SU450814A1 - The method of producing thiol phosphonates - Google Patents

Description

(54) METHOD FOR OBTAINING THIOLPHOSPHONATES

I The invention relates to organophosphorus chemistry, namely to a process for the preparation of novel thiol phosphonates of the general formula: substituted or unsubstituted phenyl or benzyl; R is unsubstituted or substituted phenyl, aralkyl, cycloalkyl, alkenyl, alkynyl, ethylthioethyl, alkoxyethyl, aryloxyethyl or the group - (C (CH)); R is alkyl or aryl. f with sulfur dioxide and the treatment of the ether formed with alcohols.J However, compounds of the indicated formula i are new. They possess physiological and biological activity and can be used in agriculture. The proposed method is that The dichlorophosphine is reacted with sulfenyl chloride in the presence of acetic acid, followed by treating the ester with phenol, phenol, alcohol or acetoxime in the presence of a tertiary amine. The proposed method is carried out by displacing approximately equimolar amounts of reagents in an inert organic plant at minus 5 ° plus 8% plus 8% plus 8%. The products are known techniques and are viscous liquids that are soluble in organic solvents and insoluble in water. In many cases, it is advisable to use the product of the reaction of the corresponding thiol or disulfide with an equimolar amount of chlorine or sulfuryl chloride as the starting sulfenyl chloride.

Example 1. Preparation of 0-4-chlorophenyl-S-methylbenzylthiophosphonate.

To a solution of 0.52 g "mol of dimethyl disulfide in 30 ml of dry chloroform, an equimolar amount of chlorine or sulfuryl chloride is added at minus 40-5 ° C. The temperature of the mixture is brought to room temperature and a solution of A. is obtained; To a mixture of 0.1 g mol of benzyldichlorophosphine and 0.1 g of mol of glacial acetic acid in D30 ml of chloroform, solution A is poured at minus 4O-ZO C, the temperature of the mixture is brought to room temperature, dissolved solvent and volatile is removed in vacuo; in the residue, the intermediate α-methyl benzyl chlorothiophosphonate is obtained. To a mixture of 0.25 g mol of intermediate efirkhlorangidri

Yes, and 0.25 g. mol of 4-chlorophenol in 30 ml of benzene at 0-15 ° C O, O25 and g-mol of triethyl mine and kygöpt T 2 hours are added. The FS reaction mass is washed with water, dried azeotropically, the solvent is removed in vacuo and the product is distilled off, m.p. 23O-232 ° C / 2 mm Hg. st., the substance crystallizes on standing, t. pl. 53-54 C, yield 72%,

Found,%: C1 11.10; P 9.65; 810.40.

Calculated,%: C1 11.35; R 9.94; 810.22.

Under conditions of || pa 1, other thiol-phosphonates are obtained, the yield and some properties of which are listed in Table 1.

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PRI mme R 2. Obtaining O-P -cresyl-S -2,5-dichlorophenyl-2,4-dimethylbenzylthiophosphate.

To a mixture of 0.03 g. Mole 2,4-dimethylbenzyl dichlorophosphine and 0.03 g. a mole of acetic acid in 30 ml of chloroform at O - minus 5 ° C, a solution of 0.03 g g of 2,5-dichlorophenylsulfenyl chloride in 2O ml of chloroform is added. The mixture is brought to room temperature, the solvent and volatiles are removed in vacuo, and the residue is intermediate S -2,5-dichlorophenyl-2,4-dimethylbenzyl chlorothiophosphonate.

Into a mixture of 0.15 g of a mole of intermediate ether and anhydride and 0.015 g of mole of fl-cresol, 0.015 g of a mole of triethylamine is introduced into 30 ml of benzene at 5-10 ° C. The mixture was boiled for 2 hours, washed with water, the organic layer was dried azeotropically, the solvent was removed in vacuo at 1 ° C / 1015 mm Hg. Art., the remainder receive the target product, fl 1,5 82 O; yield 98% .D

Found,%: C1 15.41; P 6.54;

37.62.

S2 2lC4VS

Calculated,%: C 15.75; R 6.87;

87.10 ..

PRI me R 3. Preparation of S -butyl-O- (4-chlorophenoxy) ethylbenzylthiophosphonate.

An equimolar amount of chlorine or sulphuryl chloride is added to a solution of 0, O26 gm of dibutyl disulfide in 20 ml of dry chloroform at minus 40 -50. The temperature of the mixture is brought to room temperature and a solution A is obtained. A solution of 0.05 g is obtained. mol,: benzyldichlorophosphine and 0.05 g of mol of glacial acetic acid in DL ml of chloroform at minus 30-4 ° C. solution A is introduced. The temperature of the mixture is brought to room temperature, the solvent and volatiles are removed in vacuo at 1OO C / S- 15 mmHg Art. The residue is dissolved in 30 mp of benzene and a solution of 0.05 g mol of j3 (4-chlorophenoxy) ethanol and 0.05 g is poured into the solution obtained at 0-5 C. mole

hryethylamine in 30 ml of benzene. Mixture | heated for 3 hours at 50 bO-C, washed with water, the organic solution was dried azeotropically, the solvent was removed in vacuo and the residue was used

product, p 1.5660; j20

 four

1.2233; MRjj found 106.0; calculated 106.9, yield 98%.

Found,%: C1 8.48; R 7.51; . 88.36.

 SPS Calculated%: C1 8.91; P 7.76; S 8.03.

I Example 4. Preparation of O- (S 1 -ethylbenzylthiophosphonyl) acetoxin.

Under the conditions of Example 1 of 0, O52, a mole of ethyl mercaptan and an equimolar amount of chlorine or sulphuryl chloride, solution A is obtained.

To a mixture of 0.05 gmol benzyl dichlorophosphine and 0, O5 g. Mol of glacial acetic acid, solution A is added at minus D-4O ° C. The reaction mass is brought to room temperature, the solvent and volatiles are removed in vacuo and the residue is dissolved in 30 ml of benzene. A solution of 0.05 g mol of acetoxime and 0, O5 g mol of triethylamine in 30 ml of benzene is added to the solution obtained at 5–10 ° C. The mixture is heated for 2 hours at 50 ° C, cooled, rinsed with water, dried azeotropically, the solvent is removed in vacuo and the residue is obtained the desired product,

 1,555; d 1,1676; MR

found 74.6; calculated 74.9; yield 96%.

 Found,%: N 5.36; R 11.14; 811.59.

 N 2

Calculated,%: M5,17; R 11.43; 311.81.

Under the conditions of examples 3 and 4, other substances are obtained, the yield and some properties of which are listed in Table. 2

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Example 5: Preparation of 3-2,5-dichlorophenyl-O-propargyl-2, 4-dimethylbenzylthiophosphonate. To a mixture of 0, OZ g. mol 2,4-dimesh1beni zildichlorophosphine and. 0, OZ g. mol of glacial acetic acid in 30 ml of chloroform at O-minus 5 ° C. add a solution of OOZ g. mol of 2,5-dichlorophenylsulfenyl chloride and 30 ml of chloroform. The temperature of the mixture is allowed to return to room temperature, the solvent and volatiles are removed in vacuo at 100 ° C / 10-15 mm Hg. Art. and the residue is dissolved in benzene. In the resulting solution with the input mixture of 0, OZ g mol of propargyl alcohol and 0, OZ g-g mol of triethylamine in 2 O ml of benzene. The mixture is heated for 2 hours at 50 ° C, washed with water, dried azeotropically, the solvent is removed in vacuo, the desired product is obtained in the residue, C 1.5750; i2O d At 1.2078, yield 96%. 17.56; R 7.49; Found,%; C1 S 8.37. Calculated,%: C1 17.73; R 7.75; S 8.01. Under the conditions of Example 5, the substance shown in Table 2 is obtained. 2 last. Subject of the invention. A method of producing thiol phosphonates of the general formula where R is a substituted or unsubstituted phenyl or benzyl; (- unsubstituted or substituted phenyl, aralkyl, cycloalkyl, alkenyl, alkynyl, ethylthioethyl, alkoxyethyl, aryloxyethyl or the group - N asCCCH,); alkyl or aryl, characterized in that the corresponding dichlorophosphine is reacted with sulfenyl chloride in the presence of acetic acid, followed by treating the ether formed with phenol, alcohol or acetoxim in the presence of a tertiary amine and isolating the target product by known techniques.