SU187785A1 - Method of producing alkyl (aryl) dithio dichlorophosphates - Google Patents

Description

A known method for producing alkyl (aryl) dithiodichlorophosphates by reacting ethyl dichlorophosphate with n phosphorus phosphate.

In order to expand the raw material base and increase the yield of products, it has been proposed to produce alkyl (aryl) dithiodichlorophosphates by reacting phosphorus thiotrichloride with mercaptans in the presence of catalytic amounts of a heterocyclic base, for example, pyridine.

Example 1. Obtaining diethyltriothiochlor and diethyldithiodichlorophosphate.

A. In a glass tube equipped with a bubbler and a reflux condenser, 46.9 g (0.25 g mol) of phosphorus trichloride and 0.38 g (2 mol. O /) pyridine are placed, the mixture is heated to 120-125 ° C and ethyl mercaptan gas (0.55 g mol) is bubbled in for 3 hours. With a bubble layer height of 15-20 cm, the mercaptan is almost completely absorbed. Then the temperature is increased to 150-160 ° C and the reaction mass is kept for 3 hours. Fractional distillation allocate:

Diethyltriothiochlorophosphate, 41.8 g (76 ° / o); m.p. 110-112 ° С (2 mm of mercury); df 1.2920;

20 1.6115.

Hd

Paydeno, od; C1 15.81; S 44.02. C HioClPSs.

Calculated, o / o: C1 16.09; S 43.54.

B. Fractional distillation of the mixture obtained under similar conditions from 169.5 g (1 g-mol) of trifluorine phosphorus, 61 g (1 g-mol) of ethyl mercaptan and 0.76 g of pyridine, is isolated:

Phosphorus thiotrichloride, 30 g (17.7o / o).

Ethyldithio Dichlorophosphate, 110 g (69o / o); m.p. 76-78 ° С (5 МА1 рт. Ст.).

Diethyltriothiochlorophosphate, And g (6,1o / o); t. cues. 110-112 ° С (2 mm of mercury).

Example 2

Preparation of dimethyl methylend and d and t and o d and x l o p r p and t and o x l o phosphate.

A. Fractional distillation of the mixture obtained under the conditions of example 1 from 59 g (0.35 g-mol) of phosphorus thiotrichloride and 35 g (0.75 g-mol) of methyl mercaptan in the presence of 0.2 g (1 mol. O / o iiridine is isolated:

Found CI 39.03; S 35.80.

CHsClaPSaCalculated, o / o: C1 39.20; S 35.35.

Dimethyltritiochlorophosphate, 39.8 g (59.4 Vob t. Bale 92-93 ° C (2 mmHg); 1.4153: ng 1.6503.

Found O / Q: Cl 18.10; S 49,41.

CaHfiCIPSa.

Calculated o / o: Cl 18.44; S 49,86.

B. Fractional distillation of resins obtained under similar conditions from 169.5 g (1 g mol of phosphorus trichloride and 48 g (1 g mol) of methyl mercantane in the absence of 1.5 g of niridine,

g (7.7 "/ o).

Phosphorus thiotrichloride, 13,129.3 g (77.2 e / o),

Methyldithio dichlorophosphate, so kin. 55-56 ° C (4 mm Hg. Art.).

Dnmethyltranchlorophosphate, 20 g (9,).

Example 3. Preparation of phenyldithio dichlorophosphate. To 0.1 g-mol of phosphorus thiotrichloride containing 0.076 g (1 mol. O / o) and hydrogen is added with stirring and at a temperature of 125-130 ° C. 0.1 g-mol

thiofeiol. Then the temperature is gradually increased to 150-160 ° C and the reaction mass is maintained for 3 hours. Fractional distillation allocate:

Phosphorus thiotrichloride, 2 g (11.8 o / o) Phenyldithio dichlorophosphate, 15.4 g (); m.p. 130-133 ° C (4 lsh mercury); df 1.4460; ng 1.6540. Found, “/ o: C1 26,17; S 26.05.

CoHsClaPSa.

Calculated, o / o: C1 29.63; S 26,34.

15 of the invention

The method of producing alkyl (aryl) dithiope 1 |; | chlorophosphates, characterized in that, in order to expand the raw material base and increase the yield of target products, phosphorus thiotrichloride is subjected to interaction with mercaptans in the presence of catalytic amounts of a heterocyclic base, for example pyridine.