Preparation method of pyrazolyl acrylonitrile compound

A technology of pyrazolyl acrylonitrile and compound, which is applied in the field of preparation of azolyl acrylonitrile compounds, can solve the problems of complex post-processing, large amount of three wastes, and low yield of intermediate synthesis, and achieve good dispersibility and total yield. The effect of improving the efficiency and reducing the discharge of "three wastes"

Active Publication Date: 2016-07-27
SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the synthesis yield of this intermediate is low, the post-treatment is complica

Method used

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  • Preparation method of pyrazolyl acrylonitrile compound
  • Preparation method of pyrazolyl acrylonitrile compound
  • Preparation method of pyrazolyl acrylonitrile compound

Examples

Experimental program
Comparison scheme
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Example Embodiment

[0030] Example 1

[0031] Z-2-(4-(tert-butyl)phenyl)-2-cyano-1-(1-ethyl-3-methyl-1hydro-5-pyrazolyl)vinyl pivalate (Table Synthesis of compound 1) in 1

[0032] Add 43.7g (0.8mol) of sodium methoxide, 140g (0.8mol) of p-tert-butylphenylacetonitrile and 900g of toluene into a reaction flask equipped with a rectification tower, and heat up to 60°C. A solution of 170 g (1.0 mol) of methyl 1-ethyl-3-methyl-1-hydrogen-5-pyrazolecarboxylate and 300 g of toluene was slowly added dropwise, and the dropwise was completed in about 1 hour. After the dropwise addition, the temperature was raised to reflux. During the reaction, the low boilers with a boiling point lower than 65°C were continuously separated from the top of the tower and reacted for 5 hours to obtain 2-(4-(tert-butyl)phenyl)-1-(- 1-ethyl-3-methyl-1hydro-5-pyrazolyl)-2-cyanovinyl alcohol sodium salt suspension in toluene.

[0033] At 80-90° C., 98 g (0.8 mol) of pivaloyl chloride was added dropwise to the reaction mixture...

Example Embodiment

[0036] Example 2

[0037] Z-2-(4-(tert-butyl)phenyl)-2-cyano-1-(1-ethyl-3-methyl-1hydro-5-pyrazolyl)vinyl pivalate (Table Synthesis of compound 1) in 1

[0038] In a reactor equipped with a rectification tower, 11Kg (20.2mol) of sodium methylate and 180Kg of toluene were added, and the temperature was raised to 100°C. Slowly add a solution of 33Kg (189mol) p-tert-butylphenylacetonitrile, 30Kg (177mol) 1-ethyl-3-methyl-1-hydrogen-5-pyrazolecarboxylic acid methyl ester and 50Kg toluene for about 1.5 hours. Finish. After the dropwise addition, the temperature was raised to reflux. During the reaction, the low boilers with a boiling point lower than 65°C were continuously separated from the top of the tower, and reacted for 6 hours to obtain 2-(4-(tert-butyl)phenyl)-1-(- 1-ethyl-3-methyl-1hydro-5-pyrazolyl)-2-cyanovinyl alcohol sodium salt suspension in toluene.

[0039] At 100-105° C., 24 Kg (197 mol) of pivaloyl chloride was added dropwise to the reaction mixture in the prev...

Example Embodiment

[0040] Example 3

[0041]Z-2-(4-(tert-butyl)phenyl)-2-cyano-1-(1-ethyl-3-methyl-4-chloro-1hydro-5-pyrazolyl)pivalic acid Synthesis of Vinyl Esters (Compound 5 in Table 1)

[0042] Add 54.6g (1.0mol) of sodium methoxide and 900g of toluene into the reaction flask equipped with a rectification tower, and raise the temperature to 80°C. Slowly add dropwise a solution of 205g (1.0mol) 4-chloro-1-ethyl-3-methyl-1hydrogen-5-pyrazolecarboxylic acid methyl ester, 175g (1.0mol) p-tert-butylphenylacetonitrile and 300ml of toluene , It takes about 2 hours to drip. After the dropwise addition, the temperature was raised to reflux. During the reaction, the low boilers with a boiling point lower than 65°C were continuously separated from the top of the tower, and reacted for 3 hours to obtain 2-(4-(tert-butyl)phenyl)-1-(4 - Chloro-1-ethyl-3-methyl-1hydro-5-pyrazolyl)-2-cyanovinyl alcohol sodium salt suspension in toluene.

[0043] At 105-110° C., 122 g (1.0 mol) of pivaloyl chloride was ...

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Abstract

The invention belongs to the field of organic synthesis, and concretely relates to a preparation method of a pyrazolyl acrylonitrile compound. A pyrazole carboxylic ester compound and p-tert-butylphenylacetonitrile are shown in a general formula (II), in the existence of an organic solvent and alkali, a reaction is carried out at 60-160 DEG C, 2-(4-(tert-butyl)phenyl)-1-(1-ethyl-3-methyl-1hydrogen-5-pyrazolyl)-2-cyan vinyl alcohol sodium salt or kali salt is obtained as shown in a general formula (III), a reaction is directly carried out between the obtained compound (III) and pivaloyl chloride at 60-160 DEG C, and the pyrazolyl acrylonitrile compound as shown in a general formula (I) is obtained. The method has the advantages of high yield of the target compound, low 'three wastes (waste gas, waste water and industrial residue)' discharge, and simple operation; and the method is suitable for large scale industrial production.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of a pyrazolyl acrylonitrile compound. Background technique [0002] The pyrazolyl acrylonitrile compounds represented by the general formula (I) are a class of compounds with excellent insecticidal and acaricidal activities, and can be used to control insect pests and acarids. [0003] [0004] Patent WO2010124617A1 discloses the synthesis method of this kind of compound. With the pyrazole carboxylate compound shown in general formula (II) and p-tert-butylphenylacetonitrile, in the mixed solvent of n-heptane, ethylene glycol monoethyl ether, add dropwise the methanol solution of 20% sodium methylate, After the reaction is over, pour it into water after cooling down, add ethyl acetate for extraction, adjust the pH of the water phase to 2-3 with concentrated hydrochloric acid, extract 3 times with ethyl acetate, wash the organic phase, dry and ...

Claims

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Application Information

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IPC IPC(8): C07D231/12
Inventor 于春睿薛有仁武恩明于福强叶艳明王徵
Owner SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD
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