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Method for synthesizing benzsulfamide compound from benzene sulfonyl chloride compound and triethylamine without metal catalysis

A benzenesulfonyl chloride type, metal-free catalysis technology, applied in the preparation of sulfonic acid amides, organic chemistry and other directions, can solve the problems of inaccessibility, pollution, restrictions and the like, and achieve the effects of pollution-free recovery, broad application prospects and simple recovery.

Active Publication Date: 2019-01-18
NAT UNIV OF DEFENSE TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Therefore, the existing synthesis of benzenesulfonamides requires transition metal catalysis (comprising some toxic metals), and toxic metals will pollute the environment, the atom economy is general, and most of the reaction raw materials are expensive and difficult to obtain, so that they are widely used in industrial production. subject to certain restrictions

Method used

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  • Method for synthesizing benzsulfamide compound from benzene sulfonyl chloride compound and triethylamine without metal catalysis
  • Method for synthesizing benzsulfamide compound from benzene sulfonyl chloride compound and triethylamine without metal catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0012] Embodiment 1: N,N-diethyl-2-methylbenzenesulfonamide

[0013] Substrate 57.19mg (0.3mmol) 2-methyl-1-benzenesulfonyl chloride and 60.71mg (0.6mmol) triethylamine, catalyst 4.98mg (0.03mmol) potassium iodide, oxidant tert-butyl hydroperoxide (0.12mL) and solvent THF (2mL), added to a 30mL sealed tube under air. Then the sealed tube was placed in an oil bath at 120°C for 12 h. After the reaction was finished, the reaction solution was cooled to room temperature, an appropriate amount of ethyl acetate was added to dilute the reaction solution, and it was filtered through a sand core funnel, and the filtrate was separated by silica gel column chromatography after rotary evaporation (ethyl acetate / petroleum ether: 1 / 2 as the eluent) to obtain 35.40 mg of yellow oily liquid with a yield of 54.4%.

[0014] The resulting liquid was subjected to hydrogen spectroscopy 1 H NMR (400MHz, CDCl 3 ): δ7.62(t, J=16.0Hz, 2H), 7.38(t, J=8.0Hz, 2H), 3.26-3.21(m, 4H), 2.42(s, 3H), 1.13...

Embodiment 2

[0015] Embodiment 2: N, N-diethyl-4-methoxybenzenesulfonamide

[0016] Substrate 61.99mg (0.3mmol) 4-methoxy-1-benzenesulfonyl chloride and 60.17mg (0.6mmol) triethylamine, catalyst 4.35mg (0.03mmol) ammonium iodide, oxidant tert-butyl hydroperoxide ( 0.12mL), and the solvent toluene (2mL), were added to a 30mL sealed tube in an air environment. Then the sealed tube was placed in an oil bath at 120°C for 12 h. After the reaction was finished, the reaction solution was cooled to room temperature, and an appropriate amount of ethyl acetate was added to dilute the reaction solution, and it was filtered through a sand core funnel. After the filtrate was rotary evaporated, it was separated by silica gel column chromatography (ethyl acetate / petroleum ether: 1 / 2 as eluent) to obtain 37.70 mg of yellow oily liquid with a yield of 46.7%.

[0017] The resulting liquid was subjected to hydrogen spectroscopy ( 1 H NMR (400MHz, CDCl 3 ): δ7.74(d, J=8.0Hz, 2H), 6.96(d, J=8.0Hz, 2H), 3.8...

Embodiment 3

[0018] Embodiment 3: N, N-diethyl-4-iodobenzenesulfonamide

[0019] Substrate 90.75mg (0.3mmol) 4-iodo-1-benzenesulfonyl chloride and 60.71mg (0.6mmol) triethylamine, catalyst 4.34mg (0.03mmol) ammonium iodide, oxidant tert-butyl hydroperoxide (0.12mL ), and the solvent CH 3 CN (2mL), added to 30mL sealed tube under air environment. Then the sealed tube was placed in an oil bath at 120°C for 12 h. After the reaction was finished, the reaction solution was cooled to room temperature, and an appropriate amount of ethyl acetate was added to dilute the reaction solution, and it was filtered through a sand core funnel. After the filtrate was rotary evaporated, it was separated by silica gel column chromatography (ethyl acetate / petroleum ether: 1 / 2 as eluent) to obtain 62.90 mg of yellow oily liquid with a yield of 66.9%.

[0020] The resulting liquid was subjected to hydrogen spectroscopy 1 H NMR (400MHz, CDCl 3 ): δ7.85(d, J=8.0Hz, 2H), 7.53(d, J=4.0Hz, 2H), 3.26-3.21(m, 4H),...

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Abstract

The invention relates to a method for synthesizing a benzsulfamide compound from a benzene sulfonyl chloride compound and triethylamine without metal catalysis. The benzsulfamide compound is generatedby adopting the benzene sulfonyl chloride compound and triethylamine as subtsrates, an iodine-containing compound as a catalyst and tert-butyl hydroperoxide as an oxidant to have an S-N bond couplingreaction in a solvent. The catalyst used in the method of the invention is simple and easy to obtain, stable in air, simple to recycle and pollution-free; and the method of the invention has a wide application prospect in drug synthesis and industrial production.

Description

technical field [0001] The invention belongs to the field of organic synthesis and drug synthesis, and relates to the synthesis of benzenesulfonamide compounds. In more detail, under metal catalysis conditions, benzenesulfonyl chloride compounds and triethylamine are used to catalyze the synthesis of benzenesulfonamide compounds with iodine-containing compounds. Methods. Background technique [0002] Benzenesulfonamides are often obtained by the amination reaction of benzenesulfonyl chloride. Such substances have potent antifungal, bacterial, anticancer, antipsychotic, anti-HIV protease inhibitors and other biological activities. Most have been used as potent cysteine ​​protease and carbonic protease inhibitors. Therefore, the development of synthetic methods of benzenesulfonamides has important practical value. At present, there are many synthesis methods of benzenesulfonamide compounds under the catalysis of transition metals, for example: 2 In the catalytic system, th...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C303/38C07C311/16C07C311/29
CPCC07C303/38C07C311/16C07C311/29
Inventor 刘卓靓王建方陶呈安王芳柳天雄黄坚李玉姣阳绪衡
Owner NAT UNIV OF DEFENSE TECH