SU580833A3 - Method of preparing bis-(1,3-disubstituted urea) sulfides - Google Patents

Description

The invention relates to a process for preparing not described, in the literature bis - (1, 3-disubstituted | m? Chevino) sulfides of the general formula I d O O N-t-N- -N-. Where T. is an alkyl containing 1-4 carbon atoms, unsubstituted phenyl or phenyl substituted by 1-2 halogen atoms with an atomic number of 9 - 35, T, j is a hydrogen atom, an alcohol containing 1-4 carbon atoms, unsubstituted phenyl or feiyl, substituted by 1-2 halogen atoms with an atomic number of 9-35, T.-- alkyl containing 1-4 carbon atoms. The compounds of general formula 1 possess physiological activity and are of interest as pesticides. A known method for producing aromatic sulfides by reacting substituted anilines with sulfur chlorides in the presence of an HC1 acceptor, triethyl amine, pyridine. The proposed method is based on a known reaction; The use in the known reaction of the corresponding substituted urea derivatives of the following formula makes it possible to obtain compounds of formula 1 not described in the literature, which is the aim of the invention. According to the invention, a process for the preparation of compounds of formula 1 is described, which consists in the fact that urea is of the general form. III III K-t-N-H "i , gee. i i j KtA & QT: the values given in formula 1 are reacted with sulfur dichloride in the presence of an organic solvent in the presence of an organic base. The reaction is usually carried out by adding freshly distilled sulfur dichloride to urea. The reaction is carried out in a suitable inert solvent, such as benzene, toluene, diethyl ether or a chlorinated hydrocarbon, such as methylene chloride or chloroform, acetonitrile or dimethoxyethane. After completion of the reaction, the amine salt is removed by washing with water and the product solution is dried, filtered and the solvent is distilled off. The product can be purified by recrystallization or, when it is an oil, by chromatography. Upon receipt of urea sulphides in cases where the solvent is not mixed with water, the resulting product is separated by washing with water followed by drying or removing the solvent in a vacuum or by adding Lenin a non-polar solvent, such as hexane, to precipitate the product. In those cases, when the solvent is mixed with water, the product is isolated by pouring the reaction mixture on ice, followed by filtration. Used dichloride sulfur should have a high degree of purity, for example, more than 98% degree of purity. It is often desirable that a small amount of an inhibitor, such as tributyl phosphate or triethyl phosphate, be present in sulfur dichloride to maintain its high purity. Example 1. Preparation of bis (1-methyl-3-o-fluoromethyl-i1-ureido) sulfide 5.6 g (0.05 mol) of freshly distilled sulfur dichloride in 10 ml of methylene chloride is slowly added to 16.8 g ( 0.1 mol) of 1-methyl-3-o-fluorophenylurea and 8.5 g (0.106 mol) of pyridine in 250 ml of methylene chloride. There is a partial dissolution of urea. After stirring for 2 hours at room temperature, the mixture was washed with two 200 ml portions of water, dried over magnesium sulfate, after which the solvent was removed in vacuo. The product is chromatographed on 200 ml of silica gel with elution with diethyl ether. The crystalline product isolated by chromatography is recrystallized from benzene (hexane and 5.5 g of crystals are obtained, melting at 110-114 s. The compound bis- (1-methyl-3-o-fluoromethyl-1-ureido) sulfide in the Tate of elemental analysis has the following composition: Calculated,%: 58.75; 1.38; Found,%: 58.86; 1.72. The nuclear magnetic resonance spectrum confirmed that the recrystallized material has the indicated composition. - (1-methyl-3- (3,4-dichlorophenyl) -1-ureido sulfide 5.6 g (0.05 mol) of sulfur dichloride in 10 ml of methylene chloride slowly 21.9 g- (0.1 mol) of 1-methyl-3- (3,4-dichlorophenyl) urea and 8.5 g (0.106 mol) of pyridine in 250 m of methylene chloride are added to the sludge. Dissolution occurs after Stir for 2 hours. The yellow solution is added to 200 ml of water, which results in the precipitation of a white solid from the solution. The white solid is collected on a filter and the filtrate is treated to obtain an additional amount of crude product. The filter cake is recrystallized from ethanol to obtain 3.7 g of white crystals of bis-1-methyl-3- (3, 4-dichlorophenyl) -1-ureido sulfide, melting at 188-192s. Elemental analysis results; Calculated,%: 3 6.86; 01 30.3 Found,%: 0 6.45; C1 27.87. Example 3. Obtaining bis- (1-methyl-3-p-chlorophenyl-1-ureido) sulfide. 5.6 g (0.05 mol) of sulfuric chloride in 10 ml of methylene chloride are slowly added to a flask containing 16.8 g (0.1 mol) of 1-methyl-3-p-fluorophenyl urea and 8.5 g of pyridine in 250 ml of methylene chloride. The resulting green solution was stirred at room temperature for 2 hours, then washed twice with water, dried and the solvent was removed. The residue is a thick greenish oil that solidifies on cooling. After recrystallization from ethanol (hexane and washing the crystals with hexane, 7 g of bis- (1-methyl-3-p-chlorophenyl -1-.-Ureido) sulfide, melting at 123-136 ° C., are calculated. 5 8 , 77; P 10.38. Found: 3 8.65; V 10.3. Example 4. Preparation of (1) bis- (1-methyl-3-p-chlorophenyl-ureido) sulfide and (2) 1-methyl-3-p-chlorophenyl-1-ureido-1ureido-1-p-chlorophenyl-methyl-1-ureido sulfide 5.6 g of sulfur dichloride in 10 ml of methylene chloride are slowly added to the slurry 18, 5 g of 1-methyl-3-p-chlorophenyl urea and 8.5 g of pyridine in 250 ml of methylene chloride. The resulting brown solution is stirred t for 10-15 hours at room temperature and washed with 200 ml of two portions of water, dried over magnesium sulfate and the solvent is distilled off. The product according to the obtained data is a mixture of two compounds. After separation by chromatography, they were identified and isolated Bis- (1-methyl-3-L-chlorophenyl-urendo) sulfide, melting at 191-196 ° C, the results of chemical analysis are as follows: Calculated,%: $ 8.17; C1 17.78 Found,%: SB, 18; C1 18.18 and 1-methyl-3 p-chloro-phenyl-1-ureido-1-p-chlorophenyl-3-methi.n-1 is a urea-sulfide, melting at 187-193c, the results of its chemical ana. ) 1i: and the following: Calculated,%: 6.01; 01 17.78. Found,%: 8.04; 01 17.76.

invention formula

The method of obtaining bis- (1, 3-disubstituted urea) sulfides of the general formula

BI / B,

Nt-N- $ -JN- ti-N

 i, c "

where, is alkyl containing 1-4 carbon atoms, non-amine phenyl or phenyl, substituted with 1-2 halogen atoms with an atomic number of 9-35,

T, j-atom of hydrogen,

T, .- alkyl containing 1--4 carbon atoms, unsubstituted phenyl or phenyl,

substituted with 1-2 halogen atoms with atomic number 9-35,

where P., P,, have the indicated meanings, are reacted with sulfur dichloride in the medium of an organic solvent in the presence of an organic base.

"eleven

 N, N 11

 ,

T d-alkyl containing J-4 angle atoms of the genus,

characterized in that urine guilt of the general formula