Method for preparing 4-(6-aminopyridin-3-yl) piperazine-1-carboxylate tert-butyl ester

A technology of tert-butyl carboxylate and aminopyridine, which is applied in the field of preparation of 4-piperazine-1-tert-butyl carboxylate, can solve the problems of low yield of target product, many by-products, less than comprehensive yield and the like , to avoid the use of heavy metals and hydrogen environment, reduce the generation of by-products, and shorten the synthesis path.

Active Publication Date: 2018-09-21
深圳蓝新科技有限公司
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Problems solved by technology

Therefore, the current method for photocatalytic synthesis of 4-(6-aminopyridin-3-yl)piperazine-1-carboxylate tert-butyl ester has a relatively long synthetic route and relatively many by-products, resulting in low yield of the target product , the comprehensive yield is less than 81.8%, the cost is relatively high, and there are certain hazards to the environment and health

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  • Method for preparing 4-(6-aminopyridin-3-yl) piperazine-1-carboxylate tert-butyl ester
  • Method for preparing 4-(6-aminopyridin-3-yl) piperazine-1-carboxylate tert-butyl ester
  • Method for preparing 4-(6-aminopyridin-3-yl) piperazine-1-carboxylate tert-butyl ester

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preparation example Construction

[0011] The invention provides a preparation method of tert-butyl 4-(6-aminopyridin-3-yl)piperazine-1-carboxylate. The preparation method of 4-(6-aminopyridin-3-yl)piperazine-1-carboxylic acid tert-butyl ester includes the following steps:

[0012] Add 2-aminopyridine, piperazine-1-carboxylic acid tert-butyl ester, and acridine salt photocatalyst into the solvent, and carry out light reaction in the presence of oxidant to generate 4-(6-aminopyridin-3-yl) Tert-butyl piperazine-1-carboxylate.

[0013] Specifically, in the light reaction, the 2-aminopyridine and piperazine-1-carboxylic acid tert-butyl ester are catalyzed by light and an acridine salt photocatalyst and in the presence of an oxidizing agent to form a product compound C. The chemical reaction formula of the light reaction is as follows:

[0014]

[0015] Wherein, the acridine salt promotes the condensation reaction of the 2-aminopyridine and the tert-butyl piperazine-1-carboxylate under light conditions. In one embodime...

Embodiment 1

[0026] This embodiment provides a method for preparing tert-butyl 4-(6-aminopyridin-3-yl)piperazine-1-carboxylate. The synthesis method of 4-(6-aminopyridin-3-yl)piperazine-1-carboxylic acid tert-butyl ester:

[0027] Add 2-aminopyridine, piperazine-1-carboxylic acid tert-butyl ester, acridine salt visible light catalyst, 2,2,6,6-tetramethylpiperidine-nitrogen-oxide to anhydrous dichloroethane, Then, the reaction environment was replaced with oxygen three times, and the blue LED was irradiated, and the reaction time was 10 hours. After the completion of the reaction, the filtrate was spin-dried and separated by column chromatography to obtain the target product as a colorless white solid with a yield of 95%.

[0028] Wherein, the 2-aminopyridine, tert-butyl piperazine-1-carboxylate, acridine salt, 2,2,6,6-tetramethylpiperidine-nitrogen-oxide and anhydrous dichloroethane are in accordance with Add in the following proportions: for every 2mL of anhydrous dichloroethane, add 0.2mmol...

Embodiment 2

[0033] This embodiment provides a method for preparing tert-butyl 4-(6-aminopyridin-3-yl)piperazine-1-carboxylate. The preparation method of the m-aminophenylacetylene is as follows:

[0034] Add 2-aminopyridine, piperazine-1-carboxylic acid tert-butyl ester, acridine salt visible light catalyst, 2,2,4,6,6-pentamethylpiperidine-nitrogen-oxide to anhydrous dichloroethane Then, the reaction environment is replaced with oxygen three times, and the blue LED is irradiated. The reaction time is 10h. After the reaction, the filtrate was spin-dried and separated by column chromatography to obtain the target product as a colorless white solid with a yield of 92%.

[0035] Wherein, the 2-aminopyridine, tert-butyl piperazine-1-carboxylate, acridine salt, 2,2,4,6,6-pentamethylpiperidine-nitrogen-oxide and anhydrous dichloroethyl The alkane is added in the following proportions: for every 2mL of anhydrous dichloroethane, add 0.2mmol, 1.0eq of 2-aminopyridine, 0.2mmol, 1.0eq of tert-butyl pipe...

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Abstract

The invention discloses a method for preparing 4-(6-aminopyridin-3-yl) piperazine-1-carboxylate tert-butyl ester. The method for preparing 4-(6-aminopyridin-3-yl) piperazine-1-carboxylate tert-butyl ester comprises the following steps: 2-aminopyridin, piperazine-1-formate tert-butyl ester and NSP-SA-NHS photo catalyst is added to the solvent, and the light reaction is carried out under the condition of the presence of an oxidizing agent to generate 4-(6-aminopyridin-3-yl) piperazine-1-carboxylate tert-butyl ester. According to the method, 4-(6-aminopyridin-3-yl) piperazine-1-carboxylate tert-butyl ester is synthesized by one step. On the one hand, the synthetic route of 4-(6-aminopyridin-3-yl) piperazine-1-carboxylate tert-butyl ester is effectively shortened, the generation of by-productsis effectively reduced and the yield of the target product is improved. On the other hand, only photo catalyst and oxidizing agent are used, so that the preparation method is safe and environment-friendly and low in cost.

Description

Technical field [0001] The invention belongs to the technical field of organic pharmaceutical chemistry, and specifically relates to a preparation method of 4-(6-aminopyridin-3-yl)piperazine-1-carboxylic acid tert-butyl ester. Background technique [0002] On February 3, 2015, the FDA accelerated the approval of pabociclib combined with letrozole as an endocrine-based first-line therapy for the treatment of menopausal women with estrogen receptor 2 negative advanced breast cancer. Each is used to treat ER+ / HER2- advanced breast cancer after menopause. Pabocinil can double the progression-free survival period of breast cancer compared with letrozole. It is a new hope for breast cancer patients. The curative effect has achieved a breakthrough, and it can completely replace the clinical medication of letrozole. The breast cancer market can reach tens of billions of dollars each year. In view of the good curative effect of Pabocinil, many analysts predict that annual sales can reac...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D295/205
CPCC07D295/205
Inventor 周海鹏黄湧韩珂珩张强韩辉王雷锋丁小妹余振辉
Owner 深圳蓝新科技有限公司
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