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Method for synthesizing 2-chlorine-4-trifluoromethyl phenol

A technology of trifluoromethylphenol and trifluoromethyl, which is applied in the field of herbicide preparation, can solve the problems of high production cost, long reaction time, and unsuitable use of trifluoromethylphenol, and achieve convenient post-processing and short reaction time , the effect of increasing the yield

Inactive Publication Date: 2018-07-13
JIANGSU CHANGQING AGROCHEM NANTONG
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

And because the raw material p-trifluoromethylphenol and p-trifluoromethylaniline used in the first two synthetic routes have higher production costs, so the first two synthetic routes should not be adopted
The raw material 3,4-dichloro-trifluorotoluene used in the third process route is easy to get, and the process is feasible, but the reaction time is longer and the yield is lower

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] Into a round bottom flask was added 4-(trifluoromethyl)benzaldehyde (6.75 mmol, 1.0 equiv), CH 2 Cl 2 (20 mL), then add mCPBA (6.78 mmol, 1.0 equiv), stir at room temperature for 2 h, add 15 ml saturated NaHSO 3 The aqueous solution was transferred to a separatory funnel for extraction, the organic phases were collected and combined, dried and filtered with anhydrous sodium sulfate to obtain a 4-(trifluoromethyl)phenol solution, and the monitored yield was 85%. Under inert gas conditions, add NCS (5.74 mmol) and CH in a round bottom flask 2 Cl 2 (20.0 mL), cooled to -78 °C, added ZrCl 4 (0.115 mmol), followed by adding 4-(trifluoromethyl)phenol solution, the reaction was stirred at room temperature for 6 hours, after the reaction was completed, saturated NaHCO 3 The aqueous solution was extracted, the organic phases were collected and combined, and the solvent was removed to obtain 2-chloro-4-trifluoromethylphenol with a yield of 88%.

Embodiment 2

[0016] Add 4-(trifluoromethyl)benzaldehyde (6.75 mmol, 1.0 equiv) to a round bottom flask, CH 2 Cl 2 (20 mL), then add mCPBA (0.68 mmol, 0.1 equiv), stir at room temperature for 2 h, add 15 ml saturated NaHSO 3 The aqueous solution was transferred to a separatory funnel for extraction, the organic phases were collected and combined, dried and filtered with anhydrous sodium sulfate to obtain a 4-(trifluoromethyl)phenol solution, and the monitored yield was 44%. Under inert gas conditions, add NCS (2.97 mmol) and CH in a round bottom flask 2 Cl 2 (20.0 mL), cooled to -78 °C, added ZrCl 4 (0.06 mmol), followed by adding 4-(trifluoromethyl)phenol solution, the reaction was stirred at room temperature for 6 hours, after the reaction was completed, saturated NaHCO 3 The aqueous solution was extracted, the organic phases were collected and combined, and the solvent was removed to obtain 2-chloro-4-trifluoromethylphenol with a yield of 88%.

Embodiment 3

[0018] Into a round bottom flask was added 4-(trifluoromethyl)benzaldehyde (6.75 mmol, 1.0 equiv), CH 2 Cl 2 (40 mL), then add mCPBA (67.8 mmol, 10 equiv), stir at room temperature for 2 h, add 30 ml saturated NaHSO 3 The aqueous solution was transferred to a separatory funnel for extraction, the organic phases were collected and combined, dried and filtered with anhydrous sodium sulfate to obtain a 4-(trifluoromethyl)phenol solution, and the monitored yield was 86%. Under inert gas conditions, add NCS (2.9 mmol, ) and CH in a round bottom flask 2 Cl 2 (20.0 mL), cooled to -78 °C, added ZrCl 4 (0.116 mmol), then added 4-(trifluoromethyl)phenol solution, the reaction was stirred at room temperature for 6 hours, after the reaction was completed, saturated NaHCO 3 The aqueous solution was extracted, the organic phases were collected and combined, and the solvent was removed to obtain 2-chloro-4-trifluoromethylphenol with a yield of 70%.

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Abstract

The invention discloses a method for synthesizing 2-chlorine-4-trifluoromethyl phenol. The method comprises the following steps: (1) carrying out an oxidation reaction, namely enabling 4-(trifluoromethyl) benzaldehyde, an organic solvent and an oxidant to react at 0 DEG C or a higher temperature in a reaction container so as to obtain 4-(trifluoromethyl) phenol; (2) carrying out a halogenation reaction, namely in the presence of an inert gas, adding a halogenation reagent and an organic solvent into another reaction container, sequentially adding a catalyst and the 4-(trifluoromethyl) phenol obtained in the step (1) at a low temperature, and stirring at a room temperature to enable the components to react, thereby obtaining 2-chlorine-4-trifluoromethyl phenol. The method is relatively highin raw material availability, relatively less in byproduct amount, low in pollution, and relatively short in reaction time, and has the characteristics that the operation is simple and convenient, products and reaction systems can be easily separated, aftertreatment is convenient and rapid, the obtained product is relatively high in purity, and the like, the yield is greatly improved, and a reliable foundation is provided for industrial production.

Description

technical field [0001] The invention relates to the technical field of herbicide preparation, in particular to a method for synthesizing 2-chloro-4-trifluoromethylphenol. Background technique [0002] Acifluorfen, fomesafen, lactofen, and acifluorfen are diphenyl ether herbicides, which are mainly used for post-emergence control of broad-leaved weeds, with high activity, broad herbicidal spectrum, With low toxicity, it is applied to cereal crops and has been widely used in northern my country. 2-Chloro-4-trifluoromethylphenol is an important intermediate in the synthesis of diphenyl ether herbicides, and it is also widely used in the synthesis of pesticides and medicines. So far, people have developed various methods for synthesizing 2-chloro-4-trifluoromethylphenol compounds. There are three main traditional synthetic methods: the first method is to use p-trifluoromethylphenol as raw material, through sulfur Acyl chloride chlorination reaction, and then obtain the intermed...

Claims

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Application Information

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IPC IPC(8): C07C39/26C07C37/62C07C37/60C07C39/24
CPCC07C37/60C07C37/62C07C39/24C07C39/26
Inventor 张振明粟永利吕良忠赵河万永望
Owner JIANGSU CHANGQING AGROCHEM NANTONG