SU430107A1 - METHOD OF OBTAINING DICHLORANOGIDRID ALKYL (Aryl) -TYOMETHYLPHOSPHONE ACIDS - Google Patents

Description

I

The invention relates to the field of production of phosphonic acid dichloride anhydrides, in particular, to a method for producing new alkyl dichlorides of alkyl (aryl) thiomethylphosphonic acids of the general formula

RSCHaPCU, II O

where R is alkyl or aryl. These compounds can be used as intermediates for the synthesis of physiologically active substances.

The reaction of alkyl dihalogen phosphites with α-halogenated ethers in the presence of Fridal-Crafts catalysts is known, leading to the formation of alkoxyalkano phosphonate acid dihalides.

Organochloromethyl sulfides were not previously introduced into this reaction.

The method of producing alkyl (aryl) thiomethylphosphonic acid dichlorides is based on the fact that alkyl dichlorophosphite of formula

ROPClg,

where R is alkyl,

is reacted with an alkyl (aryl) chloromethyl sulfide of the formula

where R is alkyl or aryl. The process is carried out by heating in the presence of Lewis acids, for example, FeCls, BPz, AlCl3, ZnCU, TiCU. It is desirable to maintain the temperature in the range of 100-140 ° C. The target products are recovered by known methods. The yield reaches 70%.

Example 1. Preparation of c-propylthiomethylphosphonic acid dichlorohydrin.

A mixture of 22.16 g of o-methyldichlorophosphite, 20.75 g of i-propyl chloromethyl sulfide and 0.35 g of ferric chloride is heated for 4 hours at 125-130 ° C. Then the reaction mixture is distilled in vacuum. 23.5 g (70.8%) of n-propylthiomethylphosphonic acid dichloride are obtained, t. Bale. 118-119 ° С (8 mm of mercury); 1.5484; 1.3280; MR-D found 47.27; MR-o calculated 46.72.

Paydeno,%: C 24.08; 24.48; H 3.76; 3.43; R 14.92; 14.73.

S4P9S12OR5.

Calculated,%: C 23.20; H 4.38; R 14.96.

Example 2. Preparation of c-propylthiomethylphosphonic acid dichloride.

A mixture of 22.6 g of o-methyldichlorophosphite, 21.2 g of i-propyl chloromethyl sulfide and 14 ml of boron trifluoride ethylate is heated at a temperature of 125-135 ° C for 4 hours. The reaction mixture is then distilled in vacuo. 21.7 g (61.6%) of n-propylthiomethylphosphonic acid dichloride are obtained.

Example 3. Preparation of isopropylthiomethylphosphonic acid dichloride.

A mixture of 25.2 g of o-methyldichlorophosphite, 23.6 g of isopropyl chloromethyl sulfide and 0.55 g of ferric chloride is heated for 3 hours at a temperature of 100-115 ° C. The reaction mixture is then distilled in vacuo. 27 g (68.9%) of isopropylthiomethylphosphonic acid dichloride are obtained; m.p. 80-81 ° C (0.14 mm Hg. Art.); P D 1.5130; d 1,3200; MKV found 47.25; MRn calculated 46.72.

Found,%: C 23.07; 22.80; H 3.84; 3.75; R 14.33; 14.31.

CingCbOPS.

Calculated,%: C 23.20; H 4.38; R 14.96.

Example 4. Obtaining n-butylthiomethylphosphonic acid dichloride.

A mixture of 20.3 g of n-butylchloromethyl sulfide, 19.5 g of o-methyldichlorophosphite and 0.22 g of ferric chloride is heated for 2 hours at a temperature of 95-105 ° C, then 1.5 hours at 130-135 ° C. After distillation of the reaction mixture 21.8 g (67.3%) of n-butylthiomethylphosphonic acid dichloride are obtained in vacuo; m.p. 92-93 ° C (0.2 mm Hg. Art.); on 1,5112; 1.2805; MRo found 51.75; MRc calculated 51.34.

Paydeno,%: C, 27.45; 27.49; H-4.64; 4.96; C1 31.27.

CsHnCbOPS.

Calculated,%: C 27.16; H 5.01; C1 32.07.

Example 5. Preparation of phenylthiomethylphosphonic acid dichloride.

A mixture of 10.8 g of o-methyldichlorophosphite, 12.9 g of phenyl chloromethyl sulfide and 0.1 g of ferric chloride is first heated for 2 hours at PO-125 ° C, then 1.5 hours at 130-135 ° C. After distillation in vacuum, 5 are obtained , 2 g (26.5%) of phenylthiomethylphosphonic acid dichloride, t. Bale. 124-125 ° C (0.12 mm Hg. Art.); ives 1,6008; d1 1.4210; MRo found 58.09; MRn calculated 57.54.

Found,%: C 35.69; 35.82; H 2.58; 2.01.

CrHjCbOPS.

Calculated,%: C 34.87; H 2.93.

Example 6. Preparation of ethylthiomethylphosphonic acid dichloride.

A mixture of 36.9 g of ethyl chloromethyl sulfide, 44 g of o-methyldichlorophosphide and 0.9 g of ferric chloride is heated for 7 hours at 120-125 ° C and then distilled in vacuum. 40.5 g (63.5%) of ethylthiomethylphosphonic acid dichloride are obtained; m.p. 116-117 ° С (10 mmHg); 76-77 ° C (0.15 mmHg); nf 1.5230; d 1.3820; MRo found 42.67; MRn calculated 42.11.

Found,%: C 18.78; 19.10; H 3.53; 4.00; R 15.84; 15.47.

SzNSTSORZ.

Calculated,%: C 18.56; H 3.63; P 16.05.

Subject invention

Claims (2)

1. A method for producing alkyl (aryl) thiomethylphosphonic acid dichlorides, wherein alkyl dichlorophosphite is reacted with alkyl (aryl) chloromethyl sulfide by heating in the presence of Lewis acids, followed by isolation of the target product by known techniques. 2. A method according to claim 1, characterized in that the process is carried out at 100-140 ° C.