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Novel method for preparing aliphatic tricarbonitrile and aliphatic tricarbonitrile prepared by method

An aliphatic and new method technology, applied in the field of aliphatic trinitrile and preparation of aliphatic trinitrile, can solve problems such as difficulty in large-scale industrial production, poor selectivity, unfavorable environmental protection, etc., achieve simple operation, overcome safety problems, and use raw materials Easy to get effect

Active Publication Date: 2020-08-11
SHANGHAI ROLECHEM CO LTD
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  • Abstract
  • Description
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Problems solved by technology

[0003] It is known that adiponitrile is cyclized to form 2-amino-1-cyclopentene-1-carbonitrile (journal of thechemical 1909,700) under an equivalent strong base, and it is known that adiponitrile directly reacts with acrylonitrile with a relatively high selectivity. Poor, so many researchers proposed to react 2-amino-1-cyclopentene-1-nitrile with acrylonitrile to synthesize hexanetrinitrile, Soviet Chemical Journal (journal of applied chemistry of the USSR, 1972, 2683-2684) It is proposed to use elemental sodium as a base to synthesize, but the safety hazards make it difficult to produce on a large scale
In 2001, Bayer of Germany used a weak base to open the ring in the DE1003288 patent, but the intermediate in the first step of preparation was still expensive potassium tert-butoxide
In the 2015 patent CN105037203 of Shijiazhuang Shengtai Company in China, it was proposed to react 1,6-dichloro-2-butene with NaCN to synthesize 1,6-dinitrile-2-butene, and to obtain chlorides by addition of hydrochloric acid , and then react with NaCN to obtain the product. This method uses highly toxic substances, which is not good for environmental protection

Method used

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Examples

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preparation example Construction

[0039] The raw materials for the preparation of the compound II include: compound III and acrylonitrile; the structural formula of the compound III is Wherein, a is an integer of 3-12, b≥1, c≥1, d≥0, and X is a heteroatom.

[0040] Preferably, a is an integer of 3-12, b is 1-8, c≥3, and d is 0.

[0041] More preferably, a is an integer of 3-8, b is 2, c is 5, and d is 0; further preferably, a is an integer of 3-6, b is 2, c is 5, and d is 0.

[0042] The preparation method of the compound II is: react the compound III and acrylonitrile in the first inorganic base and / or the first organic strong base system; wherein, the reaction temperature is 0-150°C; the compound III and the acrylonitrile The molar ratio is 0.1-10:1; the addition amount of the first inorganic base or the first organic strong base is 0.01-2.0 molar equivalent of compound III. Preferably, the reaction temperature is 20-100° C.; preferably, the molar ratio of compound III to acrylonitrile is 0.1-2:1.

[004...

Embodiment 1

[0058] Preparation of 2,5-dicyano-2-cyanoethyl-pentanoic acid ethyl ester (compound II)

[0059] (1) Preparation of ethyl 2,5-dicyanovalerate (compound III): 113 grams of ethyl cyanoacetate, 104 grams of 4-chlorobutyronitrile, 160 grams of potassium carbonate, 500 grams of N,N-dimethyl Dimethyl formamide, reflux reaction at 150-160°C for 6 hours, concentrated, added 500 grams of dichloromethane, washed with 500 grams of water, separated layers, concentrated the filtrate, and distilled to obtain 160 grams of ethyl 2,5-dicyanovalerate. The yield was 88.9%.

[0060] HNMR data: (CDCl3, 400MHz): 1.31(t, J=8.00Hz, 3H), 1.87(m, 2H), 2.10(m, 2H), 2.45(t, J=8.00Hz, 2H), 3.57(t , J=8.00, 1H), 4.27 (q, J=8.00Hz, 2H).

[0061] (2) Preparation of 2,5-dicyano-2-cyanoethyl-valeric acid ethyl ester (compound II): 160 grams of 2,5-dicyanoethyl-valeric acid ethyl ester was put into 480 grams of toluene, and 5 gram of sodium methoxide, add 47 grams of acrylonitrile dropwise under temperature ...

Embodiment 2

[0064] Preparation of 2,5-dicyano-2-cyanoethyl-pentanoic acid ethyl ester (compound II)

[0065] (1) Preparation of ethyl 2,5-dicyanovalerate (compound III): 113 grams of ethyl cyanoacetate and 500 grams of N-methylpyrrolidone were added to 100 grams of sodium tert-butoxide at a temperature of 40° C., and After finishing, control the temperature at 40°C, add 250 grams of n-butyronitrile p-toluenesulfonate (CAS No. 107289-42-9), react at 110-120°C for 2 hours, concentrate, add 500 grams of dichloromethane, 500 2,5-dicyanovaleric acid ethyl ester 165 grams, the yield is 91.7%.

[0066] HNMR data: (CDCl3, 400MHz): 1.31(t, J=8.00Hz, 3H), 1.87(m, 2H), 2.10(m, 2H), 2.45(t, J=8.00Hz, 2H), 3.57(t ,J=8.00,1H), 4.27(q,J=8.00Hz,2H).

[0067] (2) Preparation of 2,5-dicyano-2-cyanoethyl-valeric acid ethyl ester (compound II): put 165 grams of 2,5-dicyano-valeric acid ethyl ester into 480 grams of 1,2-di Add 5 grams of sodium hydroxide to ethyl chloride, add 49 grams of acrylonitrile dro...

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Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a novel method for preparing aliphatic tricarbonitrile and the aliphatic tricarbonitrile prepared by thenovel method. The novel method for preparing aliphatic tricarbonitrile in the invention comprises the following step: removing COOCbHcXd from a compound II to obtain aliphatic tricarbonitrile. The structure formula of the compound II is as described in the specification; and in the structure formula, a is an integer from 3 to 12, b is greater than or equal to 1, c is greater than or equal to 1, dis greater than or equal to 0, e is 2, and X is a heteroatom. The method is simple to operate, uses easily available raw materials, realizes environmental protection, has great implementation value and social and economic benefits, overcomes the safety problems of aliphatic trinitrile preparation under the condition of sodium in a traditional process, and is high in yield and product purity.

Description

technical field [0001] The application belongs to the technical field of organic synthesis, and in particular, relates to a new method for preparing aliphatic trinitrile and the prepared aliphatic trinitrile. Background technique [0002] Aliphatic trinitriles are important industrial raw materials. For example, 1,3,6-hexanetrinitrile is currently used as an electrolyte additive to improve the high-voltage stability of the battery. decomposition. In the earliest period, 1,3,6-hexanetrinitrile was a by-product of electrolysis of acrylonitrile to prepare adiponitrile, and the yield was low, requiring multiple distillation separations. [0003] It is known that adiponitrile is cyclized to form 2-amino-1-cyclopentene-1-carbonitrile (journal of thechemical 1909,700) under an equivalent strong base, and it is known that adiponitrile directly reacts with acrylonitrile with a relatively high selectivity. Poor, so many researchers proposed to react 2-amino-1-cyclopentene-1-nitrile ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/30C07C255/05
CPCC07C253/30C07C255/05C07C255/19
Inventor 成勇德常帅魏范杰
Owner SHANGHAI ROLECHEM CO LTD
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