SU427945A1 - Method of producing polyfluoroalkyl-substituted benzyl dichlorophosphates - Google Patents

Description

The invention relates to the field of production of dichlorophosphates, namely, to a method for producing new α-polfluoroalkyl-substituted benzyldichlorophosphate in the general formula I, the formula

, C1

CH-O-P

about

where R is polyfluoroal kil,

R is H, alkyl or polyfluoroalkyl.

These compounds can be used as intermediates in the synthesis of practically important substances (plasticizers, non-combustible scrubbers and additives, etc.).

The method of obtaining a-polyfluoroalkyl-substituted benzyldichlorophosphates of general formula I is based on the reaction of a-polyfluoroalkylbenzyl alcohol of the general formula I, which is not known for this class of compounds.

TO

 CH- HE I R

where R is polyfluoroalkyl,

R - H, alkyl or polyfluoroalkyl, with phosphorus oxychloride.

According to the a-polyfluoroalkylbenzyl alcohol method, total formulas II interact with phosphorus oxychloride in the presence of catalytic amounts of salts of metals of the first or second group of the periodic system, for example, magnesium chloride, with heating, preferably about 140-175 ° C, followed by separation of the target product known techniques. Phosphorus phosphorus is preferably taken in excess. The outputs of the target products 60-75%.

Example 1. a-TrifluoromethylBenzyl dichlorophosphate 0.06-0.08 mol of α-trifluoromethylbenzyl alcohol is heated with an excess of phosphorus oxychloride in the presence of a catalytic amount of the metal salt of the first or second group of the periodic system. We have a few hours at a bath temperature of 140-160 ° C the excess phosphorus oxychloride is distilled off and the residue is distilled in vacuo. Get a-trifsrmetilbenzyldichlorophosphate, t.

kip 74-75 ° C (1 mm Hg. Art.); in ° 1.4715, df 1.4768.

Found,%: C 32.6. 32.6; H 2.2, 2.3; C1 24.2, 23.9; F 19.6, 19.6; R 10.6 10.6.

CgHsCbFsOaP.

Calculated,%: C 32.8; H 2.1; C1 24.2; F 19.4; R 10.6.

The catalyst, the ratio of the reactants, the reaction time and the yield of α-trifluoromethylbenzyldichlorophosphate are given in the table.

The temperature of the bath is 150-175 ° С. After distillation in vacuo, 15.8 g (73%) of α-trifluoromethyl - m - trifluoromethylbenzyldichlorophosphate, m.p. 93 ° C (0.7 mmHg); at 1.4372; df 1.57: 01.

Found,%: C 29,8,29,8; H 1.4, 1.4; C1 19.8, 19.2; F 31.4, 31.9; R 8.5, 8.7.

Example 2. a-Heptafluoropropylbenzyldichlorophosphate.

A mixture of 12.7 g of a-heptafluoropropyl benzyl, alcohol, 6.4 ml of phosphorus oxychloride in 130 mg of anhydrous calcium chloride is heated for 15 hours at a bath temperature of 150-17.0 ° C, discharged phosphorus oxide and distilled. residue in vacuum.

. 12.9 g (71%) of a-heptafluoropropylbenzyldichlorophosphate, t. Bales are obtained. 91-93 ° C {0.7 mmHg Art.), so pl. 35-38 ° C.

Found 7 °: C 30.8, 30.9; H 1.8, 1.7; CI 18.1, 18.0; F 34.3, 33.8; R 7.7, 7.7.

SShNbSyrgogr.

C 30.6; H 1.5; CI 18.1;

O / p

Calculate) Sleno, F 33.8; R 7.9.

Example 3. a-Trifluoromethyl-g-trifluoromethylbenzyldichlorophosphate.

A mixture of 14.5 g of a-perfluoromethyl-W-trifluoromethylbenzyl alcohol and 10.9 ml of phosphorus oxychloride and 150 mg of anhydrous calcium chloride is heated for 19 hours at that CgHsClaFsOzP.

Calculated,%: C 29.9; H 1.4; C1 19.6; F 31.6; R 8.6.

The subject of the invention.

Claims (3)

1. The method obtained by α-polyfluoroalkyl-substituted benzyl dihydrogen phosphates of the general formula where R is polyfluoroalkyl, R is H, alkyl, or polyfluoroalkyl, characterized in that the a-lolyfluoroalkylbenzyl opy | mouths interact with phosphorus chloroxide in the presence of catalytic amounts of metal salts in the first or second groups of the periodic system under heating, followed by separation of the target product by known methods . 2. A method according to claim 1, characterized in that the process is carried out at 140-175 ° C. 3. A method according to claim 1, characterized in that the phosphorus chlorocyanine is taken in excess.