Synthetic method for chlorfenapyr

A synthetic method, the technology of chlorfenapyr, which is applied in the synthetic field of chlorfenapyr-1-ethoxymethyl-5--pyrrole-3-carbonitrile), can solve the problem of high raw material cost and highly toxic chemical sodium cyanide , Restricting industrial development and marketing, and poor selectivity of the reaction, etc., to achieve the effects of reducing raw material costs and safety risks, easy operation, and mild reaction conditions in the synthesis process

Inactive Publication Date: 2014-09-03
ZHEJIANG NORMAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The synthesis of 2-aryl-5-trifluoromethyl-3-cyanopyrrole is the key link in the synthesis of chlorfenapyr. At present, there are more studies on the synthesis route of sarcosine with p-chlorobenzaldehyde as the starting material. However, this route has problems such as high cost of raw materials and the use of highly toxic chemical sodium cyanide, which has potential environmental pollution risks and restricts its industrial development and market promotion.
In addition to the problem of raw material supply, these synthetic routes also have problems such as poor selectivity of reaction and low reaction yield.

Method used

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  • Synthetic method for chlorfenapyr
  • Synthetic method for chlorfenapyr
  • Synthetic method for chlorfenapyr

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Experimental program
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Effect test

Embodiment 1

[0026] Embodiment 1: the synthesis of intermediate 4-(p-chlorophenyl)-2-trifluoromethyl-3-oxazoline-5-ketone body

[0027]

[0028] Add 50 mL of acetonitrile to a 250 mL round bottom flask, add 5.0 g (0.025 mol, 1.0 eq) of p-chlorophenylglycine, stir evenly with a magnetic force, and add 2.9 mL (0.0375 mol, 1.5 eq) of trifluoroacetic acid dropwise for about 5 min. After mixing evenly, slowly add catalyst triethylamine 3.5mL (0.025mol, 1.0eq) dropwise, then slowly add phosphorus trichloride 2.4mL (0.0275mol, 1.1eq), dropwise within 0.5h. Finally, the temperature was raised to 65°C and the reaction was maintained for 4h. After the reaction was complete, it was cooled to room temperature, concentrated by rotary evaporation, and an appropriate amount of toluene was added to spin dry. A yellow viscous oily product was obtained, namely intermediate 1—(4-(p-chlorophenyl)-2-trifluoromethyl-3-oxazolin-5-one).

Embodiment 2

[0029] Embodiment 2: the synthesis of intermediate 2-(p-chlorophenyl)-5-(trifluoromethyl)-pyrrole-3-carbonitrile

[0030]

[0031]The 250mL round bottom flask used in the first step reaction was directly used for the next step reaction, and 50mL of acetonitrile was added, wherein the amount of intermediate 1 was about 5.3g (0.02mol, 1.0eq). After stirring at room temperature, 3.5 g (0.04 mol, 2.0 eq) of 2-chloroacrylonitrile was added. A quantitative catalyst triethylamine 7.2mL (0.05mol, 2.5eq) was added dropwise, and the dropping rate was controlled at 6-7min / mL. After the dropwise addition, reflux at about 78°C for 1h. After the reaction is complete, cool to room temperature, add an appropriate amount of cold water to the reaction solution, a light yellow solid precipitates, and filter under reduced pressure to obtain the product, the intermediate 2—(2-(p-chlorophenyl)-5-(trifluoromethane base)-pyrrole-3-carbonitrile), and the product was recrystallized from ethanol. ...

Embodiment 3

[0033] Embodiment 3: the synthesis of intermediate 4-bromo 2-(p-chlorophenyl)-5-(trifluoromethyl)-pyrrole-3-carbonitrile

[0034]

[0035] Add 75.0mL of acetic acid into a 250mL two-necked flask, add 25.4g (0.020mol, 1.0eq) of the intermediate, stir evenly with a magnetic force, add 1.97g (0.024mol, 1.2eq) of anhydrous sodium acetate, and after completely dissolving, slowly heat to 90.0°C, stir for 10 minutes. At a constant temperature of 90.0°C, 20.0 mL of acetic acid solution of bromine (6.4 g, 0.040 mol, 2.0 eq) was added dropwise, and the rate of addition was adjusted according to whether there was orange-red bromine vapor in the condenser tube. After the dropwise addition was completed, the stirring was continued for 30 minutes, then the temperature was raised to 110.0° C., and the reaction was maintained for 3.0 hours. After the reaction was complete, the system was cooled to room temperature, and an equal amount of ice water was added, and a large amount of white so...

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Abstract

A synthetic method for chlorfenapyr mainly comprises the following steps: (2) synthesizing an intermediate 4-(p-chlorophenyl)-2-trifluoromethyl-3-oxazoline-5-one; (2) synthesizing an intermediate 2-(p-chlorophenyl)-5-trifluoromethyl-pyrrole-3-carbonitrile; (3) synthesizing an intermediate 4-bromo-2-(p-chlorophenyl)-5-trifluoromethyl-pyrrole-3-carbonitrile; and (4) synthesizing the target product chlorfenapyr, that is 4-boromo-2-(p-chlorophenyl)-1-ethoxymethyl-5-trifluoromethyl-pyrrole-3-carbonitrile. All raw materials for synthesis of the raw pesticide are abundant in resource, the synthetic technology is mild in reaction conditions and suitable for industrialized production.

Description

technical field [0001] The invention belongs to the technical field of pesticide synthesis, in particular to chlorfenapyr (4-bromo-2-(p-chlorophenyl)-1-ethoxymethyl-5-(trifluoromethyl)-pyrrole-3-carbonitrile ) synthesis method. Background technique [0002] In 1987, the American Cyanamid Company isolated Dioxapyrlomycin from the microorganism Streptomyces and found that it had good insecticidal and acaricidal properties against a large number of insects and mites [1] , and then developed a new type of arylpyrrolenitrile insecticide and acaricide - chlorfenapyr, which can be used to control various pests and is widely used. Chromfenapyr is a natural product, which is non-toxic to insects itself. Its application principle is to use insects to convert oxidases into compounds with insecticidal activity after ingesting or touching insects, and convert the mitochondria in the insect body cells. Oxidative ortho-acidification of ADP to ATP [2] . [0003] Chlorfenapyr, also known...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D207/34
CPCC07D207/34
Inventor 谢建武邵雨波黄晓周锋王丹丹陈妍君
Owner ZHEJIANG NORMAL UNIVERSITY
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