SU566845A1 - Method of producing s-benz-hydrile thiophosphoric compounds - Google Patents

Description

The invention relates to the field of organophosphorus compounds, namely to a method for producing novel S-benzhydrylthiophosphorus compounds of the general formula

P) bCH-S-p .11 R

. .. -.

where X is oxygen or sulfur, R-alkyl, or alkoxy, alkyl, phenyl or alkoxy.

These compounds can be used as intermediates for the synthesis of physiologically active substances, lubricant additives and CH Michael reagents.

Substances of a similar structure - S-esters of thiophosphoric, thiophosphonic, thiophosphinic and dithiophosphoric acids - are widely used in the chemistry of organophosphorus compounds.

They can be obtained by the addition of phosphorus thioacids to the foremost reagents 1. This method is not universal and results in different reaction products depending on the presence or absence in the reaction mixture of hydroxyl compounds and alkaline agents.

The literature shows the possibility of adding the sodium salts of partial esters

thiophosphorous acid through the thiocarbonyl group of carbon disulfide 2. However, compounds with a P – C bond are formed in this reaction.

The aim of the invention is to obtain new S-benzhydrylthiophosphoric compounds - intermediate products of the synthesis of organophosphorus substances. The method for their preparation is based on the novel reaction of thiocarbonyl compounds with salts of phosphorus acids, leading to compounds with the P – S – C bond.

This is achieved by the fact that thiobenzophenone is reacted with sodium salts of phosphorus acids of the general formula

-R

NaXP

15

R

where X is oxygen or sulfur, R is alkyl, pl alkoxy, alkyl, phenyl or alkoxy,

or with phosphorus acids of the general formula

X. f II / R

where X, R and R have the indicated meanings, in the presence of their sodium salts. The process is carried out at a temperature of from 70 to 130 ° C. Below 70 ° C, the reactions proceed with an insignificant yield, higher than 130 ° C, the resinification of the reaction mixture occurs and the pyrolysis of the starting materials, especially dialkylphosphine oxides and thioxides, occurs. When implementing this method, it is possible to use an inert organic solvent, for example benzene. In the case of the introduction into the reaction of dialkylphosphine oxides, dialkylphosphipate thioxides, alkyl (aryl) thiophosphonous acid partial esters, in a solvent is not necessary. Target products are recovered by conventional methods, for example, fractionation. If an equimolar amount of sodium phosphorus acid is used in the process, before distillation the reaction mixture is neutralized with acetic or dilute hydrochloric acid, or the reaction mass is passed through a column with cation exchange resin in the H-form. The structure of dialkyl-5-benzhydrylthiophosphates and their analogues is confirmed by elemental analysis, IR, NMR, and spectral synthesis. In the IR spectra there are absorption bands (V, cm): 570-575 (P-S), 660-670 (PS), 980-985, 1040-1050 (P-O-C), 1150-1170 (P- O-Alk), 1270-1280 (P O in phosphates), 1510-1515, 1610-1615, 3050-3080 (benzene core), there are no absorption bands of CS, OH, Sli-rpynn. The chemical shifts of der F for dialkyl esters of S-beispdrilthiophosphoric acids are 24-28m. d., which confirms the proposed structure. . S-benzhydryldithiophosphoric acid diethyl ester was also obtained by counter synthesis from diphenyldiazometap and diethyldithiophosphoric acid. The constants, IR and NMR F-spectra of the reaction product and the counter synthesis are completely identical. The identity of the reaction products was monitored by TLC. Example 1. Preparation of S-benzhydrylthiophosphoryic acid dipropyl ester. To the sodium salt of dipropyl phosphite, obtained from 20 g (0.12 g-mol) of dipropyl phosphorous acid and 25 g (0.11 g-at) of sodium in 100 ml of dry benzene, was added 22 g (0.11 g-mol) of thiobenzophenone in 20 ml of benzene. The reaction mixture is heated at kitshenium benzene and stirring for 2-4 hours, then neutralized with an equimolar amount of acetic acid, washed with water. The benzene solution is dried over anhydrous MgSO4, the solvent is removed, the residue is subjected to distillation. 24 g (40%) of S-bezhydrylthiophosphoric acid dipropyl ester was isolated; t. cues. 171-173 ° C / 2 mm Hg. Art. On standing, it crystallizes, the crystals are washed with pentane and characterized; m.p. 2435 ° C; Found: P 8.72; S 8.60. CisHzsOsPS Calculated,%: 8.51; S 8.76; ppm Example 2. Preparation of S-benzhydryl ethylthiophosphonic acid butyl ester. 5 10 15 20 25 30 35 ° 45 50 55 60 65 To the sodium salt of the partial butyl ester of ethyl phosphonous acid obtained from 15 g (0.1 g-mol) of the partial ester and 2.3 g (0.1 g-at) sodium in 100 ml of dry benzene and 19.8 g (0.1 g-mol) of thiobenzophenone in 20 ml of benzene iribavl. The reaction mixture is heated for 2 hours and boiled with benzene and stirring, then neutralized with an equimolar amount of acetic acid, washed with water. The benzene solution is dried over anhydrous MgSO4, the solvent is removed, and the residue is fractionated. 20 g (57%) of benzhydryl ethyl thiophosphonic acid butyl ester were isolated; m.p. 173-174 ° C / 2 mm Hg. Art. On standing, crystallizes; m.p. 69-70 ° C (from pentane). Found,%: P 8.85. CisHasOsPS. Calculated,%: P 8.90. Example 3. Preparation of S-benzhydrylthiophosphoric acid dibtylate ester. Sodium dibutyl phosphite, prepared from 14.7 g (0.076 g-mol) of dibutyl phosphorous acid and 1.74 g (0.076 g-at) of sodium in 70 ml of dry benzene, and 15 g (0.076 g-mol) of thiobeisopheponone in 20 ml of benzene. The reaction mixture is heated at benzene by stirring for 2–4 and then neutralized with an equimolar amount of acetic acid and washed with water. The benzoic solution is dried over anhydrous .i the solvent is removed, the residue is fractionated. 12 g (40.4%) of S-benzhydrylthiophosphoric acid dibutyl ester were isolated; t. cues. 189-190 ° С / 2 mm Hg. Art. On standing, it crystallizes; m.p. 43-44 ° C (from peptane). Found,%: P 7.94. CsiHsgOaPS Calculated,%: P 7.90, br - 28 ppm. Example 4. Preparation of S-beishydryldithiophosphoric acid diethyl ester. To the sodium salt of diethyl thiophosphite, prepared from 7.7 g (0.05 g mol) of diethyl thiophosphorous acid and 3.4 g (0.05 g mol) of sodium ethylate in 50 ml of dry benzene, was added 9.9 g (0 , 05 g-mol) thiobenzophenone in 20 ml of benzene. The reaction mixture is heated at the boiling point of benzene and stirring for 1 hour, then neutralized with an equimolar amount of acetic acid, washed with water. The benzene solution is dried over anhydrous MgSO4, the solvent is removed, the residue is fractionated. 8.8 g (50%) of S-benzhydryldithiophosphoric acid diethyl ester was isolated; m.p. 185 ° C / 1 mm Hg Art., ng 1,5820; 1.1630. Found,%: P 8.92, S 18.05. CiyHsiOgPSa Calcd.,%: P 8.80, S 18.18. Example 5. Preparation of S. Hydroxyhydrylphenyldithiophosphonic Acid Ethyl Ester.

A mixture of 7.7 g of thiobenzophenone and 7.3 g of partial ethyl ester of phenylthiophosphoric acid, containing 0.3 g of sodium salt of the partial ester, is heated at 100-130 ° C for 5 hours, then fractionated. Collect fraction with t. Kip. 180-185 ° C / 0.6 mmHg Art., which immediately crystallizes. The crystals are washed with hexane and ether and characterized. 7.5 g (50%) of S-benzhydrylfeiyl-dithiophosphoicic acid ethyl ester are obtained; t. and l. 204 ° C.

Found,%: C 65.40; H 5.60; R 7.60.

CaiHziOPSa

Calculated,%: C 65.62; H 5.48; P 8.07; br -96 ppm

Example 6. Preparation of dibutyl dithiophosphinic acid S-benzhydryl ester.

A mixture of 7.23 g of thiobenzophenone and 6.5 g of dibutylthiophosphios acid, containing 0.5 g of sodium salt of dibutylthiophosphinic acid, is heated at 100-130 ° C for 3 hours, then fractionated. 6.8 g (50%) of dibutyl dithiophosphinic acid S-benzhydryl ester were isolated; m.p. 189-190 ° С / 0.4 mmHg v .; m.p. 54 ° C (from hexane).

Found,%: P 8.12.

C2lH29PS2

Calculated,%: P 8,24. md

Claims (2)

Invention Formula The method of obtaining S-benzhydrylphosphoric compounds of general formula .R ; X where X is oxygen or sulfur, R is alkyl or alkoxy, R is alkyl, phenyl or alkoxy, meaning that thiobenzophenone is reacted with sodium salts of phosphorus acids of the general formula .R X NaXP T1 II where X, R and R have the ordered values, or with the corresponding phosphorus acids in the presence of their sodium salts at temperatures from 70 to 130 ° C. 2. The method according to c. 1, the process being carried out in an inert organic solvent, for example benzene. Sources of information taken into account in the examination 1.W. N. Mueller, A. A. Oswald. Cationic addition of 0,0 - diethylthiophosphoric acid to olefins. Journ. Orf. Chern., 1966, 31, p. 1894-1898. 2. The patent of France No. 1197647, cl. From 07f, pub. 1959.