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Method for synthesizing alkenyl sulfone compound under metal-free condition

A synthesis method and technology of alkenyl sulfone, applied in the field of synthesis of alkenyl sulfone compounds, can solve the problems of tedious synthesis of starting materials and limited scope of application of substrates, etc., and achieve important theoretical significance and practical application value

Active Publication Date: 2020-06-12
TAIZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, almost all of these methods have disadvantages such as limited scope of substrate application, cumbersome steps required for the synthesis of starting materials, etc.

Method used

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  • Method for synthesizing alkenyl sulfone compound under metal-free condition
  • Method for synthesizing alkenyl sulfone compound under metal-free condition
  • Method for synthesizing alkenyl sulfone compound under metal-free condition

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028]

[0029] At room temperature, p-tolyldiazonium salt (0.3mmol), sodium metabisulfite (0.4mmol), propargyl alcohol (0.2mmol), Na 2 HPO 4 (0.3mmol), plugged the reaction tube with a stopper and replaced it three times in high-purity nitrogen or argon, so that the system was in anaerobic condition, then added 1,2-dichloroethane (2mL), and stirred at room temperature until TLC monitoring until complete reaction. The reaction solution was directly concentrated under reduced pressure, and the mixed system of petroleum ether and ethyl acetate was used as the mobile phase for column chromatography separation to obtain the corresponding alkenyl sulfone compound Example 1.

[0030] Structural characterization of compound example 1: 1 H NMR (400MHz, CDCl 3 )δ7.87(dt,J=8.5,1.6Hz,2H),7.77–7.73(m,2H),7.59–7.54(m,1H),7.48–7.42(m,2H),7.30(dd,J= 8.5,0.5Hz,2H),6.93(d,J=15.3Hz,1H),6.26(d,J=15.3Hz,1H),2.85–2.78(m,2H),2.42(s,3H),1.89– 1.83(m,2H),1.12(s,6H); 13C NMR (100MHz, CDCl 3 ...

Embodiment 2

[0032]

[0033] At room temperature, phenyldiazonium salt (0.3mmol), sodium metabisulfite (0.4mmol), propargyl alcohol (0.2mmol), Na 2 HPO 4 (0.3mmol), plugged the reaction tube with a stopper and replaced it three times in high-purity nitrogen or argon, so that the system was in anaerobic condition, then added 1,2-dichloroethane (2mL), and stirred at room temperature until TLC monitoring until complete reaction. The reaction solution was directly concentrated under reduced pressure, and the mixed system of petroleum ether and ethyl acetate was used as the mobile phase for column chromatography separation to obtain the corresponding alkenyl sulfone compound Example 2.

[0034] Structural characterization of compound example 2: 1 H NMR (400MHz, CDCl 3 )δ7.91–7.83(m,4H),7.64–7.49(m,4H),7.45(t,J=7.7Hz,2H),6.97(d,J=15.3Hz,1H),6.28(d,J =15.3Hz,1H),2.86–2.78(m,2H),1.91–1.83(m,2H),1.13(s,6H); 13 C NMR (100MHz, CDCl 3 )δ199.2, 154.7, 140.6, 136.6, 133.2, 133.1, 129.2, 128.5, ...

Embodiment 3

[0036]

[0037] At room temperature, 4-chlorophenyldiazonium salt (0.3mmol), sodium metabisulfite (0.4mmol), propargyl alcohol (0.2mmol), Na 2 HPO 4 (0.3mmol), plugged the reaction tube with a stopper and replaced it three times in high-purity nitrogen or argon, so that the system was in anaerobic condition, then added 1,2-dichloroethane (2mL), and stirred at room temperature until TLC monitoring until complete reaction. The reaction liquid was directly concentrated under reduced pressure, and the mixed system of petroleum ether and ethyl acetate was used as the mobile phase for column chromatography separation to obtain the corresponding alkenyl sulfone compound Example 3.

[0038] Structural characterization of compound example 3: 1 H NMR (400MHz, CDCl 3 )δ7.89–7.84(m,2H),7.83–7.77(m,2H),7.61–7.54(m,1H),7.51–7.42(m,4H),6.98(d,J=15.3Hz,1H) ,6.24(d,J=15.3Hz,1H), 2.85–2.78(m,2H),1.91–1.84(m,2H),1.13(s,6H); 13 C NMR (101MHz, CDCl 3 )δ199.1, 155.3, 139.9, 139.1, 136.5, 1...

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Abstract

The invention belongs to the technical field of organic chemistry, and particularly relates to a method for synthesizing an alkenyl sulfone compound under a metal-free condition. The structure of thecompound is characterized by 1H NMR, 13C NMR and other methods and is confirmed. The preparation method comprises the following steps: with 1,2-dichloroethane as a solvent, generating aryl sulfonyl free radicals on site from aryl diazonium salt and sodium pyrosulfite (Na2S2O5) at room temperature without a metal catalyst, performing free radical addition reaction on propargyl alcohol to generate alkenyl free radicals, and then performing intramolecular 1,5-hydrogen transfer and functional group transfer to obtain the alkenyl sulfone compounds. The alkenyl sulfone compound synthesis method hasthe advantages of simple and easily available raw materials, mild conditions, no use of a metal catalyst, simplicity, high efficiency, wide substrate application range, accordance with the environmental protection concept of green chemistry, and very high economic utilization value.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, in particular to a method for synthesizing alkenyl sulfone compounds under metal-free conditions Background technique [0002] Alkenyl sulfone compounds are not only an important class of organic and pharmaceutical synthetic intermediates, widely used in the synthesis of natural products, drugs and material molecules, but also the basic structural units of many biologically active molecules, such as cysteine ​​protease inhibitors . [(a) C. Meadows, J. Gervay-Hague, Med. Res. Rev., 2006, 26, 793; (b) I. Forristal, J. Sulfur Chem. 2005, 26, 163.] At present, the The synthesis methods mainly include Knoevenagel condensation, oxidation of alkenyl sulfides or sulfoxides, β-elimination of cyclic selenyl sulfones or halogenated sulfones, sulfonylation of alkenes / alkynes, etc. However, almost all of these methods have shortcomings such as limited scope of substrate application and tedious ste...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C315/00C07C317/24C07D333/22
CPCC07C315/00C07D333/22C07C317/24
Inventor 何福生吴劼叶盛青
Owner TAIZHOU UNIV
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