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Green catalytic synthesis method for N-(phenylimino)indazole-1-thioamides

A technology of phenylimino and thioamide, applied in organic chemistry and other directions, can solve the problems of easy hydrolysis of ionic liquids, unsatisfactory catalytic efficiency, unsuitable for biodegradation, etc., and achieves easy industrialized large-scale production and less catalyst usage. , the effect of not easy to hydrolyze

Active Publication Date: 2014-05-28
ANHUI UNIVERSITY OF TECHNOLOGY
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Problems solved by technology

[0005] The purpose of the present invention is to overcome the ionic liquid consumption and the loss in the recycling use in the process of utilizing acid and alkaline ionic liquids to catalyze the synthesis of indazole compounds in the prior art, the catalytic efficiency is not ideal, and the ionic liquids are prone to hydrolysis and Not suitable for biodegradation and other shortcomings, and provide a kind of polysulfonic acid-based Bronster acidic ionic liquid that is easy to biodegrade, has high acidity, is not easy to hydrolyze, and has low preparation cost as a green catalyst, and catalyzes the synthesis of indazole compounds under solvent-free conditions Methods

Method used

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  • Green catalytic synthesis method for N-(phenylimino)indazole-1-thioamides
  • Green catalytic synthesis method for N-(phenylimino)indazole-1-thioamides
  • Green catalytic synthesis method for N-(phenylimino)indazole-1-thioamides

Examples

Experimental program
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Effect test

Embodiment 1

[0022] Example 1: 2mmol of benzaldehyde, 2mmol of dithizone, 2mmol of 5,5-dimethyl-1,3-cyclohexanedione and 0.6mmol of BAIL were added to a 25ml single-necked flask equipped with a stirring bar and a condenser. React under vigorous stirring at 80°C for 35 minutes, TLC (thin-plate chromatography) tracking detection (developing solvent is n-hexane: ethyl acetate = 4:1), the raw material point disappears, ice water cooling, suction filtration, the filter residue is passed through a silica gel chromatography column (flow The phase is n-hexane:ethyl acetate=4:1) to obtain pure 2,3,4,5,6,7-hexahydro-6,6-dimethyl-4-oxo-2,3-diphenyl Base-N-(phenylimino)indazole-1-thioamide, the yield was 85%. The filtrate (the main components are BAIL and water) can be reused after successively rotary evaporation and vacuum drying.

[0023] 2,3,4,5,6,7-Hexahydro-6,6-dimethyl-4-oxo-2,3-diphenyl-N-(phenylimino)indazole-1-sulfur Substituted amides: m.p.186~188℃; 1 H NMR (400MHz, CDCl3): δ=0.78(s, 3H),...

Embodiment 2

[0024] Example 2: 2mmol p-chlorobenzaldehyde, 2mmol dithizone, 2mmol 5,5-dimethyl-1,3-cyclohexanedione and 0.7mmol BAIL were added to a 25ml single-necked bottle with a stirring bar and a condenser . React under vigorous stirring at 90°C for 40 minutes, TLC (thin-plate chromatography) tracking detection (developing solvent is n-hexane: ethyl acetate = 4:1), the raw material point disappears, ice water cooling, suction filtration, the filter residue is passed through a silica gel chromatography column (flow The phase is n-hexane:ethyl acetate=4:1) to obtain pure 3-(4-chlorophenyl)-2,3,4,5,6,7-hexahydro-6,6-dimethyl- 4-Oxo-2-phenyl-N-(phenylimino)indazole-1-thioamide, the yield was 82%. The filtrate (the main components are BAIL and water) can be reused after rotary evaporation and vacuum drying.

[0025] 3-(4-Chlorophenyl)-2,3,4,5,6,7-hexahydro-6,6-dimethyl-4-oxo-2-phenyl-N-(phenylene Amino) indazole-1-thioamide: m.p.87~89℃; 1 H NMR (400MHz, CDCl 3): δ=0.80(s, 3H), 0.95(s,...

Embodiment 3

[0026] Example 3: 2mmol p-phenylbenzaldehyde, 2mmol dithizone, 2mmol5,5-dimethyl-1,3-cyclohexanedione and 0.6mmol BAIL were added to a 25ml single-necked bottle with a stirring bar and a condenser middle. React under vigorous stirring at 95°C for 40 minutes, TLC (thin plate chromatography) follow-up detection (developing solvent is n-hexane: ethyl acetate = 4:1), the raw material point disappears, ice water cooling, suction filtration, the filter residue is passed through a silica gel chromatography column (flow The phase is n-hexane:ethyl acetate=4:1) to obtain pure 3-(4-diphenyl)-2,3,4,5,6,7-hexahydro-6,6-dimethyl-4 -Oxo-2-phenyl-N-(phenylimino)indazole-1-thioamide, the yield was 81%. The filtrate (the main components are BAIL and water) can be reused after successively rotary evaporation and vacuum drying.

[0027] 3-(4-diphenyl)-2,3,4,5,6,7-hexahydro-6,6-dimethyl-4-oxo-2-phenyl-N-(phenylimino ) Indazole-1-thioamide: m.p.179~181℃; 1 H NMR (400MHz, CDCl 3 ): δ=0.84(s, 3...

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Abstract

The invention discloses a green catalytic synthesis method for N-(phenylimino)indazole-1-thioamides, which belongs to the technical field of organic synthesis. In a synthetic reaction, a mol ratio of aromatic aldehyde to dithizone to 5,5-dimethyl-1,3-cyclohexanedione is 1: 1: 1, the molar weight of a Mucopolysacchariden Bronsted acidic ionic liquid catalyst is 20 to 50% of that of aromatic aldehyde, reaction temperature is 80 to 100 DEG C, and reaction time is 25 to 60 min; after the reaction, ice water is used for cooling, pumping filtration is carried out, and a filter residue undergoes separation by a silica gel chromatographic column so as to obtain pure N-(phenylimino)indazole-1-thioamides. Compared with other methods using ionic liquid as a catalyst for synthesis of indazoles, the method provided by the invention has the characteristics of good catalytic activity, a small application amount of the catalyst, a small loss amount of the catalyst in cyclic usage of the catalyst, easy biodegradation of the catalyst, convenient industrial large-scale production, etc.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a green catalytic method for synthesizing N-(phenylimino)indazole-1-thioamide compounds. Background technique [0002] Indazole is the biological isostere of indole, and many of its indazole compounds are not only widely used in pesticides, but also in the preparation of antidepressant, anti-inflammatory, analgesic and antipyretic, dopamine antagonistic, anti-tumor, anti-HIV and Intermediates of contraceptives and other drugs. For example, the indazole ring on Cu 2+ Catalyzed reaction with aryl boronic acid can give 1-aryl indazole, 1-aryl indazole can be used as a contraceptive; indazole can be reacted with acid anhydride or acid chloride to get N-acyl indazole, some of which have N-acyl indazole Anthelmintic activity. Therefore, it is of great significance to study the synthesis of indazole compounds. However, the traditional preparation methods of ind...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D231/56
CPCC07D231/56
Inventor 岳彩波高学频吴胜华储昭莲
Owner ANHUI UNIVERSITY OF TECHNOLOGY
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