SU466242A1 - Method for preparing dithiol phosphoric acid esters - Google Patents

Description

This invention relates to a new process for the preparation of dithiol-sforic esters of an acidic general formula.

RS.

R-oe

-. about

where R m R is alkyl, aryl or aralkyl; alkyl.

These compounds possess fungicidal, insecticidal, acaricidal, as well as bactericidal and nematicidal activity.

A known procedure for the preparation of dithiol-phosphoric acid esters is mutually dependent on dithiol-phosphoric acid chlorides with alcohols, but: in the presence of hydrogen chloride acceptor.

The starting chlorides | reads are synthesized by the interaction of pyoldichlorophosphite with sulfenyl chlorides and acetic acid. This method is universal and allows one to obtain eff, ir d-ittiol phosphonic acid with both the same and different radicals, but M is notadiene.

In order to simplify the process according to the proposed method, organothyodichlorophosphite is reacted with sulfenyl chloride.

and alcohol in a milk rpo, m ratio of 1: 1 at a temperature of (-40) to (+ 20) ° C.

The parent orethanothiiodichlorophosphites are available as compounds. As

sulfonyl chlorides, it is advisable to use an ave-zinc preparation of the reaction mass, obtained by the interaction of an organic thiol or disulfide with an eq (ImoIt is a chemical amount of chlorine or sulfuryl chloride.

Target products are recovered by known techniques. They are obtained in good yield and as pesticides can be used without distillation.

P pI m 6 p 1. 5-isobutyl-5-2,5-dichlorfen l - 0-p ro P and l d ity ofaf t

0.05 moles of dry prapyl alcohol, while being transported and cooled to -30 ° C, are simultaneously added 0.05 liters of isobutylthiodichlorophosphite and 0.05 mol of 2.5-d Chlorophenylsulfipyl chloride in 5 ml of chloroform. The temperature of the resulting mixture is brought to room temperature, held / under vacuum (10-15 mm Hg) at three 100 ° C and the desired product is obtained in the residue, pb 1.5315, d 1.2246. The yield is 100%.

Found,%: C1 18.71; S 17.43. MR 94.2.

CisHigCbOgPSa. Calculated,%: C1 19.03; S 17.15. MRo 94.1.

Example 2. 5-Propyl-5-Isobutyl-0-actyldithiofosfate.

To a solution of 0.05 mol of propylmarcaptan, 0.05 mol of chlorine (or sulfuryl chloride) is added to 30 ml of chloroform. At (-30) - (-40) ° C. Then the temperature of the mixture is brought to room temperature, the resulting solution is added simultaneously with 0.05 mol of isobutylthiodichlorophosphite to 0.15 mol of isooctyl alcohol: while cooling to (-30) - (- 20) ° C. The temperature of the reaction mass is brought to room temperature, the solvent and volatile are removed under vacuum (10–15 mm Hg) at 100 ° C, and then at a residual pressure of 1–2 mm Hg. Art. and 100 ° C. In the residue receive the target product, "20 1,4572, df 0,9506. Exit 98%.

Found,%: S 18.46. M.RD 97.5.

С15НззО2Р2Calculated,%: S 18,82. MRo 97.2.

Example 3. 5-Vutyl-5-benzyl-0-ethyldithiopho spat.

To pacTEQpy 0.02 mol of dibenzyl disulfide in 30 ml of chloroform tr-and (-30) - (-20) ° C, 0.02 mol of sulfuryl chloride was added. Then the temperature of the mixture was adjusted to O-5 ° C and the resulting solution, simultaneously with 0.04 mol of butylthiodichlorfo-fuffite in 10 ml of chloroform, was added to 0.2 mol of absolute ethanol while cooling to (-40) - (-30) ° C. More the temperature of the mass is brought to room temperature and kept in vacuum (10-15 mm Hg) at 100 ° C. The remainder receive the target pro, 5242, dl ° 1,0921. Exit 99%.

duct,

Found: MRo 85.0.

Calculated: MRo 84.3.

Under the conditions of Examples 2 and 3, other compounds are obtained, and the by-pass and some of the properties 20 of which are listed in the table.

Subject invention

The method of obtaining the esters of dithiol phosphoric acids of the general formula

ES

p-ok

g 4/1

AT&

where R and R are alkyl, aryl or aralkyl;

 alkyl,

aa based on phosphorus acid chlorohydrides and

alcohols, characterized in that, in order to simplify the process, organoiodiodichlorophosphite under the reaction with sulfenyl chloride, and alcohol in a molar ratio

1: 1 br: and temperature from (-40) to

(-f20) ° C.