THE SYNTHESIS OF SOME MIXED ESTERS OF DITHIOPHOSPHORIC ACID

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CIA-RDP80-00809A000700130139-2
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RIPPUB
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C
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7
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December 22, 2016
Document Release Date: 
September 23, 2011
Sequence Number: 
139
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Publication Date: 
August 31, 1953
Content Type: 
REPORT
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Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 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 ~ .lilt Ix. f..} , .I . ,. .. lo.. I , OllTxf Y ~fT[f, . eIF Ix[~[fxlw6 0I .I [ .. ? . 0 )16 f>, (Tx v. pCl, p ul[xp[0. I Iw III w ..(vf, f fll OM 01 ITf [ x}[M Tf f0 0 ([[II} f} [Il vx(v }x0[I}(p I y .[px .f,.~,(ef.. 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 Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 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 Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 ~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 Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 50X1-HUM Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 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 Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 (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 Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 6 2E Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 ~?~ {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. Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2 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)? Declassified in Part - Sanitized Copy Approved for Release 2012/02/08: CIA-RDP80-00809A000700130139-2