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A method for synthesizing β-thiocarbonyl compounds with arylsulfonyl chloride as sulfur source

An arylsulfonyl chloride and thiocarbonyl technology, which is applied in the field of synthesizing beta-thiocarbonyl compounds, can solve the problems of pre-functionalization of substrates, unfavorable practical production, long reaction time, etc., and achieves wide applicability of substrates, Considerable application prospect, efficient response effect

Active Publication Date: 2022-04-08
JIANGXI UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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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

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  • A method for synthesizing β-thiocarbonyl compounds with arylsulfonyl chloride as sulfur source
  • A method for synthesizing β-thiocarbonyl compounds with arylsulfonyl chloride as sulfur source
  • A method for synthesizing β-thiocarbonyl compounds with arylsulfonyl chloride as sulfur source

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039]

[0040] In 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 (100 MHz, 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...

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Abstract

The invention discloses a method for synthesizing β-thiocarbonyl compounds by using arylsulfonyl chloride as a sulfur source. In air atmosphere, arylsulfonyl chloride, enone, triphenylphosphine, potassium carbonate, sodium bisulfoxylate formaldehyde , added to a mixed solvent, magnetically stirred, and monitored by TLC during the reaction until complete reaction; after-treatment, add an appropriate amount of extractant to extract, dry with a desiccant, spin the solvent under reduced pressure, and obtain pure β-thiocarbonyl through column chromatography compound. Through the method of the invention, arylsulfonyl chloride is directly used as a sulfur source, avoiding the use of thiophenol raw materials with bad smell, and green and efficient preparation of β-thiocarbonyl compounds. The reaction condition is mild, the substrate has wide applicability, the operation is simple, the cost is low, and the yield is high.

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

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Application Information

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Patent Type & Authority Patents(China)
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
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