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Method for synthesizing cyanoacetylene derivatives

A synthetic method and derivative technology, applied in the field of chemistry, can solve the problems of toxic, expensive raw materials, troublesome separation, etc., and achieve the effects of simple process operation, simple post-processing, and low production cost

Active Publication Date: 2010-03-17
HANGZHOU ALLSINO CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0016] Comprehensive above-mentioned each route: method one will use poisonous, difficult-to-operate reagent, quite expensive raw material, has brought very big potential safety hazard in the chemical synthesis; , and the thermal decomposition of acyl ylides requires a very high temperature; the raw material propiolic acid used in method three is a kind of compound that is difficult to synthesize, and is not suitable as a raw material for propionitrile; The existence of making debromination reaction can not be carried out in the DMSO solution of conventional alkaline reagents such as potassium tert-butoxide, potassium hydroxide, etc., and the reaction yield is very low
In summary, there is no method for the synthesis of propyne nitrile derivatives suitable for industrial production so far

Method used

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  • Method for synthesizing cyanoacetylene derivatives
  • Method for synthesizing cyanoacetylene derivatives
  • Method for synthesizing cyanoacetylene derivatives

Examples

Experimental program
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Effect test

Embodiment 1

[0030] The synthetic method of embodiment 1 cyclopentyl propylonitrile (R is cyclopentyl)

[0031] 1) Preparation of cyclopentylformyl chloride: Add 115g (1mol) cyclopentylformic acid into a 250ml there-necked flask, and add 165g (1.4mol) thionyl chloride dropwise at room temperature, and the time for dropping is about 1 hour. After the dropwise addition, react at room temperature, monitor the reaction by GC and show that there is no remaining formic acid after this period of time, then heat up, evaporate excess thionyl chloride under normal pressure, and carry out vacuum distillation on the residue to obtain about 118g~125g of product. The rate is 90% to 95%.

[0032] 2) Preparation of ethyl α-cyano-β-carbonylcyclopentylpropionate: under nitrogen protection, dissolve 100g (1.0mol) of ethyl cyanoacetate in 1000ml tetrahydrofuran and add 95g (1mol) of anhydrous magnesium chloride to cool to 0°C. Add 200g (2mol) of triethylamine dropwise to this system, and control the dropwis...

Embodiment 2

[0036] The preparation of embodiment 2 3-phenyl propylonitrile (R is 3-phenyl)

[0037]At room temperature, 50 g (0.5 mol) of triethylamine was dripped into 87 g of the crude product of α-cyano-β-chlorophenylacrylic acid (using 1 mol of benzoic acid as the starting material according to the steps 1-4 in Example 1) obtained by imitation) and 300ml of dichloroethane and heated to reflux for 24 hours. Cool to room temperature and add 100ml of water, stir to dissolve and then let stand to separate layers. The lower organic layer was separated, and the organic layer was washed once with 50 ml of saturated aqueous sodium bicarbonate solution and then allowed to stand for separation. The organic phase was separated, dried over anhydrous magnesium sulfate and filtered with suction. After dichloroethane was evaporated under normal pressure, the residue was distilled under reduced pressure to obtain 43 g of the product. The crude product was crystallized with 30 ml of n-hexane and dri...

Embodiment 3

[0038] The preparation of embodiment 3 3-isopropyl propylonitrile (R is 3-isopropyl)

[0039] At room temperature, 75g (0.75mol) of triethylamine was dripped into 109g of the crude product of α-cyano-β-chloroisopropylacrylic acid (using 1mol of isobutyric acid as the starting material according to 1- 4 steps were imitated) and 300ml of dichloroethane and heated to reflux for 24 hours. Cool to room temperature and add 100ml of water, stir to dissolve and then let stand to separate layers. The lower organic layer was separated, and the organic layer was washed once with 50 ml of saturated aqueous sodium bicarbonate solution and then allowed to stand for separation. The organic phase was separated, dried over anhydrous magnesium sulfate and filtered with suction. After dichloroethane was distilled off under normal pressure, the residue was distilled under reduced pressure to obtain 48.6 g of oily substance, with a total yield of 52%.

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Abstract

The invention discloses a method for synthesizing cyanoacetylene derivatives. The prior preparation method has high production cost and low yield, and is not suitable for industrial production. The method comprises that: in the presence of a dehydrating agent, organic formic acid generates organic formyl chloride; in the presence of Lewis acid and organic alkali, the organic formyl chloride is reacted with ethyl cyanoacetate to generate alpha-cyano-beta-carbonyl ethyl propionate compounds; in the presence of chlorinating agent and organic alkali, the alpha-cyano-beta-carbonyl ethyl propionatecompounds are subjected to chlorination reaction to generate alpha-cyano-beta-chloroacrylate ethyl ester compounds; in the presence of inorganic alkali and lower alcohol solution, the alpha-cyano-beta-chloroacrylate ethyl ester compounds are hydrolyzed to generate alpha-cyano-beta-chloroacrylate compounds; and in the presence of organic alkali, the alpha-cyano-beta-chloroacrylate compounds are subjected to decarboxylation and dehalogenation elimination reaction to generate the cyanoacetylene derivatives. The whole process operation is simple and convenient, the post treatment is simple and the yield is high, so the method is quite suitable for industrialized production.

Description

technical field [0001] The invention relates to the field of chemistry, in particular to a method for synthesizing propyne nitrile derivatives. Background technique [0002] The structural formula of propyne nitrile derivatives is as follows: R-C≡C-CN, wherein R is a lower cycloalkyl group, an alkyl group or a phenyl group. [0003] The preparation method of most propylonitrile derivatives is as follows at present: [0004] Method 1: first generate terminal acetylene compounds corresponding to the R group, and then react with phenyl cyanate and pyridine cyanate to prepare or react with cuprous cyanide to obtain propyne nitrile derivatives. [0005] Usually, the corresponding ketones can be reacted in the presence of phosphorus pentachloride, phosgene, phosphorus oxychloride and catalysts to generate 2-chloro-1-alkenes, and then dehydrochlorinated by potassium tert-butoxide to generate terminal alkynes hydrocarbon compounds; [0006] 1,1-dihalo-1-alkene compounds can also ...

Claims

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Application Information

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IPC IPC(8): C07C255/06C07C253/30
Inventor 郑立强
Owner HANGZHOU ALLSINO CHEM
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