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Synthesis method of tert-butyl 6-benzyl-4-oxyylidene octahydro-1h-pyrrolo[3,4-b]pyridinecarboxylate

A synthesis method and benzyl technology are applied in the synthesis field of tert-butyl 6-benzyl-4-oxyidene octahydro-1H-pyrrolo[3,4-b]picolinate, which can Solve problems such as no suitable industrial synthesis method, and achieve the effects of reasonable reaction process design, convenient operation and easy reaction

Active Publication Date: 2019-04-30
WUXI APPTEC (TIANJIN) CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Mainly solve the technical problem that there is no suitable industrial synthesis method at present

Method used

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  • Synthesis method of tert-butyl 6-benzyl-4-oxyylidene octahydro-1h-pyrrolo[3,4-b]pyridinecarboxylate

Examples

Experimental program
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Embodiment 1

[0010] Under nitrogen protection, a solution of 2,3-dichloro-5,6-dicyano-p-benzoquinone ((461 g, 2.03 mol) in dioxane (2.0 L) was slowly added dropwise to the stirring Compound 1 (500 g, 1.85 mol) in dioxane solution. The mixture was stirred overnight at 16 degrees Celsius. TLC (DCM / MeOH volume ratio = 20 / 1, R f = 0.5) shows that the raw material is completely consumed. The reaction solution was filtered, and the filter cake was washed with dioxane (500 mL x 2). The mother liquors were combined and spin-dried to obtain the crude product. The crude product was washed with ethanol (600 mL x 3) to obtain compound 2 (160 g, yield 35%) as a white solid.

[0011] Under nitrogen protection, N-methoxymethyl-N-(trimethylsilylmethyl)benzylamine (321 g, 1.48 mol) was slowly added dropwise to compound 2 (200 g, 0.74 mol) at 0-10 degrees Celsius and TFA (25.0 mL) in THF. The reaction solution was returned to 17°C and stirred overnight. TLC (petroleum ether / ethyl acetate volume ratio=...

Embodiment 2

[0015] Under nitrogen protection, a solution of 2,3-dichloro-5,6-dicyano-p-benzoquinone ((400 g, 1.77 mol) in dioxane (1.0 L) was slowly added dropwise to the stirring Compound 1 (430 g, 1.61 mol) in dioxane (3.0 L) solution. The mixture was stirred overnight at 25 degrees Celsius. TLC (DCM / MeOH volume ratio = 20 / 1, R f = 0.5) shows that the raw material is completely consumed. The reaction solution was filtered, and the filter cake was washed with dioxane (500 mL x 2). The mother liquors were combined and spin-dried to obtain the crude product. The crude product was washed with ethanol (500 mL x 3) to give compound 2 (145 g, 36%) as a white solid.

[0016] Under nitrogen protection, N-methoxymethyl-N-(trimethylsilylmethyl)benzylamine (232 g, 1.06 mol) was slowly added dropwise to compound 2 (145 g, 0.53 mol) at 0-10 degrees Celsius and TFA (18.0 mL) in THF. The reaction solution was returned to 20°C and stirred overnight. TLC (petroleum ether / ethyl acetate volume ratio=...

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Abstract

The invention relates to a synthetic method of 6-benzyl-4-oxo-octahydro-pyrrolo[3,4-b]pyridine-1-carboxylic acid tert-butyl ester and mainly solves the technical problem that an industrial synthetic method is inavailable at present. The synthetic method mainly comprises three steps as follows: step 1, 1(1-tert-butyl3-ethyl 4- oxo-ylidene piperidine-1,3-diformyl ester) and 2,3-dichloro-5,6-dicyano-p-benzoquinone react at the room temperature in a dioxane solvent, and a compound 2 is obtained; step 2, N-(methoxymethyl)-N-(trimethylsilylmethyl)benzylamine is added to a tetrahydrofuran solution of the compound 2 and trifluoroacetic acid at a low temperature, the substances react at the room temperature and stay overnight, and a compound 3 is obtained; step 3, the compound 3 is subjected to reflux in hydrochloric acid and stays overnight, and the final compound is obtained. The product is widely applied to medicinal chemistry and organic synthesis.

Description

technical field [0001] The present invention relates to the synthetic method of compound tert-butyl 6-benzyl-4-oxyethylene octahydro-1H-pyrrolo[3,4-b]pyridine carboxylate, namely (4aS,7aS)-tert-butyl Synthetic method of 6-benzyl-4-oxyylidene octahydro-1H-pyrrolo[3,4-b]pyridine-1-carboxylate. Background technique [0002] Compound (4aS,7aS)-tert-butyl 6-benzyl-4-oxyylidene octahydro-1H-pyrrolo[3,4-b]pyridine-1-carboxylate (CAS: 1310381-21-5 ) and related derivatives are widely used in medicinal chemistry and organic synthesis. Currently, there are few reports on the synthesis of (4aS,7aS)-tert-butyl 6-benzyl-4-oxyylidene octahydro-1H-pyrrolo[3,4-b]pyridine-1-carboxylate. Therefore, it is necessary to develop a synthetic method that is easy to obtain raw materials, easy to operate, easy to control the reaction, suitable for overall yield, and suitable for industrial production. Contents of the invention [0003] The purpose of the present invention is to develop a kind of...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D471/04
CPCC07D471/04
Inventor 徐学芹周强于凌波王瑞琪刘月领何燕平焦家盛安自强吴艳徐富军马汝建
Owner WUXI APPTEC (TIANJIN) CO LTD