RU1803404C - Method of n- arylsulfonyldiarylsulfoximides synthesis - Google Patents

Abstract

Usage: as pesticides. SUMMARY OF THE INVENTION: Products of the formula: n-RrCe H4-S02N-S (0) - (C6H4-R2-) 2, where RI H, Cl, R2 H, CH3, F, CI, Br. Products where, yield 94.2%, where RI H, R2 CH3, yield 99%, where RI H, R2 F, yield 96.0%, where RI H, R2 CI, yield 97.7%, where RI H , R2 Vg, yield 86.0%, where Ri CI, R2 H, yield 98.0%, where Ri CI, R2 F, yield 97.5%, where Ri R2 CI, yield 96.8%, where Ri CI, R2 CH3, yield 96.0%, where Ri CI, R2 Br, yield 94.0%, where Ri CI, R2 H, yield 43.0%. Reagent 1: diaryl sulfoxide. Reagent 2: M, M-dichloroarenesulfamide. Reaction conditions: carbon tetrachloride, solvent boiling point. 2 tab.

Description

Ri H, CI; R2 H, CH3, F, CI, Br, which can be used as pesticides, also exhibit pharmacological activity.

An object of the invention is to provide a process for the preparation of new compounds in high yield by a simpler technology.

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The method is carried out as follows.

An equimolar mixture of diaryl sulfoxide a and M, M-dichloroarenesulfonamide is dissolved by heating in carbon tetrachloride. The solution was boiled in a flask under reflux until the evolution of chlorine was stopped, which was analyzed qualitatively by the color of the iodine starch indicator paper. The process time was usually 8-10 hours. The yield was 85-99% of theory. The reaction is carried out at the boiling point of the solvent. Lowering the temperature is impractical, since it leads to a decrease in the yield of the target product and requires additional energy due to the increase in the process time. The temperature rise is limited by the boiling point of the solvent. The conditions for the preparation of N-arylsulfonyl diaryl sulfoximides are given in Table 1.

The structure of sulfoximide (X) is proved by the X-ray diffraction method. The structure of the remaining compounds was compared with this sulfoximide according to the data of PC and PMR spectra.

Example 1. To a solution of 1.00 g (5.0 mmol) of diphenyl sulfoxide in 20 ml of carbon tetrachloride, 1.13 g (5.0 mmol) of N-benzenesulfonic acid N. N-dichloramide are added. The reaction mass is heated in a flask under reflux until the chlorine evolution ceases (10 hours). The solvent was removed by vacuum of a water-jet pump. The remaining viscous mass crystallizes upon trituration with hexane (30 ml). 1.68 g (94.2%) of compound (I) are obtained. The product is purified by recrystallization from carbon tetrachloride.

Physico-chemical characteristics of compounds 1-X are presented in table.2.

Example 2. Same as in Example 1, but 1.15 g (5.0 mmol) of diethyl sulfoxide and 1.13 g (5.0 mmol) of N-benzenesulfonic acid N. N-dichloroamide were taken in the reaction. 1.91 g (99.0%) of compound (II) are obtained. The product is purified by recrystallization from acetone.

Example 3, Same as in example 2, but 1.07 g (4.5 mmol) of di- (4-fluorophenyl) sulfoxide and 1.02 g (4.5 mmol) of M, benzenesulfonic acid M-dichloramide are taken in the reaction . 1.70 g (96.0%) of compound (Ml) are obtained.

Example 4, Same as in example 2, but 1.22 g (4.5 mmol) of di- (4-chlorophenyl) sulfoxide and 1.02 g (4.5 mmol) of M, benzenesulfonic acid M-dichloramide are taken in the reaction . 2.03 g (97.7%) of compound (IV) are obtained.

Example 5. Same as in example 2, but to the reaction take 8.65 g (24 mmol) of di- (4-bromophenyl) sulfoxide and 5.46 g (24 mmol) of N.N-benzene sulfonic acid.

The reaction time is 10 hours. 10.6 g (86%) of compound (V) are obtained.

Example 6. 1.00 g (5.00 mmol) of diphenyl sulfoxide and 1.30 g (5.00 mmol) of 4.N. N-trichlorobenzenesulfonamide are dissolved in 20 ml of carbon tetrachloride. The reaction mass is heated in a flask under reflux until the chlorine evolution is complete (8.5 hours). The solvent is removed under

vacuum water jet pump. The isolated viscous mass crystallizes upon trituration with hexane (30 ml). 1.90 g (98.0%) of compound (VI) are obtained. The product is purified by recrystallization from acetone.

5 Example 7. Also, as in example 6, but 1.04 g (4.5 mmol) of ditolyl sulfoxide and 1.17 g (4.5 mmol) of 4, M, M-trichlorobenzenesulfonamide are taken into the reaction. Reaction time 6.5 hours. 1.81 g (96.0%) of the compound are obtained.

0 (VII),

Example 8. The same as in example 6, but in the reaction take 1,07 g (4.5 mmol) of di- (4-fluorophenyl) sulfoxide and 1.17 g (4.5 mmol) of 4, M, L- trichlorobenzenesulfonamide. Time

5 reaction 10 hours. 1.88 g (97.5%) of compound (VIII) are obtained.

Example 9. The same as in example 6, but in the reaction take 1,09 g (4.0 mmol) of di- (4-chlorophenyl) sulfoxide and 1.04 g (4.0 mmol)

0 4, M, M-trichlorobenzenesulfonamide. The reaction time was 11 hours. 1.78 g (96.8%) of compound (IX) were obtained.

Example 10. Same as in example 6, but 0.73 g (2.0 mmol) of di- (45 bromophenyl) sulfoxide and 0.53 g (2.0 mmol) of 4, M, M-trichlorobenzenesulfonamide are taken into the reaction . Time - reaction 10.5 hours. 1.05 g (94.0%) of compound (X) are obtained.

EXAMPLE FOR EXTREME VALUES

0 selected synthesis modes of M-arylsulfonyl diaryl sulfoximides.

. Example 11. 2.00 g (10 mmol) of diphenyl sulfoxide and 2.60 g (10 mmol) of 4.N. N-trichlorobenzenesulfonamide are dissolved in

5 50 ml of carbon tetrachloride. The reaction mass is heated at 50 ° C in a flask under reflux for 11 hours. No cessation of chlorine evolution is observed. The solvent was evaporated.

0 The remaining mass is washed with hot hexane. 1.69 g (43%) of compound (VI) are obtained. Thus, the proposed method allows to obtain a wide variety of substituted N-arylsulfonyl diaryl sulfoximides, while in the known method only water-soluble sulfox can be involved in the amidation reaction. - seeders; to carry out the amidation of sulfoxides without catalysts; raise

Table2