THE SYNTHESIS OF SOME MIXED ESTERS OF DITHIOPHOSPHORIC ACID

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000700130139-2
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 7
• Document Creation Date: December 22, 2016
• Document Release Date: September 23, 2011
• Sequence Number: 139
• Publication Date: August 31, 1953
• Content Type: REPORT

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CLAS"IFICATION CONFIDENTIAL
SECIkiITY INFORMATION
CENTRAL INTELLIGENCE AGENCY REPORT
INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS CD NO.
COUNTRY ~~ ~
SUBJECT Scientific - Chemistry, organophosphorus
compounds
How
PUBLISHED Thrice-monthly peri.udical
WHERE
PUBLISHED Moscow
DATE
PUBLISHED sep 1952
LANGUAGE Russian
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DATE OF
INFORMATION 1952
DP.TE DIST..~ ~ Aug 1953
NO. OF PAGES 7
SUPPLEMENT TO
REPORT NO.
THIS IS UNEVALUATED INFORMATION
SOURCE Doklady Academli Nauk SSSR, Vol LXXXVI, No 3, PP 543-546.
PI. N. Mel'nikov and K. D. Shvetsova-Shilovakaya
Sci Inst of Fertilizers and InaectofuTigicidea
Mixed esters of thiophosphoric acids attracted the attention of many in-
vestigatora in recent years, because some compounds of this type were useful
in agriculture in the fight against plant pests (1-5 )?
Some esters of dithiophosphoric seem interesting in this respect, even
though they are leas active than thiophosphoric acid esters.
Only a few methods are described for obtaining esters of dithiophosphoric
acid, the most important of which is the reactions between salts of dialkyl-
dithiophosphoric acid and halogen derivatives (6, 7):
(RO)2PS2Na t R1X -i (HO)2P52R1 t NaX
The maJority of the mixed esters of dithiophosphoric acid known at
present were prepared in this way. However, this method g' ~~. good yields
only when the halogen atom in the halogen derivative is suss, iently mobile.
It seemed of interest to us to study the reaction of the addition of di-
alkyldithiophosphoric acid to the double bond of I~nsaturated compounds, clari-
iying the possibility of obtaining mixed esters of dlthiophospharic acid in
this manner. Such an addition of dialkylphoaphorous acids to unsaturated com-
pounds was successfully accomplished recently by A. N. Pudovik and B. A.
Arbuzov (8-12).
As a result of experiments carried out in the beginning of 1951, it was
possible to establish that the reaction between dialkyldithiophosphoric acid
and unsaturated compounds follows the~Ischeme:
(RO)2PS2H-~~ . CC-~(RO)2PS2- ~ -~ -H
STA7E
ARMY
THE SYNTHESIS OF SOME MIXED ESTERS OF DITHIOPHOSPHORIC ACID
MAW
AIR
DISTRIBUTION
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The yield of mixed esters of dithiophosphoric acid by this method is very satis-
factory. In the presence oP solid potassium hydroxide, the reaction proceeds
in the cold. lie studied the reaction between dialkyldithionhosphoric acid and
styrene, methyl s:rylate, acrylonitriie, vinyl acetate, acroleine, eatnra of
malefic acid; and some other compounds. The compounds thus obtained and their
properties are listed in the appended table.
It is necessary to note that in 1952 a report appeared (13) describing
the use of the above reaction for the synthesis of esters of 2tthiophosphoric
acid, Which prompted us to publish the present research. It should be noted
that tte addition reaction of dialkyldithiophosphoric to unsaturated compounds
was studied by us on 31 examples, while the American authors cited only six
instances.
Experi_ metal part
The preparation of mixed esters of dithiophosphoric acid from practically
all of the compounds was carried out under the following standard condiLiona:
to one mole of olefin, one mole of dialkyldithiophoaphoric acid was gradually
added with constant stirring. The addition was done at such a rate that the
temperature of the reaction mixture did not exceed 40-45?. After addition of
the ent t~e amount of dialkyldithiophosphoric acid to the reaction mL?-ture,
the mixture was left standing at room temperature until the amount of free di-
alkyldithiophosphoric acid no longer changed. The dialkylthiophosphoric acid
was determined in special samples by titrating with 0.1 N KOA. The unreacted
olefin was then distilled from the reaction mixture. and the remainder was
fractionated under vacuum.
The dialkyldi~hlophosphoric acid was obtained by ttie interaction of
pentavalent phosphorus with the corresponding alcohol (14 ).
50X1-HUM
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~d~oina gage 4 here
Phosphorus Con-
tent of Product
20
d4
Calcu-
fated
Found
1.2076
1.1742
9.36
8.65
8.95
8.5
8.62
8.5
8.3
1.1706
8.03
8.42
8.32
1.0702
8.03
8.3
? ~
7 72
1.1078
7.5
7.92
7.94
1.0642
7.5
7.84
12.75
1.1704
13.09
12.88
1.0505
11.7
11.71
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50X1-HUM
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LAd~oins page 3 here]
(c4HQo)2PS,H cat- cH-cx 27.5 121-3/0.03 1.5050 1.0816 10.5
(i-C4H90)2PS2H CH2 = CH-CN 44 122-3/0.05 1.5010 1.0986 10.5
(CH30)2P52H CH2 =CH-COOCH3 38 100-103/2 1.5252 1.1558 12.71
(C2H5g)2PS2H CH2 =CH-COOCH3 71 115-7/1.5 1.4948 1.1517 11.4
(c3H.~o)2rs2H cat =cH-coocH3
(i-C3H70)2PS2H CH2 . CH-COOCH3
(i-c4H9o)~ >;2H cH2 = cH-coocH3
(c4a9o)2rs2H cH2 =cH-coocH3
(CH30)2PS2H CH2 =CH-C6H5
43 104/0.075 1.4858 1.0926 9.43
~Ad~oina page 5 here
13.3
13.4
11.37
11.34
13.0
10.9
9.96
10.1
10.22
10.48
11.5
11.65
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(c2H5o)2PS2x
(c3x7o)2rs2x
(i-C3H70)2PS2H
(C4Hy0)2~~
(i-c4x~o)2ps2H
(CH30 )2~2H
(C2H50)2PS2H
(:-c4H9o)2rs2a
(cH3o)2PS2H
cH2= c(cH3)-coocH3
35
135-137/0.15
1.5498
1.1444
10.67
28
129-131/0.1
1.5381
1.0990
9.73
38.5
121-124/0.2
1.5365
1.0966
9.73
13
137-140/0.025
1.5320
1.0890
8.94
17.5
117-122/0.04
1.5301
1.0860
8.94
67
145/3
1.5160
1.2625
12.69
83
167/1.5
1.5050
1.1911
11.38
58
1211-129/0.2
1.4915
1.1162
9.43
38
133-135/2
1.5100
1.2330
12.01
d~oins page 6 here)
il.o
11.28
9.82
9.92
9.81
9.95
8.82
8.8
9.1
9.18
12.71
12.78
11.92
11.98
9.62
9.72
12.01
11.8
!!? ~;~r
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6 2E
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{i-e3x7o)2PS2II cx2 = c(cx3)-coocx3
(i-C4H90)2P52II CAS = C(Cx3)-COOCF13
(e4x90 )2PS2II
(i-c3x7)2rs2x
cx2_ c(cx3)-coocx3
~d,joins page 5 here]
59 154.5/5 1.4995 1,1577
I+7
81+-85/0.02
1.4435
1.1203
56
115-116/0.04
1.4915
1.1138
38
110/0.025
1.4918
1.1132
3?
74/0.15
1.5040
1.1348
8.8
11.31
11.35
10.15
10.28
9.32
2.26
* This product decarbo:cyl=zes during distillation; the phosphorus content is coaputed on the basis oY the decar-
boxylated ester.
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1. N. N. Mel'nikov, p, Ya. Mandel'baum, P. V. Popov, Dok Akad Nauk SSSR,
Vol LXXI, 185 (1950).
2, N. N. Mel'nikov, P. V: Popov, XIX Plenum Sektsil Zashchity Rea:enii
VASKhNII., Tezisy Dokladov (XIX Plenary Session of the Section on Plant Protec-
tion VASKhftIL, Theses of Reports), 4, Stallnabad, 1949, pages 20 and 200.
3. N. N. Mel'nikov, Tr. XX Plenums Sektsii Zashchity Raetenii VASKhNIL,
(Prot. XX Plenary :ieasion of the Section on Plant Protection VASKhNII?), Moscow,
1952, page 3.
4. P. I. Mitrofanov, T. !d. Demosbo, Byu11. Vsesoyuzn. N.-I. In-Ta Chaya
1 Subtropicheskikh kul'tur (Hull. All-Union Sci-Research Inst of Tea any? Sub-
tropical Cultures), No 2, 1951.
6. P. S. Pishchemuka, Zhur Russ Khim Obsh, Vol XLIV, 1406 (1912).
7. US Patend 2 494 126, 10 I 1950 (C. A., Vol XLIV, 3515 (19;0)1.
8. A. N. Pudovik, " A. Arbuzov, Izv Akad PTauk, Otde1 Khim Ns .s, No 5,
9. A, N. Pudovik, B. A. Arbuzov, Zhur Obsh Khim, Vol X%I, 1837 (1951).
10. A, N. Pudovik, Zhur Obsh Khim, Vol XXII, 462 (1950),
11. A, N. Pudovik, Yu. P, Kitayev, Zhur Obsh Khim, vol XXII, 46 (1952)?
12. A, iT. Pudovik, Zhur Obsh Khim, Vol XXI~, 473 (1952)?
13. G. R. "~rman, W. M. Le Suer, T. W. IM.stin, J. Am. Chem. Sac.,
Vol LXXIV, 161 (1952},
14. T. W. Mastin, G. R. Norman, E. A. Weilmanster, J. Am. Chem. Soc ?
Vol LXVII, 1662 (1945)?
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