
insecticidal settee. All *.'Wd out to be weakly tease to inseets. Their
tests, as with all ssbsset objects, were rrs on adult . speoiNSS of
surrgaster takes Iron the` Ito et ' hiborsaties, and se, the post of citrus
plants the Marie floor WOe+s. Is the system of wemewelatsre used is
the present report (table 1) ewe plus means that 95-100% of dead and
paralysed insects were observed after the settee of the compound takes
in concentration of 0.3% or greater. Two pluses correspond to the ninisus
lethal concentration of 0.1%, throe pluses 0.05%, ate. as shows in
the table. The results of tests of the first three groups of compounds
are shown in tables 2, 3 and 4.
As can be sees, dialkyl thiepbosphites, dialkyl dithiopbosphates and
trialkyl dithiophesphate? ware poorly effective substances. From the
dialkyl dithiophesphhtes we prepared and ?este their potassium and
nickel salts. These were also poor issecticidis. It so* compares these
three classes of cospeuads, the most effective of this are dialkyl thio-
phosphites, derivatives of trivalent phosphorus.
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Insecticidal action of srgasephospherus oe peunde So isiscets (95-100% kill).
Cesoestratien,
?Nottation
0.3
0.1
++
OAS
+++
0.005
0.0005
!able 2
Constant. and iissctieidal aetieu N tested preparatiee?
Preparation Formula
l.Ot: 0 420 Action
p fn me.
1 M-1
(1120)2MS
52-3/17 1.4768 1.1892 +
2 X-4
(Its) 2 Pa
67-8/12 1.4597 ?1.0828 +
3 M-7
(Pro) 2
42-3/3 1.4581 1.0290
4 M-9
(ise-TrO)2MM
..
49-SO/3 1.4541 1.013.5 +
S K-13
(aso) 2hs
89-90/4 1.4583 M974
6 M-1S
(CM2sCSCS20)2P
77-8/6. 1.4911 1.OS94
The work on the systhesis'ef insecticides proper wasi begun with the
prepartioa of the simplest derivatives of dithiephesphoric acid. There
were prepared disulfides of the general fornssla (R0)2P(8)ABA, where A
^ay be the simplest alkyl radical or a residue of dithiephesphoric acid.
The former were prepared by the reacties of salts of dialkyl dithbophos-
phates with sulfeayl chlorides (6) (this study was performed with the
participation by the collaborator of our laboratory $.I.Oedyny) $
(RO)2t(S)M + RIaCi ? (RO)2'(3)f-t' 4 MCI
2(RO)2T(S)a1 + 12 -w (R0)2P(S)i-SP(s)(fl)2 + 2 1Q,
while the latter eespersde were prepared by enidaties of the same salts
by a solution of iediie ($). The resulting disulfides were tested both
in the form of emulsiess as well as dusts. 1owver they also turned out
to be rather weak iiseetieides (table S). The eempiuads Sited were but
weak phosphorylating agents. They are very. stable, are hydrolyzed with
difficulty and are sufficiently stable in respect to alkalies. 'e had to
go on thus to the more labile anhydride terms.
As such we selected the acyl derivatives of dialkyl ditkiephosphoric
acids. These were prepared in'geod yields from sodium, petassius and lead
salts of the corresponding acids and aryl halides (7).
(RO)2P(S)SM + R'COCl ? (RO)2P(8)$COR' + 1101
(R0) . r e l ter. ? s s eencl .. (801.P (f) RCOGI' + IaC1.
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Table 3
i;,,:stante and insecticidal action of the prepared substances
Frepn.
g.pt
Mo.pt. 0020
d20
Action
p in as
M-3
(Me0)2PSSH
62-3/5
- 1.5343
1.2888
M-5
(EtO)2PSSH
81-2/5
- 1.5070
1.1654
M-8
(PrO)2PSSH
85-6/3
- 1.4987
1.1040
M--11 (iso-PrO)2PSSH
71-2/3
- 1.4918
1.0911
4
M-36,(iso-BuO)2PS3H .
93/4
- 1.4889
1.0558
- (Et0)2PSSK
-
194-S -
-
+
((EtO)2PSS)2]Pb
-
75-6
[(Me0)2PSS]2Mi
-
124-5 -
-
+
Table 4
Constants and insecticidal action of the tested compounds
Nc. Frepn. Formula pt nD20 d20 Action
C
p
aa
M-2 (MeO)2PS(SMe) 101/17 1.5292 1.2415
14-6 (8t0)2PS(SEt) 115/10 1.5013 1.1168 +
M-9 (PrO)2PS(SPr) 115-6/3 1.4955 1.0561
J M-12 (iso-PrO)2PS(SPr-iso) 91-2/3 1.4843 1.0351
5 M-14 (iso-BuO)2P8(SBu-iso)148-9/4 1.4859 1.0159
Table 5
C,)nstante? and insecticidal action of tested coapounds.
No.
Prepn.
B.pt. M.pt.
n20
d20 Action
i
M-44
(Et0)2PS3Me
101-2/3 -
1.5500
1.2142 +
2
M-48
(Eto)2PS3at
106-7/3 -
1.5431
1.1810 +
3
M-49
(Et0)2P83Bu
139-40/4 -
1.5306
1.1246 4
4
14-43
(iso-Pr0)2P53Me
99-100/2 -
1.5297
1.1471
5
M-50
(iso-Pr0)2PS3Bt
117-8/3 -
1.5240
1.1189
6
M.-52
(iso-Bu0)2P838t
129-30/3 -
1.5183
1.0866
M-16
[(Me0)2PSSJ2
51-2
M-11
[(Eto)2PSSJ2
28-9
M-16
[(iso-PrO)2PSS]2
91-2
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It is of interest to note that the acetyl derivatives are obtainer:
-i~.h equal success from the potassium and sodium, as well as lead says
of dialkyl dithiophosphoric acids. The bensoyl derivative may be prepared
or.;v from the lead salt. In turn the carbonate derivatives could be
,11'.iined only from the salts of the alkali metals. As it is evident from
+t,,e h, the acyl derivatives prepared by us turned out to. be more
:.vc~ive poisons, but still left much to be desired.
Even more active phosphorylating agents should be the oxygen analogy
if the above cited aryl derivatives. These are constructed like the
.J!-ove compounds but contain one less atom of sulfur than the correspon-
ding -'erivatives of dialkyl dithiophosphoric acids:
~R0)2P(S)0Acyl . (RO)2P(O)SAcyl
1{o~vF r, the chemistry of these compounds is but poorly explored. The
svnthrsis of aryl derivatives from the salts of dialkyl thiophosphoric
.,('ids required special work on clarification of the reactivity of these.
The rt-sults of this work may be expressed by the following scheme:
(RO)2P(S)OM
(RO)2t(0)SR
(R0)2P(S)000R'
(R0)2P(0)S000R'
Tbble 6
Constants and effectiveness of action of aryl derivatives
Prepn. Formula
B. pt.
20
nD
d20 Action
M-25
(EtO)2PS2come
98/2
1.5154
1.1898 +
M-26
(iso-PrO)2PS2C0Me
100-1/3
1.4979
1.1177
M-,R
(iso-BuO)2PS2COMe
125-6/3
1.4929
1.0793
M-30
(iso-PrO)2PS2COPh
^.51.2
M 2'
(EtO)2PS2C02Me
105-6/4
1.5063
1.2171 +
M-20
(EtO)2PS2C02Et
115/4
1.5001
1.1891
M-30
(EtO)2PS2CO2Pr
125/6
1.4981
1.1620 +
i
M 34
(EtO)2PS2CO2Bu
162-3/6
1.4889
1.1281
4
M-31
(EtO)2PS2CO2As
137-8/4
1.4925
1.1179
10
M-32
(iso-PrO)2PS2CO2Bt
109/3
1.4894
1.1301
M--33
(iso-PrO)2PS2C02Am
138/3
1.4841
1.0773
During the study of the reactions of alkylation and acylation of the
sodium, potassium and silver salts of dialkyl ^onothiophosphoric acid we
eatdbl1Rhed the dual character of reaction of these salts. In the reac".i.,~,
cf alkyl halides (8) the alkylation occurred at the sulfur atom (see the
reaction scheme),while in acetylation -at the oxygen atom (9). The
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-oroearoonaLs em .qr ? - I' ugaw -~w~~w -~? -~-7 y
ue ri.vatives.
By means of the infrared spectra we established the structure of the
e.kali and the silver salts of dialkyl ^onothiophosphoric acids. For the
salts we confirmed t is data of %Gcref who had found that they have
th thiono structure. The spectra of the silver salts were determined
as for the first time. These speak of the thiolo structure of the
salt with strong association of the molecules]
0 .......... S
(RO)2 AS. OR) ....... 2
The data concerning.the structure of the salts in the absence of
their tautomerims which is apparently improbable in this case speak of
he fact. that their reactions of alkylation and acylation may proceed
with or without the transfer of the reactive center. This study was made
in connection with work in the area of tautonerism and reactivity of
orw.+nophosphorus compounds and is described in more detail in the report
~?y fit. I .. Kabachnik.
Tests of the acyl derivatives of thiolophosphoric acid showed that
;.heeie are weak insecticides. Similarly poorly effective turned out to
t,e some of the alkyl derivatives (table 7). Strong insecticidal properties
are had in the carbonate derivatives[ their effectiveness is such that
;1r.y cause a 95-100% kill of the flour worn after use in the concentration
0.05% or greater (table 7, substances 6-7).
We also prepared mixed alkyl phosphoric disulfides from the corres-
p ,d4,g s'd!wa salts of dialkyl ^onothiophosphoric acids
,RO)2PIS)OXa + R'SC1 + (RO)2P(O)S-SR' + laCl.
r.. eulfenyl chlorides (8). The thus obtained derivatives showed high
*.o'cic.ty to the Eprygaster insect, especially substance M-51. For us
t.h:s was a certain degree of success, although substance M-51 is less
active than Tiofos in its contact action.
Thum, it seemed that monothiophosphoric derivatives give more chances
for success in finding practically interesting substances. However, we
did not consider it rational to develop this area insofar as it is belna
stL ;iied in many other laboratories.
A further study was directed along two main paths: 1) preparation
of derivatives of the simplest alkyl-thiophosphonic acids and 2) the
synthesis of trialkyl dithiophosphates containing definite substituents
fn predominantly the 9-positions.
Alkyl-thiophosphonic derivatives may, Judging from literature data,
t,e more powerful inhibitors of cholinesterase than the corresponding
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thiophosphoric derivatives.
Among the derivatives of alkyl-thiophosphonic acids we studied the
d-ilkyl esters of alkylthiblophosphonic and alkylthionophosphonic acids
These substances were prepared'by the action of alkyl halides on
d:dikyl thiophosphits sodium salt. For preparation of the thiolo deriv-
atives, the thiono forms were isomerized by heating in a sealed tube in
trio presence, of alkyl halides, according to Pishchimuka method. The
thiolo derivatives were also prepared from the appropriate halides of
alkyiphosphonic acid and aleohol or aercaptan, as well as by alkylation
of the alkali salts of esters of alkylthionophosphonic acids (this work
wab .-arr*ed out with participation of the degree aspirant N.I.Kurochkin
and E.d.Kugucheva).
P4S6 ? ROM + (RO)2P(8)H low
H2O
RSH
R'POC1 +
2ROM
(RO)2PSlla R+Br R 'P(S)(OR)2
R'PSC12 ? ROM
R'P(S)(OR)2 R'P(8)(OR)OH
R'Br 4 RCMN2
RIP(O)(SR)OR RCHN
RBr T
R'P(S)(OR)OWa
? Table I
Constants and insecticidal action of the tested
No. Prepn. Formula
B.pt. D20
K-2
*ePS(Ost)2
76-8/13
1.4610
1.0SS3
2
K-19 .
BtrS(OMe)(0st)
74-5/10
1.4665
1.0647
3
M-21
9tPS(OSt)2
80-3/10
1.4576
1.0324
4
K-3
Pr?S(O6t)2
64-6/2
1.4596
1.0158
5
K-4
BuPS(OBt) 2
74-7/2
1.4600
1.0004
6
K-5
PhCH2PS(OBt)2
123-6/2
1.S30S
1.1031
?
K-10
McPS(OBu)2
72-4/1
1.4535
0.9843
K-11
BtPS(OBu)2
80-3/2
1.4533
0.9775
K-22
EtPS(OBt)(OCOM.)
68-9/1.5
1.4701
1.1232
The first representatives of this group of substances were prepared
FY on back in 19SOtM-24). The thiono and the thiolo eaters (tables 8-9)
differ considerably in the insecticidal properties. While the thiono
--sters, as should be expected, were only rather weak insecticides, the
-h:.>1o derivatives turned out to be quite effective. Thus, substances
M-24, K-6 and K-9 were quite close to Tiofos.
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compounds,
d20
4
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By this path we first reached effective insecticides which along
vith the contact action also possessed the systemic action. However.
none of the compounds posh bsed properties superior to the known
insecticides in use now.
Somewhat different considerations lay in the foundation of the second
path. I remind you that disulfide derivatives turned out to be too stable
while the acyl derivatives, conversely, were too labile in order to make
good insecticides. We stopped on the trialkyl dithiophosphates.which
-arry substituents in the alkyl group connected with sulfur, especially
in the B-position. Us expected of these derivatives the optimum phos-
phorylati*g ability; Naturally only the experimental method could be used
to prove this expectation.
Thus, by the reaction of ethylene oxide with dialkyl dithiophosphat.es
we ( together with the degree aspirant at Y.W.I.I.V V.$.Odnoralova)
prepared e-hydroxy derivatives
PC1
(RO)2PS(BCH2CH2OH) + S (RO)2P3(SCH2CH2C1)
e1i2CH2- C2H4Ci2
(RO)2P(S)SH
CH -CH -INN
L
2_.. Z!
(RO)2P(S)SCH2CH2$H2
and from these we prepared 8-acetoxy and B-ehloro derivatives (11). We
also prepared B-aminoethyl dithiophosphate, previously prepared in
V.I.Z.R. in the A.I.Kulikev's laboratory. There were prepared other
- aaino eaters, as well as their derivatives. If one compares the activ-
ity effectiveness of compounds shown in table 10 it is easy to see that
?_ho~ introduction of substituents in the B-position increases the insecti-
cidal properties in this series apparently along with the electronegati
ity of the substituents. The most active was the chloro derivative
which had been prepared by Schrader (12).
The next step should be the synthesis of sulfur analogs
(RO)2P(S)SCH2CH2SR'
especially since at that time there had appeared the patent of Schrader
(13) on Systox, which is a a-substituted derivative of ^onothiophosphori-
acid. At first it was proposed to use for the synthesis of 8-alkylmer
capto substituted compounds the reaction of addition of dialkyl dithio
phosphates to vinyl thio ethers (this work was carried out in collabor-
at .oii with 6oworkers of Institute of Organic Chemistry M.F.Shostakovsk.
z_,.F.f r.'ezhaeva and N.N.Uvarova).
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Table 9
Constants and insecticidal action of the compounds tested
No.
Frepn.
Formula
B.pto
nn20
d20
Action
K-9
McPO(SEt)(OEt)
106-8/18
1.4718
1.0904
++?
2
Ku-1
McPO(SEt)(OPr)
71-2/3
1.4510
1.0356
+
3
Ku-3
McPO(SEt)(0Pr-iso)
60-2/1
1.4749
1.0555
++
4
Ku-2
McPO(SEt)(OBu-iso)
69-70/1
1.4666
1.0222
++
5
K-23
McPO(SCH2OMe)(06t)
117-20/2
1.4778
1.1538
+(+)
t
K-18
EtPO(SMe)(OSt)
93/9
1.4790
1.1058
+(+)
7
MU-24
EtPO(SEt)(0Et)
66-8/2.5
1.4747
1.0670
+++
8
K-12.
BtPO(SBu)(OBu)
92-4/2
1.4660
9.9951
-
Q
K-6
PrPO(SBt)(OBt)
85-6/3
1.4733
1.0447
++
IQ
K-7
BuPO(OEt)(SBt)
98-100/3
1.4728
1.0262
+
11
K-8
PhCH2PO(SEt)(OIt)
134-6/2
1.5350
1.1263
+
Table 10
No.
Constants and insecticidal action of the compounds tested
Prepn. Formula d.pt. nD20 d20
Action
at 2 mm.
1
MO-5
(MeO)2Pa2C2H40H
-
1.5380
1.2911 +
2
MO-1
(EtO) 2PS2C2H4OH
119-20
1.5250
1.2042 +
3
M0-2
(PrO)2PS-2C2H4OH
124-6
1.5140
1.1440 +
4
MU-4
(iso-PrO)2PS2C2H4OH
118-9
1.5083
1.1323 -
mu-3
(iao-Bu0)2PS2C2H40H
8
135-
0
1.5 45
1.0965 +
MO-6
(Et0)2PS2C2H40Ac
135-6
1.5010
1.1845 ++
MO-7
(iso-BuO)2PS 2C 2H40Ac
140-1/1
1.4890
1.0948 +
MO-9
(EtO)2P32C204C1
103-4
1.5230
1.2270 +++
9
MO-14
(dtO)2P3 2C2H411H2
-
1.5287
10
M0-19 (PrO)2PS2C2H41H2
-
1.5130
1.1099
11
MO-21 (is*-Buo)2PS2C2H41H2
-
1.5065
1.0705
12
MO-18
(EtO)2P82C2H411H2 a.p.102-3
(picrate)
-
-
However it appeared that under the usual conditions there are not formed
sstahaa the 0- heb the a-derivatii'es, the structure of the addition prod
ductb being determined by a known synthesis from a-chlorodiethyl sulfide
as shown in the following scheme, and by other means (14).
(RO) PSSH ? CH2O, RaN-)-(R0)2P(S)SCH2SRI ~C1CK2SRI
2 ? KOH /(RO)2P(S)SK
+ CH:-CHSRI~(R0)2P(S)SCHMeSR"C C1CHMeSR'
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 Approved For Release 2009/07/09: CIA-RDP80T00246A003900400002-3
12
The substances prepared were tested on the Eurygaster insects. They
turned out to be weak insecticides against this insect (table 11).
The synthesis of the first representatives of 0-alkylmercapto subst-
ituted trialkyl dithiophosphates was achieved by us in 1953 in good yield
,f shout 90-5% starting with sodium or potassium salts of dialkyl dithio-
phosphoric acids and d-chloroalkyl sulfides:
~P4S10 4 ROM
IR012PSSN 'POH (RO)2P(S)SNa
_r. H2eCNSR' ,/ C1C2H4SR'
(RO)2P(S)8CN112`L-CH2SR'
Thp latter were prepared in the beginning of the study by the reaction of
hydroken chloride with products of addition ?f mercaptans and vinyl ethers.;
The substances proved to be highly effective insecticides with contact-
svstesic action, exceeding by many orders the eisting organophosphorus
chemical poisons (table 12). Therefore in the course of the following
study we found a new and better method of synthesis, based on ethylene
oxide, ethyl mercaptan and dialkyl dithiophosphoric acid.
Table 11
Constants and insecticidal properties of the compounds tested
No. Prepn. Formula B.pte
nD20
d20
Action
1
2
3
M-65
M-54
M-59
(Bt0)2P$2CHN.Ut 109-10/3
(Et0)2PS2CHMe8Bu 109-10/2
(6t0)2P82C1104.8C2N40Bu 123-5/3
1.5290
1.5198
1.5125
1.1392
1.0965
1.0940
4
+
+
4
M-56? (isos u0)2PS2CIOMRt 113-5/2
1.5070
1.OSS6
+
5
6
7
8
M-55
M-53
M-86
M-87
(iso-Bu0)2PS2CHMeSIu 121-2/2
(iso-Bu0)2P82CMM.8C2H405u 124-6/3
(Eto)2PS2CH2Srr 145-6/4
(EtO)2PS2CH2srr-iso 133-4/4
1.5070
1.5012
J.S270
1.5210
1.0384
1.0422
1.1308
1.1312
+
4
-
-
Tabl. 12.
1
M-82
(NeO)2P3 2C2H45M e 71-1.5/0.004 1.5580
1.2493
4+4++
2
M-81
(N.0)2P82C2N4sat 91-2/0.003 1.SS98
1.2065
++++
3
M-80
(Et0)2P82C2N4S1e 127-8/2
1.5405
1.1699
44+4
4
M-74
(EtO)2PS2C21448$t 129-30/2
1.5350
1.1445
44+44
5
M-85
(Et0)2P82C2N4SPr 143-4/2
1.5275
1.1260
4++
6
M-77
(BtO)2P82C2H48su 150/1
.1.5255
1.1040
++
7
M-75
(iso-PrO)2PS2C2H4Stt 134-5/3
1.5}8gg
1.0887
+4
8
14-76
(is*-Pro) i PS 2 C 2 N 4 Sbu 148-9/4
1.5096
1.0622
4
9
M-58
(Et0)2P3 2C2N48C2H40Bu 188/3
1.5160
1.1050
++4
10
M478
(iso-Pr0)2PS2C21443C2H40Bu 172-3/2
1.5090
1.0967
+
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 Approved For Release 2009/07/09: CIA-RDP80T00246AO03900400002-3
-Li
E.N,Prilezhaeva also realised the addition of dialkyl dithiophosphates
to thiovinyl ethers contrary to the Markovnikov rule In the presence of
isopropylbensene hydroperosids. Were there were formed $-substituted tri-
a1kyl dithiophosphates in 50-60% yields.
Tests of properties of compounds of this type xssxds were conducted
mainly with the specimen M-74. These tests were run on various plant
cultures with several species of insects. Substance M-74 turned out to he
a highly effective poison against the red apple site, and at concentration
of 0.05% protected the apple trees for up to a month and a half. M-74
remained effective up'to two months against the Tetramychus alto on roses.
At this concentration substance M-74 was effective up to three weeks
against the green plum aphid. The duration of action of the substance in
many experiments was greater than for Merkaptofos on the same objects.
Especially promising is the preaseeding treatment of summer wheat grains.
=seeds treated with 2% solution of the M-74 concentrate ( with 30% content
of the active substance) yield sprouts which are poisonous to Burygaster
for 2-3 weeks (100% kill). The norm of consumption of the substance is
120-150 grams of the active principle of M-74 per hectare of the field
which fact shows the highly economic feature of M-74?
Interesting data, sequiring further tests, were obtained in control of
pests of sugar beet, corn, etc.
Not less interesting are substances M-81 and M-82. Their study was run
:~n,aller scale than that of 11-74. These are also contact-systemic insec-
ticides. In effectiveness they are very close to M-74. However these
nmpounds are weakly toxic to warm-blooded animals in comparison with
.iptufos or M-74. On intravenous application to rabbits they are almost
times less toxic than Tiofos. Thus, as the result of the study we
ri in finding a group of insecticides - 8-alkylmercaptoethyl enters
'kyl dithiophosphoric acid, which have high insecticidal and
-tivity with contact and systemic action.
References.
J,Biol.Ches. 202,67(1953)
t al. Izvest.Akad.Nauk Otdel.Khim.Nauk No.4,427(1952)
Ct al. Helv.Chim.Acta 16,1161(1935)
I.K shichn;k et, al. Izvest.Akad.Nauk, Otdel.Khim.Nauk No.1,212(1953)
r' :.Pi&%hchiruka, J.Russ.Phys.Chem.Soc.44,1406(1912)
M i.kabachnik et al. Izvest.Akad.Nauk, Otdel.Khim.Nauk No.4,743(1954)
M?I Kahachnik et al. Ibid. No.3,436(1954)
"' ~.' Obshchei Khia.25,1924(1955)
Zhur.Obshchei Khia. 26,120(1956)
Akad.Nauk, Otdel.Khim.Mauk Io.2,193(195601
;hchei Khia.2S,2274(19SS)
'ler Insectiside out Grundlage d.Pluorsr
d edition
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 t ~T
Approved For Release 2009/07/09: CIA-RDP80T00246AO03900400002-3
1 %
G.Schrader. Ger.Pat.830,309
14. M.I.Kabachnik et al. Isvest.Akad.Kauk, Otdel.[hia.$auk 1956, 443.
Remarks
(t. E?Arbuzov Cht m.Inst ? ; Kazan Section, Acade'mv 0
TA ; Mastryukova illustrated well the meaning of sy nthr s;.e
a;,iorus insecticides on the basis of phosphorus sulfide cc
e is very cheap and in addition has great possibilit;.? f
~?r~e Synthesis.
i ice. in the area of thiopho~phoric compounds art- only
t,ese studies.
(Brain Institute, Acad. Med. Sciences USSR)
-eports the speakers already have touched upon -.he'-
,!on ion of active centers of enzymes. At this time the
this area. The results given by T.A.Mastryukova j.st:.:'
:tn of,development of the previous study of the action
rasic substance.. For the reaction of insecticides
tine phosphorylation reaction must proceed. For clare
.-l as to which functional groups in the molecule of n i
pr:osphorylated, modern means of study were used (chrom ' : .
ctive phosphorus) by means of which it was possible t-,
phosphoric acid in yield of 40%. This is a proof
>f cholinesterase the hydroxyl group is phosphorylaterL.
s,. - _ ne as such, its hydroxyl group does not react w-'th
isecticides. It is necessary to may that all these st
?a yr ' opment stage.
h acart kKiev Institute for Labor Hygiene and Oc lip,
!.xz.ir and Bodansky it is known that the mechanism
t :?ue and pseudo cholinesterases differs. Thr,rF fcr.=
i ;.tit