Preparing method of 2,3-dicyanopropionate

A technology of ethyl dicyanopropionate and ethyl cyanopropionate is applied in the field of preparation of 2,3-ethyl dicyanopropionate, an intermediate of phenylpyrazole pesticides, and can solve the problem of improper operation , safety accidents, high requirements for operation and safety and environmental protection, to achieve the effect of low production cost, good product quality, and low processing difficulty

Active Publication Date: 2016-04-13
HUNAN CHEM RES INST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0011] The biggest problem with the existing synthetic methods of ethyl 2,3-dicyanopropionate is that the raw materials used are α-substituted (hydrogen or ethylenic, hydroxymethyl, etc.) cyanoacetates generally use metal cyanide or hydrocyanic acid Preparation, one-step synthesis is the direct use of highly toxic metal cyanide, there are problems with high requirements for operation and safety in terms of process operation and waste treatment, and improper operation may easily cause safety accidents

Method used

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  • Preparing method of 2,3-dicyanopropionate
  • Preparing method of 2,3-dicyanopropionate
  • Preparing method of 2,3-dicyanopropionate

Examples

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Embodiment 1

[0028] Put 168.2g (1.05mol) of diethyl malonate and 168.2g of methanol into the reaction flask for miscibility, drop in 272.3g (mass fraction 25%, 1.26mol) of methanol solution of sodium methoxide within 3 hours below 10°C, and drop it Cool to 0°C, slowly add 57.1g (1mol) of hydroxyacetonitrile dropwise within 1h, keep the temperature at 0°C for 1h after dropping; adjust the pH value of the reaction solution to 5 with saturated hydrochloric acid below 10°C, filter, and remove the solvent in the filtrate under reduced pressure Finally, the concentrated material was obtained, and 336.4g of dichloroethane was used to dissolve the concentrated material and soak the filter cake. The soaking liquid was combined into the concentrated material solution, filtered, and the filtrate was precipitated to obtain 173g of yellow liquid intermediate Iα-cyanomethyl- Diethyl malonate, content 95.2%, yield 82.7% (based on hydroxyacetonitrile).

[0029] Put 173g (0.83mol) of intermediate I and 138...

Embodiment 2

[0031] Put 168.2g (1.05mol) of diethyl malonate and 168.2g of methanol into the reaction flask for miscibility, drop in 272.3g (mass fraction 25%, 1.26mol) of methanol solution of sodium methoxide within 3 hours below 10°C, and drop it Cool to 0°C, slowly add 57.1g (1mol) of hydroxyacetonitrile dropwise within 1h, keep the temperature at 0°C for 1h after dropping; adjust the pH value of the reaction solution to 5 with saturated hydrochloric acid below 10°C, filter, and remove the solvent in the filtrate under reduced pressure Finally, the concentrated material was obtained, and 336.4g of dichloroethane was used to dissolve the concentrated material and soak the filter cake, and the soaking liquid was combined into the concentrated material solution, filtered, and the filtrate was precipitated to obtain 172.1g of yellow liquid intermediate Iα-cyanomethyl -diethyl malonate, content 95.3%, yield 82.3% (calculated as hydroxyacetonitrile).

[0032]Put 172g (0.82mol) of intermediate...

Embodiment 3

[0034] Put 176.2g (1.1mol) of diethyl malonate and 176.2g of methanol into the reaction flask for miscibility, drop in 285.2g (mass fraction 25%, 1.32mol) of methanol solution of sodium methoxide within 3 hours below 10°C, and drop it Cool to 0°C, slowly add 57.1g (1mol) of hydroxyacetonitrile dropwise within 1h, keep the temperature at 0°C for 1h after dropping; adjust the pH value of the reaction solution to 5 with saturated hydrochloric acid below 10°C, filter, and remove the solvent in the filtrate under reduced pressure Finally, the concentrated material was obtained, and 352.4g of dichloroethane was used to dissolve the concentrated material and soak the filter cake, and the soaking liquid was combined into the concentrated material solution, filtered, and the filtrate was precipitated to obtain 171.3g of yellow liquid intermediate Iα-cyanomethyl - Diethyl malonate, content 95.5%, yield 82.1% (calculated as hydroxyacetonitrile).

[0035] Put 171.3g (0.82mol) of intermedi...

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Abstract

The invention discloses a preparing method of 2,3-dicyanopropionate, which comprises: taking diethyl malonate and glycolonitrile as raw materials, reacting in a methanol solvent of sodium methoxide to obtain an intermediate I alpha-cyanmethyl-diethyl malonate, reacting the intermediate with ammonia gas in a methylbenzene solvent to obtain an intermediate II 2-acylamino-3-cyan ethyl propionate reaction solvent, and finally reacting the intermediate II reaction solvent with phosgene in presence of a catalyst 1,4-diazabicyclo[2.2.2]octane (DABCO for short) to obtain the product 2,3-dicyanopropionate. A highly toxic product of metal cyanide is not used as a raw material, alpha replaced (replacing hydrogen or olefinic bond, hydroxymethyl) cyanoacetic acid ester is not used as an initial raw material, the produced three wastes do not contain a metal cyanide highly toxic product and are low in processing difficulty, a recycled solvent can be used indiscriminately; an operation process is simple and safe and used raw materials are cheap and easy to obtain. A reaction yield is high, the product quality is high, the production cost is low, postprocessing is easy and easiness for industrialization is realized.

Description

technical field [0001] The invention relates to a preparation method of ethyl 2,3-dicyanopropionate, an intermediate of phenylpyrazole insecticides. Background technique [0002] Ethyl 2,3-dicyanopropionate is an important intermediate for the synthesis of phenylpyrazole insecticides fipronil and ethiprole, the chemical structural formula of ethyl 2,3-dicyanopropionate: [0003] [0004] Ethyl 2,3-dicyanopropionate was discovered and prepared by Higson and Thorpe in 1906. The specific synthesis process is to react ethyl cyanoacetate with sodium methoxide to form the sodium salt of ethyl cyanoacetate, and then react with hydroxyacetonitrile Prepare ethyl 2,3-dicyanopropionate, the reaction formula is as follows: [0005] [0006] Dickinson et al. repeated this preparation process in the process of synthesizing tricyanoethylene. In the information disclosed in patent 2005060749, potassium carbonate was used to replace sodium methoxide to synthesize ethyl 2,3-dicyanoprop...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C255/19C07C253/20
CPCC07C253/20C07C253/30C07C255/22C07C255/19
Inventor 周勇徐建兵臧阳陵王宇
Owner HUNAN CHEM RES INST
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