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

Method for synthesizing beta-thiocarbonyl compound by taking aryl sulfonyl chloride as sulfur source

A technology of arylsulfonyl chloride and thiocarbonyl, which is applied in the field of synthesizing β-thiocarbonyl compounds, and can solve problems such as unfavorable practical production, easy volatilization, and long reaction time

Active Publication Date: 2020-10-27
JIANGXI UNIV OF SCI & TECH
View PDF7 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, mercaptans (phenols) are mostly toxic, and have a very bad smell and are volatile, which is unfavorable for practical production
In addition, β-thiocarbonyl compounds can also be synthesized by using substituted thiols as odorless substrates, but this method has disadvantages such as pre-functionalization of substrates, noble metal catalysts, and long reaction time.

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
  • Method for synthesizing beta-thiocarbonyl compound by taking aryl sulfonyl chloride as sulfur source
  • Method for synthesizing beta-thiocarbonyl compound by taking aryl sulfonyl chloride as sulfur source
  • Method for synthesizing beta-thiocarbonyl compound by taking aryl sulfonyl chloride as sulfur source

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039]

[0040] In the air atmosphere, add 0.3mmol of p-toluenesulfonyl chloride, 0.6mmol of triphenylphosphine, 0.3mmol of potassium carbonate, 0.6mmol of sodium bisulfite formaldehyde, 0.3mmol of 2-cyclohexenone, and add 3mL of mixed solvent ( THF:DMSO=1:1; volume ratio), magnetically stirred at 25-50° C. for 1-2 h, and monitored by TLC during the reaction until complete reaction. After-treatment, an appropriate amount of ethyl acetate was added for extraction, dried over anhydrous sodium sulfate, and the pure 3a was separated by column chromatography after spin-drying the solvent under reduced pressure. Isolated yield: 82%.

[0041] 1 H NMR (CDCl 3 ,400MHz)δ7.32(d,J=8.0,2H),7.11(d,J=8.0,2H),3.33-3.32(m,1H),2.66-2.62(m,1H),2.38-2.28(m ,6H),2.12-2.09(m,2H),1.71-1.68(m,2H); 13 C NMR (CDCl 3 ,100MHz)δ208.99,138.26,134.08,129.96,129.28,47.92,46.60,41.00,31.40,24.19,21.26.

Embodiment 2

[0043]

[0044] In air atmosphere, add 0.3mmol of benzenesulfonyl chloride, 0.6mmol of triphenylphosphine, 0.3mmol of potassium carbonate, 0.6mmol of sodium bisulfite formaldehyde, 0.3mmol of 2-cyclohexenone, and add 3mL of mixed solvent (THF :DMSO=1:1; volume ratio), magnetically stirred at 25-50°C for 1-2h, and monitored by TLC during the reaction until complete reaction. After-treatment, an appropriate amount of ethyl acetate was added for extraction, dried over anhydrous sodium sulfate, and the pure 3b was separated by column chromatography after spin-drying the solvent under reduced pressure. Isolated yield: 81%.

[0045] 1 H NMR (400MHz, CDCl 3 )δ7.43-7.40(m,2H),7.33-7.25(m,3H),3.45-3.40(m,1H),2.70-2.65(m,1H),2.40-2.27(m,3H),2.16- 2.10(m,2H),1.78-1.65(m,2H); 13 C NMR (100MHz, CDCl 3 )δ208.6, 133.10, 133.02, 129.04, 127.61, 47.72, 46.03, 40.82, 31.12, 24.03.

Embodiment 3

[0047]

[0048] Add 0.3mmol p-methoxybenzenesulfonyl chloride, 0.6mmol triphenylphosphine, 0.3mmol potassium carbonate, 0.6mmol sodium bisulfite formaldehyde, 0.3mmol 2-cyclohexenone to 3mL In a mixed solvent (THF:DMSO=1:1; volume ratio), magnetically stirred at 25-50° C. for 1-2 h, and monitored by TLC during the reaction until complete reaction. After-treatment, an appropriate amount of ethyl acetate was added for extraction, dried over anhydrous sodium sulfate, and the pure 3c was separated by column chromatography after spin-drying the solvent under reduced pressure. Isolated yield: 85%.

[0049] 1 H NMR (400MHz, CDCl 3 )δ7.32(d, J=8.4Hz, 2H), 6.77(d, J=8.4Hz, 2H), 3.71(s, 3H), 3.17(dd, J=10.5, 7.7Hz, 1H), 2.54( dd,J=14.2,4.2Hz,1H),2.26–2.17(m,3H),2.05–2.01(m,2H),1.59(dd,J=11.5,6.6Hz,2H); 13 C NMR (100MHz, CDCl3) δ208.86, 159.91, 136.38, 122.90, 114.54, 55.26, 47.66, 46.93, 40.76, 31.12, 23.94.

[0050] Example 3 mainly investigates the applicability of substrates ...

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 method for synthesizing a beta-thiocarbonyl compound by taking aryl sulfonyl chloride as a sulfur source, comprising the following steps of: in an air atmosphere, adding arylsulfonyl chloride, ketene, triphenylphosphine, potassium carbonate and sodium formaldehyde sulfoxylate into a mixed solvent, magnetically stirring, and monitoring by using TLC (Thin Layer Chromatography) in the reaction process until complete reaction; adding a proper amount of an extraction agent for extraction, drying with a drying agent, carrying out reduced pressure spin-drying on the solvent, and carrying out column chromatography separation to obtain a pure beta-thiocarbonyl compound. According to the method disclosed by the invention, aryl sulfonyl chloride is directly used as a sulfursource, so that the use of a thiophenol raw material with unpleasant smell is avoided, and the beta-thiocarbonyl compound is prepared in a green and efficient manner. The method is mild in reaction condition, wide in substrate applicability, simple and convenient to operate, relatively low in cost and relatively high in yield.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry and relates to using arylsulfonyl chloride as a sulfur source, in particular to a method for synthesizing β-thiocarbonyl compounds using arylsulfonyl chloride as a sulfur source. Background technique [0002] β-thiocarbonyl compounds are commonly found in natural products and drug molecules, and are a very important class of molecular skeletons, such as the following literature: (a) Corey, E.J.; Clark, D.A.; Goto, G.; Marfat, A.; Mioskowski , C.; Samuelsson, C.; Hammarstrom, S.J.Am.Chem.Soc. 1980, 102, 3663; (b) Bakuzia, P.; Bakuzis, M.L.F.J.Org.Chem. Yi, N.; Soderquist, J.; Stein, H.; Cohen, J.; Perun, T.J.; [0003] For the synthesis of β-thiocarbonyl compounds, it is generally available through the Michael addition reaction of thiols (phenols) with α, β-unsaturated carbonyl compounds. However, most of the mercaptans (phenols) are poisonous, extremely smelly and volatile, which is un...

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
IPC IPC(8): C07C319/14C07C323/22
CPCC07C319/14C07C2601/14C07C2601/08C07C323/22
Inventor 刘晋彪任尚峰任淼峰
Owner JIANGXI UNIV OF SCI & TECH
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