Synthetic method for catalyzing imine to be reduced into amine

Abstract

The invention discloses a synthesis method for catalyzing imine to be reduced into amine, wherein the synthesis method is characterized by comprising the following steps: 1, sequentially putting a sulfonyl imine compound and a catalyst I into a reaction bottle according to a reaction molar ratio of 1:0.01 at normal temperature and normal pressure, adding formic acid and a triethylamine solution according to a volume ratio of 5:2, and reacting in a solvent for 1-15 minutes to obtain a reaction product; and 2, after the reaction in the step 1 is finished, sequentially and slowly adding water and ethyl acetate into an obtained reaction product, sufficiently stirring, standing for layering, extracting a separated water layer by using ethyl acetate, combining an extract of ethyl acetate with a separated organic layer, washing by using saturated edible salt water, and drying by using anhydrous sodium sulfate, evaporating to remove the ethyl acetate solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain the amine compound.

Description

technical field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a synthesis method for catalyzing the reduction of imine to amine. Background technique

[0002] Amines are a class of organic compounds that widely exist in nature and are commonly used in industry, agriculture, and pharmaceutical industries. For example, sulfonamides are a class of well-known compounds with antibacterial activity. There is also Amprenavir, which is a fifth-generation antiretroviral protease inhibitor that inhibits viral proteases by blocking the formation of new, mature virion particles released from the surface of infected host cells, etc. .

[0003] In recent years, the synthesis of sulfonamides has become a research hotspot in recent years. Chemists are still committed to the development of highly efficient and environmentally friendly synthesis of amines or sulfonamides. The method for synthesizing sulfonamides compound has followi...

Examples

preparation example Construction

[0046] A kind of synthetic method that catalytic imine is reduced into amine, the method comprises the following steps:

[0047] Step 1: Under normal temperature and pressure, place the sulfonimide compound and catalyst I in the reaction flask according to the mass molar ratio of 1:0.01, then add formic acid and triethylamine solution according to the volume ratio of 5:2, React in the solvent for 1-15 minutes to obtain the reaction product; the reaction expression is as follows:

[0048]

[0049] R1 represents aromatic rings with different substituent groups, R2 is halogen, methyl and other groups

[0050] Step 2: After the reaction in step 1 is completed, slowly add water and ethyl acetate to the obtained reaction product in sequence, leave to stand for layering after fully stirring, extract the separated water layer with ethyl acetate, and extract the ethyl acetate After being combined with the separated organic layer, they were washed with saturated brine, dried over an...

Embodiment 1

[0077] Add compound N-benzylbenzenesulfonimide (1a) (0.5mmol), catalyst Cat-3 (1mol%), water (2.0mL) into the reaction tube, add HCOOH:Et 3 N(5:2)(1mL), react for 2-10min, until the raw materials are completely reacted. After the reaction, slowly add water and ethyl acetate to the obtained reaction product successively, leave to stand for layering after fully stirring, extract the separated water layer with ethyl acetate, combine the extract of ethyl acetate with the separated organic After the layers were combined, they were washed with saturated brine, dried over anhydrous sodium sulfate, and the ethyl acetate solvent was distilled off to obtain a crude product, which was then separated and purified by silica gel column chromatography to obtain amine compounds. After removal of the solvent, the crude residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate) to give the corresponding product N-benzylbenzenesulfonamide (2aa) (refer to the corresp...

Embodiment 2

[0080] Add the compound N-(4-methylbenzyl)benzenesulfonimide (0.5mmol), catalyst I (1mol%), water (2.0mL) into the reaction tube, add HCOOH:Et3N (5:2) (1mL ), react for 2-10min, and wait for the raw materials to react completely. After the reaction, slowly add water and ethyl acetate to the obtained reaction product successively, leave to stand for layering after fully stirring, extract the separated water layer with ethyl acetate, combine the extract of ethyl acetate with the separated organic After the layers were combined, they were washed with saturated brine, dried over anhydrous sodium sulfate, and the ethyl acetate solvent was distilled off to obtain a crude product, which was then separated and purified by silica gel column chromatography to obtain amine compounds. After removal of the solvent, the crude residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate) to give the corresponding product N-(4-methylbenzyl)benzenesulfonamide (2ab). ...

technical field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a synthesis method for catalyzing the reduction of imine to amine. Background technique

[0002] Amines are a class of organic compounds that widely exist in nature and are commonly used in industry, agriculture, and pharmaceutical industries. For example, sulfonamides are a class of well-known compounds with antibacterial activity. There is also Amprenavir, which is a fifth-generation antiretroviral protease inhibitor that inhibits viral proteases by blocking the formation of new, mature virion particles released from the surface of infected host cells, etc. .

[0003] In recent years, the synthesis of sulfonamides has become a research hotspot in recent years. Chemists are still committed to the development of highly efficient and environmentally friendly synthesis of amines or sulfonamides. The method for synthesizing sulfonamides compound has followi...

Examples

preparation example Construction

[0046] A kind of synthetic method that catalytic imine is reduced into amine, the method comprises the following steps:

[0047] Step 1: Under normal temperature and pressure, place the sulfonimide compound and catalyst I in the reaction flask according to the mass molar ratio of 1:0.01, then add formic acid and triethylamine solution according to the volume ratio of 5:2, React in the solvent for 1-15 minutes to obtain the reaction product; the reaction expression is as follows:

[0048]

[0049] R1 represents aromatic rings with different substituent groups, R2 is halogen, methyl and other groups

[0050] Step 2: After the reaction in step 1 is completed, slowly add water and ethyl acetate to the obtained reaction product in sequence, leave to stand for layering after fully stirring, extract the separated water layer with ethyl acetate, and extract the ethyl acetate After being combined with the separated organic layer, they were washed with saturated brine, dried over an...

Embodiment 1

[0077] Add compound N-benzylbenzenesulfonimide (1a) (0.5mmol), catalyst Cat-3 (1mol%), water (2.0mL) into the reaction tube, add HCOOH:Et 3 N(5:2)(1mL), react for 2-10min, until the raw materials are completely reacted. After the reaction, slowly add water and ethyl acetate to the obtained reaction product successively, leave to stand for layering after fully stirring, extract the separated water layer with ethyl acetate, combine the extract of ethyl acetate with the separated organic After the layers were combined, they were washed with saturated brine, dried over anhydrous sodium sulfate, and the ethyl acetate solvent was distilled off to obtain a crude product, which was then separated and purified by silica gel column chromatography to obtain amine compounds. After removal of the solvent, the crude residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate) to give the corresponding product N-benzylbenzenesulfonamide (2aa) (refer to the corresp...

Embodiment 2

[0080] Add the compound N-(4-methylbenzyl)benzenesulfonimide (0.5mmol), catalyst I (1mol%), water (2.0mL) into the reaction tube, add HCOOH:Et3N (5:2) (1mL ), react for 2-10min, and wait for the raw materials to react completely. After the reaction, slowly add water and ethyl acetate to the obtained reaction product successively, leave to stand for layering after fully stirring, extract the separated water layer with ethyl acetate, combine the extract of ethyl acetate with the separated organic After the layers were combined, they were washed with saturated brine, dried over anhydrous sodium sulfate, and the ethyl acetate solvent was distilled off to obtain a crude product, which was then separated and purified by silica gel column chromatography to obtain amine compounds. After removal of the solvent, the crude residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate) to give the corresponding product N-(4-methylbenzyl)benzenesulfonamide (2ab). ...

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