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Synthesis of 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile

A technology of benzodioxol and dioxol, applied in 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole In the field of synthesis of -3-nitrile, it can solve problems such as difficult control of product quality, high equipment requirements, and easy hydrolysis and deterioration, and achieve the effects of low production cost, good purity, and easy control of reaction conditions

Active Publication Date: 2016-05-25
XIAN MODERN CHEM RES INST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] Its two, in the synthesis of intermediate 2,2-dichlorobenzo-1,3-dioxole, its stability is relatively poor, very easy to hydrolyze and deteriorate, and product quality is difficult to control
[0012] Third, when the intermediate 2,2-dichlorobenzo-1,3-dioxole is fluorinated, the equipment requirements are high, polytetrafluoroethylene materials are required, and the preparation process is relatively polluted and corroded

Method used

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  • Synthesis of 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile
  • Synthesis of 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile
  • Synthesis of 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0056] (1) In a 1000mL autoclave, mix catechol 55.0g (0.5mol), potassium carbonate 85.0g (0.62mol), NMP (N-methylpyrrolidone) 200ml, tetrabutylammonium iodide 0.5g and di Add bromodifluoromethane 157g (0.75mol) into the reaction kettle, heat up to 100°C, react for 8h, cool down to room temperature, pour the reaction solution into 500ml of crushed ice, stir until the ice is completely dissolved, let stand to separate the liquid, and remove the water phase, add 10g of anhydrous sodium sulfate to dry the organic phase to obtain the crude product 2,2-difluorobenzo-1,3-dioxole, and then perform rectification to obtain the refined product 2,2-difluorobenzo- 1,3 dioxole 63g (0.4mol);

[0057] 1 HNMR (CDCl 3 , 500MHz): 7.05 (s, 4H, ArH); IR (KBr, cm -1 ): 3076 (νAr-H), 1642, 1486 (νC=C), 1239 (νC-F), 1040 (νC-0-C), 905 (νO-C-O).

[0058] (2) Cool down to -50°C, under nitrogen protection, add 100ml of n-hexane and 90ml (0.2mol) tert-butyllithium solution into a 500ml four-neck flas...

Embodiment 2

[0067] (1) In a 1000mL autoclave, add 55.0g (0.5mol) of catechol, 85.0g (0.62mol) of potassium carbonate, 200ml of DMF, 0.5g of 18-crown ether and 157g (0.75mol) of dibromodifluoromethane In the reaction kettle, raise the temperature to 80°C, react for 8 hours, cool down to room temperature, pour the reaction solution into 500ml of crushed ice, stir until the ice is completely dissolved, let stand to separate the liquid, remove the water phase, add 10g of anhydrous sodium sulfate to dry the organic phase to obtain the crude product 2,2-difluorobenzo-1,3-dioxole, and then rectify to obtain the refined product 2,2-difluorobenzo-1,3-dioxole 67 g (0.43 mol).

[0068] (2) In a 500ml four-neck flask equipped with a stirring and condenser, cool down to -50°C, under the protection of nitrogen, add 100ml of n-hexane and 90ml (0.2mol) of n-butyllithium solution, and then dropwise add 2,2 -Difluorobenzo-1,3-dioxole 32g (0.2mol), heat preservation reaction for 4h, 47.6g (0.28mol) ethyl e...

Embodiment 3

[0074] (1) In a 1000mL autoclave, mix catechol 55.0g (0.5mol), potassium hydroxide 85.0g (0.62mol), DMSO 200ml, 18-crown ether 0.5g and dibromodifluoromethane 157g (0.75mol) Add it into the reaction kettle, raise the temperature to 80°C, react for 8 hours, cool down to room temperature, pour the reaction liquid into 500ml of crushed ice, stir until the ice is completely dissolved, let stand to separate the liquid, remove the water phase, add 10g of anhydrous sodium sulfate to dry Organic phase, to obtain the crude product 2,2-difluorobenzo-1,3-dioxole, and then carry out rectification to obtain the refined product 2,2-difluorobenzo-1,3-dioxole Alkene 66g (0.41mol).

[0075] (2) In a 500ml four-neck flask equipped with a stirring and condenser, cool down to -50°C, under nitrogen protection, add 100ml tetrahydrofuran and 90ml (0.2mol) tert-butyllithium solution, and then dropwise add 2,2- Difluorobenzo-1,3-dioxole 32g (0.2mol), keep warm for 4h, add 47.6g (0.28mol) of ethyl eth...

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Abstract

The invention discloses a synthetic method of 4-(2,2-difluoro-1,3-benzodioxole-4-yl)pyrrole-3-nitrile. The method comprises the following steps of: preparing an intermediate 2,2-difluorobenz-1,3-dioxole through reacting catechol with dibromodifluoromethane, and preparing an intermediate 2-cyano-3-(2,2-difluorobenz-1,3-dioxole-4-yl)-2-acrylate. The fludioxonil prepared by the synthetic method provided by the invention has the purity of more than 99.0% and the total yield of more than 45.0%; the synthetic method has the advantages of cheap and easily available raw materials, simple process, high product yield in each step, good purity, low production cost, applicability to batch industrial production and the like.

Description

technical field [0001] The invention relates to a synthesis method of 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile. Background technique [0002] The structural formula of 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile (Fludioxonil) is shown in (I): [0003] [0004] It is a new type of non-systemic phenylpyrrole fungicide developed by the former Ciba-GeigyAG and now Syngenta, also known as fludioxonil, and its trade name is Shileshi. Other English names: Saphire, Celest, mixture Product names: Maxim, MaximXL, Switch. Fludioxonil is derived from the natural product nipyrrolidin, which is a new type of non-systemic broad-spectrum fungicide of pyrroles. As a foliar fungicide, it is mainly used to control Fusarium nivale, Tilletia tritici, and R. blight, etc. It has special effects on Botrytis cinerea; as a seed treatment agent, it is mainly used to prevent and control species in grains and chives. Inherited and soil-borne pathogens, such as Al...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D405/04
CPCC07D405/04
Inventor 王列平宁斌科黄晓瑛钱一石刘军徐泽刚张晓光林双政王月梅张建功王威王安勇
Owner XIAN MODERN CHEM RES INST
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