Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Preparation method of 2-(2',2'-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride

A technology of trifluoromethylbenzenesulfonyl chloride and difluoroethoxy is applied in the field of preparation of 2--6-trifluoromethylbenzenesulfonyl chloride, and can solve the problems of high price, reduced yield, potential safety hazards and the like, To achieve the effect of simple operation and improve synthesis efficiency

Inactive Publication Date: 2016-02-03
TIANJIN MODERN VOCATIONAL TECH COLLEGE
View PDF5 Cites 8 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

It has little impact on animals and the ecological environment, and so far there is no relevant report on penoxsulam-resistant weeds
The preparation of penoxsulam involved in the US patent of Dow AgroSciences (DowAgroSciences) in 1999 is to prepare 6-trifluoromethyl-2- Fluorobenzenesulfonyl chloride, the market level of this raw material is not high, and the price is expensive
In the other two patents of Dow Company, the preparation method of using methoxymethylene chloride as the protecting group of phenolic hydroxyl was mentioned respectively, but the cumbersome steps of protection and deprotection were added in the synthesis, which reduced the yield
In addition, the introduction of difluoroethoxy requires expensive and unmarketable 2,2-difluorobromoethane as a reagent
[0008] At present, 2-(2',2'-difluoroethoxy)-6-trifluoromethylbenzenesulfonyl chloride is used as a key intermediate, and its preparation method uses m-trifluoromethylphenol as a raw material, and the reaction steps are 6 long step, the yield is low; and wherein chlorine is used as an oxidant, which is highly toxic and explosive
Serious safety hazards during mass production

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Preparation method of 2-(2',2'-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride
  • Preparation method of 2-(2',2'-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride
  • Preparation method of 2-(2',2'-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] A preparation method of 2-(2',2'-difluoroethoxy)-6-trifluoromethylbenzenesulfonyl chloride, comprising the steps of:

[0035]

[0036] (1) 100 g of 2,2-difluoroethanol, 160 g of triethylamine and 900 mL of anhydrous dichloromethane were added to a 2 L round bottom flask. At 0°C, 146.6 g of methanesulfonyl chloride was slowly added dropwise to the above solution, and after naturally rising to room temperature, the reaction was carried out for 4 hours. The reaction solution was poured into ice water, the organic phase was separated, washed with water, washed with salt water, dried, and spin-dried to obtain a crude product. After rectification, compound (Ⅲ) (173.9 g, light yellow liquid) was obtained, with a yield of 89%. Proton NMR spectrum (400MHz, CDCl 3 ) δ: 3.13(s, 3H), 4.39(dt, J=3Hz, J=13Hz, 2H), 6.02(tt, J=3Hz, J=55Hz, 1H).

[0037]

[0038] (2) Add 160g of compound (Ⅲ), 162g of m-trifluoromethylphenol and 207g of anhydrous potassium carbonate into 1000mL o...

Embodiment 2

[0042] A preparation method of 2-(2',2'-difluoroethoxy)-6-trifluoromethylbenzenesulfonyl chloride, comprising the steps of:

[0043]

[0044] (1) 100 g of 2,2-difluoroethanol, 205 g of triethylamine and 900 mL of anhydrous dichloromethane were added to a 2 L round bottom flask. At 0°C, 200 g of trifluoromethanesulfonic anhydride was slowly added dropwise to the above solution, and after naturally rising to room temperature, the reaction was carried out for 5.2 hours. The reaction solution was poured into ice water, the organic phase was separated, washed with water, washed with brine, dried, and spin-dried to obtain a crude product. After rectification, compound (IV) (120.1 g, light yellow liquid) was obtained, with a yield of 61%. Proton NMR spectrum (400MHz, CDCl 3 ) δ: 4.58 (dt, J=3.6, 12.8Hz, 2H), 6.05 (tt, J=3.6, 54Hz, 1H).

[0045]

[0046] (2) Under ice bath conditions, 160 g of compound (IV), 90.8 g of m-trifluoromethylphenol and 55 g of anhydrous pyridine were a...

Embodiment 3

[0050] A preparation method of 2-(2',2'-difluoroethoxy)-6-trifluoromethylbenzenesulfonyl chloride, comprising the steps of:

[0051]

[0052] (1) 100 g of 2,2-difluoroethanol, 160 g of triethylamine and 900 mL of anhydrous dichloromethane were added to a 2 L round bottom flask. At 0°C, 146.6 g of methanesulfonyl chloride was slowly added dropwise to the above solution, and after naturally rising to room temperature, the reaction was carried out for 4 hours. The reaction solution was poured into ice water, the organic phase was separated, washed with water, washed with salt water, dried, and spin-dried to obtain a crude product. After rectification, compound (Ⅲ) (173.9 g, light yellow liquid) was obtained, with a yield of 89%. Proton NMR spectrum (400MHz, CDCl 3 ) δ: 3.13(s, 3H), 4.39(dt, J=3Hz, J=13Hz, 2H), 6.02(tt, J=3Hz, J=55Hz, 1H).

[0053]

[0054] (2) 160 g of compound (III), 162 g of m-trifluoromethylphenol and 207 g of anhydrous potassium carbonate were added t...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a preparation method of 2-(2',2'-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride. The preparation method comprises following steps: (1) a sulfonyl chloride or a sulfonic anhydride is added into an organic solvent containing 2,2-difluoroethanol and an alkali, and a compound I is obtained via complete reaction, wherein the sulfonyl chloride is selected from alkyl sulfonyl chloride or benzene sulfonyl chloride, and the sulfonic anhydride is selected from alkyl sulfonic anhydride or benzene sulfonic anhydride; (2) m-trifluoromethylphenol, the compound I, and an alkali are added into an organic solvent, an obtained mixture is heated and stirred, and a compound II is obtained via complete reaction; and (3) an accelerant and the compound II are added into an organic solvent, a strong alkali is added, the sulfonyl chloride is added into an obtained reaction solution, and 2-(2',2'-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride is obtained via complete reaction and purifying. The preparation method is simple, is high in efficiency, is safe and reliable, and is capable of increasing synthesis efficiency of penoxsulam greatly; and operation is simple and convenient.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a preparation method of 2-(2',2'-difluoroethoxy)-6-trifluoromethylbenzenesulfonyl chloride. Background technique [0002] 2-(2’,2’-difluoroethoxy)-6-trifluoromethylbenzenesulfonyl chloride is a key intermediate in the synthesis of the herbicide penoxsulam. The structure of penoxsulam is as follows: [0003] [0004] Penoxsulam structure [0005] Penoxsulam is a triazolopyrimidine sulfonamide herbicide newly developed by Dow AgroSciences in recent years. The common name of penoxsulam is penoxsulam, and the trade names are Clipper25OD, GraniteGR, GranieeSC, Daojie. [0006] Penoxachlor is a traditional herbicide, absorbed by leaves, young shoots and roots, and transmitted to meristems through xylem and phloem, inhibiting plant growth, necrosis of terminal buds in 7-14 days after treatment, and plant death in 2-4 weeks. The main mechanism of action of penoxsulam is to inhibit...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): C07C309/87C07C303/10
Inventor 袁文蛟刘雅莉孙皓干浩
Owner TIANJIN MODERN VOCATIONAL TECH COLLEGE
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com