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The preparation method of 4-(6-aminopyridin-3-yl)piperazine-1-carboxylic acid tert-butyl ester

A technology of tert-butyl carboxylate and aminopyridine is applied in the field of preparation of tert-butyl 4-piperazine-1-carboxylate, and 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: 2020-08-07
深圳蓝新科技有限公司
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  • Abstract
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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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  • The preparation method of 4-(6-aminopyridin-3-yl)piperazine-1-carboxylic acid tert-butyl ester
  • The preparation method of 4-(6-aminopyridin-3-yl)piperazine-1-carboxylic acid tert-butyl ester
  • The preparation method of 4-(6-aminopyridin-3-yl)piperazine-1-carboxylic acid 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 described 4-(6-aminopyridin-3-yl) piperazine-1-carboxylic acid tert-butyl ester comprises the steps:

[0012] Add 2-aminopyridine, piperazine-1-carboxylic acid tert-butyl ester, and acridinium salt photocatalyst into the solvent, and carry out light reaction under the condition of oxidizing agent 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 generate the product compound c. The chemical reaction formula of the light reaction is as follows:

[0014]

[0015] Wherein, the acridinium salt promotes the condensation reaction of the 2-aminopyridine and piperazine-1-carboxylic acid tert-butyl ester under light conditions. In one embodiment, the acridinium salt photocatalyst includes at least one of ...

Embodiment 1

[0026] This example provides a preparation method of tert-butyl 4-(6-aminopyridin-3-yl)piperazine-1-carboxylate. The synthetic method of described 4-(6-aminopyridin-3-yl) piperazine-1-carboxylic acid tert-butyl ester:

[0027] Add 2-aminopyridine, piperazine-1-carboxylic acid tert-butyl ester, acridinium salt visible light catalyst, 2,2,6,6-tetramethylpiperidine-nitrogen-oxide into anhydrous dichloroethane, Then, the reaction environment was replaced with oxygen three times, irradiated with a blue LED, and the reaction time was 10 h. After the reaction was completed, 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, piperazine-1-carboxylic acid tert-butyl ester, acridinium salt, 2,2,6,6-tetramethylpiperidine-nitrogen-oxide and anhydrous dichloroethane according to Add in the following ratio: for every 2mL of anhydrous dichloroethane, add 0.2mmo...

Embodiment 2

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

[0034] Add 2-aminopyridine, piperazine-1-carboxylate tert-butyl ester, acridinium salt visible light catalyst, 2,2,4,6,6-pentamethylpiperidine-nitrogen-oxide into anhydrous dichloroethane , and then replace the reaction environment with oxygen three times, irradiate with blue LED, and the reaction time is 10h. After the reaction was completed, 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] Among them, the 2-aminopyridine, piperazine-1-carboxylic acid tert-butyl ester, acridinium salt, 2,2,4,6,6-pentamethylpiperidine-nitrogen-oxide and anhydrous dichloroethyl Alkanes were added according to the following ratio: for every 2mL of anhydrous dichloroethane, 0.2mmol, 1.0eq of 2-aminopyridine...

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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 medicinal chemistry, and in particular 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 palbociclib (palbociclib) combined with letrozole as endocrine-based first-line therapy for the treatment of postmenopausal women with estrogen receptor 2-negative advanced breast cancer. Each is indicated for the treatment of ER+ / HER2- postmenopausal advanced breast cancer. Compared with letrozole, palbociclib can double the progression-free survival of breast cancer. It is a new hope for breast cancer patients. It has a breakthrough in efficacy and can completely replace the clinical use of letrozole. The breast cancer market can reach tens of billions of dollars every year. In view of the good curative effect of palbociclib, many analysts predict that the annual sal...

Claims

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Application Information

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Patent Type & Authority Patents(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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