Method for selectively synthesizing allylic sulfone compound by utilizing nonmetal catalyst

A non-metallic catalyst and allyl sulfone technology, which is applied in the field of selective synthesis of allyl sulfone compounds, can solve the problems of difficult operation, long reaction time, unstable raw materials, etc., and achieve the effect of shortening the reaction time and increasing the rate

Inactive Publication Date: 2017-12-01
WUHAN INSTITUTE OF TECHNOLOGY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In 2005, Nozhnin et al. reported the method of generating allyl sulfone compounds with sulfonyl chloride and α-methylstyrene derivatives under the catalysis of ketones, but the versatility of the reaction was limited, and pungent odor was used in the reaction triethylamine
In 2012, Li et al. reported a method for synthesizing allyl sulfone compounds with sulfonyl hydrazide and α-methylstyrene derivatives as raw materials under the action of TBAI and TBHP. This reaction has the instability of sulfonyl hydrazide and the reaction time is too long. long-term disadvantages
The main disadvantage of this method is that it requires strict anaerobic conditions and lacks practicality.
[0004] Although various methods for preparing allyl sulfone compounds have been disclosed in the present technology, these methods have disadvantages such as unstable raw materials, long reaction times, difficult operation or expensive catalysts.

Method used

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  • Method for selectively synthesizing allylic sulfone compound by utilizing nonmetal catalyst
  • Method for selectively synthesizing allylic sulfone compound by utilizing nonmetal catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] The specific steps are: add 0.3mmol 1-nitro-2-phenylpropene, 0.4mmol sodium benzenesulfinate, 0.03mmol I 2 , 0.6mmol TBHP and 3mL DMSO, after magnetically stirring at 80°C for 3 hours, the reaction solution was extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by column separation with ethyl acetate / petroleum ether=1:10 / V as the eluent to obtain the desired product as a white solid with a yield of 88%.

[0023] The proton nuclear magnetic spectrogram result of gained product is: 1 H NMR (600MHz, CDCl 3 ,ppm)δ7.77(d,J=7.8Hz,2H),7.52(t,J=7.2Hz,1H),7.40(t,J=7.8Hz,2H),7.27–7.20(m,5H), 5.57(s,1H), 5.20(s,1H), 4.26(s,2H).

Embodiment 2

[0025] The specific steps are: add 0.3mmol 1-nitro-2-phenylpropene, 0.35mmol sodium p-methoxybenzenesulfinate, 0.06mmolTBAI, 0.3mmol K to a 50mL round bottom flask 2 S 2 o 8 and 3mL DMF, stirred and reacted with magnetic force at 100°C for 3 hours, extracted the reaction solution with ethyl acetate, washed the organic layer with saturated brine, dried over anhydrous sodium sulfate, and evaporated the solvent under reduced pressure to obtain the crude product. Ethyl acetate / petroleum ether=1:15 / V was used as the eluent for column separation and purification to obtain the desired product, which was a white solid with a yield of 92%.

[0026] The proton nuclear magnetic spectrogram result of gained product is: 1 H NMR (600MHz, CDCl 3 ,ppm)δ7.67(d,J=9.0Hz,2H),7.26–7.20(m,5H),6.85(d,J=9.0Hz,2H),5.57(s,1H),5.19(s,1H ), 4.23(s,2H), 3.80(s,3H).

Embodiment 3

[0028] The specific steps are: add 0.3mmol 1-nitro-2-(4-bromophenyl)propene, 0.44mmol sodium p-methoxybenzenesulfinate, 0.06mmolI 2 , 0.3mmol TBHP and 3mL DMSO, reacted with magnetic stirring at 80°C for 2.5 hours, extracted the reaction solution with ethyl acetate, washed the organic layer with saturated brine, dried over anhydrous sodium sulfate, evaporated the solvent under reduced pressure to obtain the crude product, The crude product was purified by column separation with ethyl acetate / petroleum ether=1:10 / V as the eluent to obtain the desired product, which was a white solid with a yield of 87%.

[0029] The proton nuclear magnetic spectrogram result of gained product is: 1 H NMR (400MHz, CDCl 3 ,ppm)δ7.71(d,J=8.8Hz,2H),7.30–7.26(m,2H),7.00–6.89(m,4H),5.55(s,1H),5.20(s,1H),4.24 (s,2H), 3.87(s,3H).

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Abstract

The invention relates to a method for selectively synthesizing an allylic sulfone compound. The method comprises the following steps: under the conditions of taking nitroolefin and sodium sulfinate stable and convenient to operate as raw materials and having participation of a non-metal catalyst and an oxidant, adding a solvent for heating and stirring, and processing to obtain the allylic sulfone compound. The method has the beneficial effects that by adopting low-cost and easily available I2 or TBAI as a catalyst, nitroolefin is activated by iodine, and sulfonate can be used as a mild lewis base in reaction. The key step of the reaction is that lewis base can promote the balance of nitroolefin and ally-nitro compound, and through the step, stable nitroolefin is converted into ally-nitro compound, and due to the compounding of ally-nitro, free radical addition reaction can occur easily, so that the reaction is more easily conducted under mild conditions, the reaction rate is increased, the reaction time is shortened, and the compound of allylic sulfone compound structure can be more conveniently and effectively synthesized.

Description

technical field [0001] The invention relates to a method for selectively synthesizing allyl sulfone compounds under the action of a non-metallic catalyst and an oxidant, and belongs to the technical field of organic and pharmaceutical synthesis. technical background [0002] Allyl sulfone compounds can be used as reactants or intermediates in many organic synthesis reactions. It can be used as a synthon in many reactions, such as the addition of 1,1- or 1,3-dipole. Meanwhile, allyl sulfone compounds exhibit various pharmacological activities such as: antitumor activity, anti-inflammatory efficacy, antifungal and inhibition of HIV-1 reverse transcriptase. Allyl sulfone compounds and their derivatives also widely exist in many natural compounds, organic synthetic molecules and drug molecules, and are a very important functional group in drug synthesis and organic synthesis. Therefore, the research on the synthesis method of allyl sulfone compounds has aroused great interest o...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C317/14C07C317/22C07C315/00C07D333/18
CPCC07C315/00C07D333/18C07C317/14C07C317/22
Inventor 陈云峰雷雪郑镭张传新
Owner WUHAN INSTITUTE OF TECHNOLOGY
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