SU673166A3 - Method of producing sulphoxide or sulphonic derivatives of carbamates - Google Patents

Description

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The invention relates to methods for producing new compounds, specifically sulfoxide or sulfone derivatives of carbamates of the general formula O "H 1

and - $ о п-С- (; О). .to

in which P may be 1 or 2; Rhalogenphenyl, phenylpropyl, substituted benzyl, in which the substituents are selected from chlorine, methylfluoro and methyl, RI and Rj are identical or different and mean alkyl Cj-Cj, cycloalkyl Cj-Cfi, alkenyl Cj-Cj, alkynyl Cj-Cg and benzyl, which can be applicable in agriculture, as they are characterized by herbicidal activity.

Sulfoxide and sulfone derived carbamates of general formula (1) possess greater herbicidal activity than the previously used rajpencides.

The aim of the invention is to obtain new compounds.

The proposed method is based on the known oxidation reaction of sulfides with perbenzoic acid 1.

However, the use of sulfide as the starting compound.

g

carbamate derivative of general formula

S /

R-s-c-tfc

(2.1

where R, RJ and R have the indicated meanings, it allows to obtain new compounds of the general formula (, 1) with improved herbicidal properties.

The essence of the proposed method consists in obtaining sulfoxide and sulfone derivatives of carbamates of general formula (1) by reacting the carbamate of general formula (2) with an oxidizing agent, m-chloroperoxybenzoic acid, at a temperature of from -16 to 41 seconds.

The reaction is carried out in the presence of a solvent, such as chloroform, methylene chloride, or benzene, and at a reduced temperature of from about -16 to 41 ° C. The amount of oxidizing r1 used in the reaction must be at least one molar equivalent in order to form Sulfoxide derivatives and at least two molar equivalents to form sulfonic derivatives. P p and m e p II O A solution containing 7.5 g of m-chloroperoxybenzoic acid in 100 ml of methylene chloride is prepared in the reaction vessel. At this temperature, at a temperature of 30 ° C, 4.4 g (0.017 mol) of S-4-chlorobenzyl diethyl thiocarbamate is added over 1 minute. At the end of the addition, rapid refluxing was started and the temperature was raised to. The reaction time is up to 40 minutes. Then the mixture is cooled and filtered, and the pressed precipitate is washed with two portions of 25 ml of methylene chloride. The combined filtrate is washed. four portions of 50 ml of 5% carbonate solution, ji and three portions of 50 ml of water, dried over magnesium sulphate and concentrated in a rotary evaporator, first with a vacuum water pump and finally under high vacuum to get 4, 4 g of the product Pv 1,5425. After the liquid has stood for a short period, it crystallizes. Yield: 4.4 g, melting point 64-72 0. Example 2 .1.H5 / V Ha- - A solution is prepared containing 10.7 g (0.0525 mol) m-chloro-peroxybenzoic acid and 200 ml of methylene chloride. This solution is cooled: 12.9 g (0.05 mol) of S-4-chlorobenzyl diethyl thiocarbamate are added to and within 4 minutes. The duration of the reaction up to 1 h, in

Table Reaction time is lapsed. lopetion T € “tmper - ggury to -5s. In the next 30 minutes, the temperature is maintained at a level, then it is increased to 21.5 seconds. Then the solution is cooled in an ice bath, the cold mixture is filtered, and the pressed precipitate is washed with two portions fv and 25 mp of methylene chloride. The combined filtrate is washed with four 100 ml each of 5% sodium carbonate solution and two times with 100 ml each of water, dried over magnesium sulfate and concentrated on a rotary evaporator, first under a vacuum water pump and finally under a high vacuum. Get 12.3 g of the product, p 1,5678. This product is further converted and 10.6 g of product are obtained, p 1.5680. Example 3 .. tt2-i -V (; In a flask with a capacity of 500 ml, equipped with a thermometer and actuator, 250 ml of methylene chloride and 12.6 g (0.05 mol) of S-benzylisobutyl thiocarbamine dissolved in 25 ml of methylene chloride are placed With stirring, reduce the temperature with dry ice to, Then add 8.7 g of m-chloroperoxybenzoic acid (add quickly) and raise the temperature to 0 ° C for 30 minutes and then until. The cold mixture is filtered and the filtrate is washed with three portions 50 ml of 5% potassium carbonate solution, in two portions of 50wn water, and then dried over magnesium sulfate, desorb, distill with steam to obtain 14.0 g of the product, 1.5255. Other compounds were prepared in a similar way.The table shows the compounds of formula (1).

-Cr%

H-CjH,

Sn

-sn.

sn

-CgHy

2 64-72 C89,8

nf 1,5680

-CgH

njf1,558277,4

,

nf 1,5705-92

-CH (Cf -CrCH

n 1,540595

Continuation of table 13 CipoeHHe compounds confirmed by the IR and NMR spectra. of the invention The method for producing sulfoxide sulphonic derivatives of carbamates of the general formula (1) (jB- (0) p- (-H is 1 or 2; - halophenyl, phenylpropyl, substituted benzyl in which the substituents are selected from joiopa, methyl fluorine and methyl; R, and P are the same or different and mean alkyl 6 C, -Q, pn-clochalkyl rfV, al to en and l C, - (v,, 3 l and n and l bene.p, which is because where the aforementioned R, R (and R are as defined above, is reacted with an oxidizing agent, m-chloroperoxybenzoic acid, at a temperature of from -16 to 4 ° C. regular enrollment information received note in the examination 1. P. Karrer course of organic chemistry. L., Goskhimizdat, 1966, p. 646.