SU292985A1 - METHOD OF OBTAINING TRITIOPHOSPHONATE - Google Patents
METHOD OF OBTAINING TRITIOPHOSPHONATEInfo
- Publication number
- SU292985A1 SU292985A1 SU1299654A SU1299654A SU292985A1 SU 292985 A1 SU292985 A1 SU 292985A1 SU 1299654 A SU1299654 A SU 1299654A SU 1299654 A SU1299654 A SU 1299654A SU 292985 A1 SU292985 A1 SU 292985A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- acid
- tritiophosphonate
- obtaining
- pyridine
- hydrogen sulfide
- Prior art date
Links
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- NJLHHACGWKAWKL-UHFFFAOYSA-N ClP(Cl)=O Chemical compound ClP(Cl)=O NJLHHACGWKAWKL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N Phosphoryl chloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N Methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N Benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005524 benzylchlorides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- -1 dibenzyltrithiophosphonates Chemical class 0.000 description 1
- WXJXBKBJAKPJRN-UHFFFAOYSA-N dihydroxy-methyl-sulfanylidene-$l^{5}-phosphane Chemical compound CP(O)(O)=S WXJXBKBJAKPJRN-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- UZZHGKFIGVRMNT-UHFFFAOYSA-O hydroxy-oxo-sulfanylphosphanium Chemical compound O[P+](S)=O UZZHGKFIGVRMNT-UHFFFAOYSA-O 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Description
Изобретение относитс к новому способу получени тритиофосфоиатов общей формулыThis invention relates to a new process for the preparation of tritiophosphonates of the general formula
RP(SR)2RP (SR) 2
где R и R - алкил, арил.where R and R are alkyl, aryl.
Известен сиособ получени дибензилтритиофосфонатов взаимодействием днхлорангидридов тиофосфоновых кислот с бензилхлоридами и сероводородом в присутствии в качестве катализатора пиридина при нагревании до 120-170°С.There is a known method for the preparation of dibenzyltrithiophosphonates by reacting thiophosphonic acid dichlorides with benzyl chlorides and hydrogen sulfide in the presence of pyridine as a catalyst when heated to 120-170 ° C.
Дл расширени сырьевой базы с использованием легкодоступных исходных соединений предложено примен ть в качестве хлорангидрида кислоты фосфора дихлораигидрид фосфоновой кислоты. В предлагаемом способе в качестве побочных продуктов получаютс ангидриды фосфоновых кислот, важных дл создани фосфорорганических соединений .In order to expand the raw material base using readily available starting materials, it has been proposed to use phosphonic acid dichlorohydride as the phosphorus acid chloride. In the proposed method, phosphonic acid anhydrides important for the production of organophosphorus compounds are obtained as by-products.
Способ получени тритиофосфонатов осуществл ют взаимодействием дихлорангидрида фосфоновой кислоть с галоидными алкилами и сероводородом. Реакцию ведут в ирпсутствии в качестве катализатора пиридина при температуре 120-170°С в растворителе или без него.The method of producing tritiophosphonates is carried out by reacting phosphonic acid dichloride with halide alkyls and hydrogen sulfide. The reaction is carried out in the presence of pyridine as a catalyst at a temperature of 120-170 ° C in a solvent or without it.
Пример 1. Дибензилметилтритиофосфопат .Example 1. Dibenzylmethyltriothiophosphate.
В раствор 0,05 г-моль дихлораигидрида метплфосфоповой кислоты, 0,1 г л{оль бензилхлорида и I мол. % пиридина в 15 мл хлорбензола при 130-140°С пропускают сухой сероводород до прекращени выделени хлористого водорода. К концу реакции на дне пробирки образуетс нерастворима в зка масса (анг 1дрид метилфосфоновой кислоты). Охлажденный раствор сливают с в зкой массы и фракционируют в вакууме, т. кип. 210- (1 м.п рт. ст.). При сто нии кристаллизуетс , т. пл. 47-48°С. Найдено, %: S 30,1.In a solution of 0.05 g-mole of methylphosphonic acid dichlorohydride, 0.1 g l {ol benzyl chloride, and I mol. % pyridine in 15 ml of chlorobenzene at 130-140 ° C. dry hydrogen sulfide is passed until the release of hydrogen chloride is stopped. By the end of the reaction, an insoluble viscous mass is formed at the bottom of the tube (ang1drid of methylphosphonic acid). The cooled solution is drained with a viscous mass and fractionated in vacuo, t. Kip. 210- (1 mp Hg). On standing, it crystallizes, mp. 47-48 ° C. Found,%: S 30.1.
С.гПпРЗз.S.gPPRZZ.
Вычислено, %: S 29,65.Calculated,%: S 29.65.
Выход 81%. Смешанна проба с СМзР(5) (5СН2СбП5)2, полученным из дихлораигидрида метилтиофосфоновой кислоты, депрессии температуры плавлени не дает.Yield 81%. A mixed sample with SMR (5) (5CH2SbP5) 2, obtained from methylthiophosphonic acid dichlorohydride, does not give a depression of the melting point.
Остаток в пробирке раствор ют в воде и упариванием полученного раствора выдел ют метилфосфоновую кислоту, т. пл. 100-102°С. Выход 93%, кислотиый экв. 50,0, вычислено 48,0. Смешанна проба с известпым образдом дспресспи температуры плавлени не дает .The residue in the tube was dissolved in water and methylphosphonic acid was recovered by evaporation of the resulting solution, m.p. 100-102 ° C. 93% yield, acid eq. 50.0, calculated 48.0. A mixed sample with limestone does not give a melting point.
Получают в услови х примера 1 из 0,05 г-моль дихлорапгидрида феиилфосфоновой кислоты и 0,1 г моль 4-хлорбензилхлорида . После отгонки растворител и избытка исходного бензилхлорида в остатке получают кристаллический продукт, выход 95,5%; т. пл. 65-67°С (из смеси бензола и петролейного эфира).Prepared under the conditions of Example 1 from 0.05 gmol feiylphosphonic acid dichlorohydride and 0.1 g moles 4-chlorobenzyl chloride. After distilling off the solvent and an excess of starting benzyl chloride, a crystalline product is obtained as a residue, yield 95.5%; m.p. 65-67 ° C (from a mixture of benzene and petroleum ether).
Пайдено, %: С1 15,21; Р 6,44; S 21,30.Paydeno,%: C1 15.21; P 6.44; S 21.30.
CaoHijCbPSsВычислено , %: С1 15,60; Р 6,81; S 21,09.CaoHijCbPSsCalculated,%: C1 15.60; R 6.81; S 21.09.
Пз в зкой массы кип чением в воде и выпаривапием раствора выдел ют феиилфосфоновую кислоту, т. пл. 159-160°С, кислотный экв. 81,0; вычислено 79,0.Feiylphosphonic acid was isolated by boiling in water and evaporation of the solution, mp. 159-160 ° C, acid eq. 81.0; calculated 79.0.
Предмет изобретени Subject invention
Claims (2)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU292985A1 true SU292985A1 (en) |
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