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The preparation method of ethyl 2-oxo-3-piperidinecarboxylate

A technology of ethyl piperidinecarboxylate and diethyl malonate, which is applied in the field of preparation of ethyl 2-oxo-3-piperidinecarboxylate, can solve the problems of low yield, and achieve easy-to-obtain raw materials and simple operation Effect

Active Publication Date: 2021-01-05
上海泾维化工科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] In summary, from 1949 to the present, the ethyl 2-oxo-3-piperidinecarboxylate reported in domestic and foreign literature is all adopted in the classic N F Albertsm method, and this synthetic method has the disadvantage of low yield

Method used

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  • The preparation method of ethyl 2-oxo-3-piperidinecarboxylate
  • The preparation method of ethyl 2-oxo-3-piperidinecarboxylate
  • The preparation method of ethyl 2-oxo-3-piperidinecarboxylate

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Experimental program
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Effect test

Embodiment 1

[0025] 1000mL dry four-necked reaction flask, equipped with mechanical stirring, thermometer, dropping funnel, and reflux condenser. Add 560 g (3.5 mol) of diethyl malonate, 0.6 g (solid powder) of sodium tert-butoxide as a basic catalyst, and 70 g (1.3 mol) of acrylonitrile into the dropping funnel. Add acrylonitrile dropwise to the reaction bottle under stirring, the reaction exotherms, control the reaction temperature at 30-32°C with a water bath, and complete the addition in 4-5 hours. Then the reaction was stirred at the same temperature for 1 hour.

[0026] Transfer the feed liquid into a 1000mL vacuum short column rectification device, remove the raw material diethyl malonate at a vacuum of 18-20 mmHg, then increase the vacuum to 0.6-0.8 mmHg, and distill the distillate at a temperature of 106-206 mmHg. The positive fraction at 110°C was 227.6 g in total, the GC content of the intermediate 2-cyanoethyldiethylmalonate was 98.6%, and the reaction yield was 80.9% (calcula...

Embodiment 2

[0030] The 1000 liter glass-lined reactor was washed and dried in N 2 Under protection, 620 kg (3.87 kmol) of diethyl malonate and 0.9 kg of solid powder of potassium tert-butoxide were added. 72kg of acrylonitrile is introduced into the overhead tank. (1.35kmol) Start the stirring of the reactor, and drop acrylonitrile into the reactor within 5 hours when the internal temperature is lower than 35°C. After the addition of acrylonitrile, the reaction was carried out at 32°C for 1 hour.

[0031] The reaction feed liquid is transferred from the reactor to the short-column rectification tower of the 1000-liter tower tank. Start the vacuum system to make the vacuum degree reach 20-25mmHg, turn on the cooling water circulation of the condenser at the top of the tower, introduce steam into the reboiler of the tower to heat, and distill out the solvent diethyl malonate at a reflux ratio of 1:1. When the diethyl malonate is completely evaporated, turn on the multi-stage Roots vacuum...

Embodiment 3～8

[0039] Embodiment 3~8 all repeats the operation of embodiment 2, but the diethyl malonate of raw material diethyl malonate is reclaimed the diethyl malonate of redistilling and adds fresh substance again to reach requirement feeding amount; After 0.5kg, put it into the next kettle for reaction; all the recrystallization operations of the product use fresh solvents.

[0040] The reaction results are as follows:

[0041]

[0042]

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Abstract

The invention provides a preparation method of 2-oxo-3-ethyl piperidinecarboxylate. The preparation method comprises the following steps: S1, mixing diethyl malonate and a base catalyst uniformly, andthen dropwise adding acrylonitrile at 10 to 50 DEG C for reaction to obtain diethyl 2-(2-cyanoethyl)malonate; S2, reacting 2-(2-cyanoethyl)malonate, an organic solvent and a Raney cobalt catalyst at75-130 DEG C in a hydrogen atmosphere, and carrying out recrystallization to obtain 2-oxo-3-ethyl piperidinecarboxylate. Compared with the prior art, the preparation method has the beneficial effectsthat the raw materials are easily available, the operation is simple, and the total yield reaches 77% or higher compared with a classic N.F.Albertsm method (which is improved by 20%), so that the preparation method is very suitable for industrial production.

Description

technical field [0001] The invention relates to a preparation method of ethyl 2-oxo-3-piperidinecarboxylate, which belongs to the technical field of chemical intermediates. Background technique [0002] Ethyl 2-oxo-3-piperidinecarboxylate is a fine chemical intermediate used in the manufacture of melatonin, a brain health product. As early as 1949, N.F.Albertsm and others published the synthesis method of ethyl 2-oxo-3-piperidinecarboxylate in the American Journal of Chemistry (JACS). They used the condensation reaction of diethyl malonate and acrylonitrile to obtain the intermediate cyanoethyldiethyl malonate, which was then hydrogenated and cyclized in the presence of catalyst Raney Ni to obtain the product 2-oxo-3-piperidine Ethyl formate, the total yield of the two-step reaction is 57.3%. Its reaction scheme is as follows: [0003] [0004] The method of synthesizing ethyl 2-oxo-3-piperidinecarboxylate proposed by N·F·Albertsm has become a classic method for synthe...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D211/78C07D211/02
CPCC07D211/02C07D211/78
Inventor 姚虎生赵珠琳张明
Owner 上海泾维化工科技有限公司
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