Method for synthesizing aromatic primary amine through OTf amination

An aromatic primary amine, chemical synthesis technology, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problems of difficult purification, low preparation yield, and unfavorable industrial scale-up production.

Pending Publication Date: 2021-09-14
成都泰和伟业生物科技有限公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is that the existing chemical preparation method of aromatic primary amine

Method used

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  • Method for synthesizing aromatic primary amine through OTf amination
  • Method for synthesizing aromatic primary amine through OTf amination
  • Method for synthesizing aromatic primary amine through OTf amination

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062] Embodiment 1, the preparation of formula A compound

[0063] step 1,

[0064] Add 2mmol of compound A-1 (0.93g) to 14mL of toluene, then add 2eq of cesium carbonate and 7eq of Pd 2 (dba) 3 , 6mol% BINAP, and 2eq of benzophenone imine; the reaction solution was pumped and ventilated three times, heated to 110 degrees under Ar protection, and stirred for 12 hours; the reaction solution was cooled to room temperature and filtered to remove solids, and the filtrate was concentrated under reduced pressure. Purified to obtain compound A-2 (0.5g, yield 50%);

[0065] Step 2,

[0066] 0.25 mmol of compound A-2 (123 mg) was dissolved in 1 mL of THF, after stirring, 20 mL of 2M HCl solution was added, and stirred for 20 min; the reaction solution was extracted with ethyl acetate, and the saturated NaOH solution of the aqueous layer was taken to adjust the pH to 9, extracted with DCM, The organic phase was dried, concentrated under reduced pressure, and purified by a silica ge...

Embodiment 2

[0067] Embodiment 2, the preparation of formula A compound

[0068] step 1,

[0069] Add 4mmol of compound A-1 (1.86g) into 18mL of benzene, then add 1.5eq of cesium carbonate and 6eq of Pd 2 (dba) 3 , 6mol% BINAP, and 1.5eq of benzophenone imine; the reaction solution was pumped and ventilated three times, heated to 100 degrees under Ar protection, and stirred for 14 hours; the reaction solution was cooled to room temperature and filtered to remove solids, and the filtrate was concentrated under reduced pressure. Column purification to obtain compound A-2 (1.5 g, yield 76%);

[0070] Step 2,

[0071] 1 mmol of compound A-2 (492 mg) was dissolved in 2.5 mL of dioxane, after stirring, 37 mL of 2M HCl solution was added, and stirred for 60 min; the reaction solution was extracted with ethyl acetate, and the saturated NaOH solution of the aqueous layer was taken to adjust the pH to 9. DCM was extracted, the organic phase was dried, concentrated under reduced pressure, and pur...

Embodiment 3

[0072] Embodiment 3, the preparation of formula A compound

[0073] step 1,

[0074] Add 1mmol of compound A-1 (0.46g) to 10mL of xylene, then add 2.5eq of cesium carbonate and 6.5eq of Pd 2 (dba) 3 , 6mol% BINAP, and 2.5eq of benzophenone imine; the reaction solution was pumped and ventilated three times, heated to 130 degrees under Ar protection, and stirred for 10 hours; the reaction solution was cooled to room temperature and filtered to remove solids, and the filtrate was concentrated under reduced pressure. Column purification to obtain compound A-2 (0.4g, yield 81%);

[0075] Step 2,

[0076] 0.5mmol of compound A-2 (246mg) was dissolved in 2.5mL of THF, after stirring, 62mL of 2M sulfuric acid solution was added, and stirred for 10min; the reaction solution was extracted with ethyl acetate, and the saturated NaOH solution of the aqueous layer was taken to adjust the pH to 9, and extracted with DCM , the organic phase was dried, concentrated under reduced pressure, ...

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Abstract

The invention discloses a method for synthesizing aromatic primary amine through OTF amination. Amination reaction is carried out on OTF of an aromatic group and benzophenone imine, and then benzhydryl is removed to obtain an aromatic primary amine compound. According to the method for synthesizing the primary aromatic amine through OTF amination, the raw materials are cheap and easy to obtain, the preparation cost is greatly reduced, meanwhile, the operation condition is mild, the operation difficulty is reduced, the energy consumption is low, no pollution is caused to the environment, and the method is suitable for green and environment-friendly industrial production and beneficial to enlarged production and industrial popularization.

Description

technical field [0001] The invention relates to the technical field of synthesis of organic intermediate compounds, more specifically, to a method for synthesizing primary aromatic amines through OTF amination. Background technique [0002] Aromatic primary amines are chemical structures containing amino groups on aromatic groups. They are important active functional groups in the process of new drug development, and are also important reactive functional groups that participate in reactions to prepare other structures; they are widely used. Among them, especially the introduction of aromatic primary amines on amino acid compounds with aromatic groups has a more important modification effect on the molecular structure of drugs. [0003] The methods for introducing aromatic primary amino groups disclosed in the prior art include methods such as nitro group reduction, nitrile group reduction, and reaction of aryl halides with ammonia water. There are many defects in the prepa...

Claims

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Application Information

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IPC IPC(8): C07C269/06C07C271/22
CPCC07C269/06C07C271/22
Inventor 祁伟徐燕军吴逢伟付熙牟勇
Owner 成都泰和伟业生物科技有限公司
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