Chemical synthesis method for substituting alpha, beta unsaturated ketone by sulphonyl

A chemical synthesis, unsaturated technology, applied in chemical instruments and methods, organic chemistry, preparation of organic compounds, etc., to achieve the effect of cheap raw materials, cost reduction, and easy availability of raw materials

Inactive Publication Date: 2007-10-24
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the second method overcomes some shortcomings of the first method, it can only be used for the synthesis of aromatic products and still has its limitations

Method used

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  • Chemical synthesis method for substituting alpha, beta unsaturated ketone by sulphonyl
  • Chemical synthesis method for substituting alpha, beta unsaturated ketone by sulphonyl
  • Chemical synthesis method for substituting alpha, beta unsaturated ketone by sulphonyl

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Example 1: Preparation of 4-phenyl-1-benzenesulfonyl-3-butene-2-one

[0029]

[0030] In a 500ml three-necked flask equipped with a mechanical stirring device, add 1.0 g (6.8 mmol) of 4-phenyl-3-buten-2-one, 2,4,4,6-tetrabromo-2,5-cyclohexyl 2.8 g (6.8 mmol) of dien-1-one was then added to 100 ml of 1,4-dioxane dissolved in 1% (g / ml) HCl, and stirred at room temperature for 2 hours. Stop the reaction and saturate with NaHCO 3 Neutralize, CH 2 Cl 2 It was extracted and dried, concentrated, dissolved in 100ml of ethanol, reacted with sodium benzenesulfinate dihydrate, post-treated, and recrystallized from ethanol to obtain 1.15g of the product with a yield of 65%, m.p.96-98°C. 1 H-NMR (CDCl 3 ): δ7.86-7.90 (m, 2H), 7.42-7.67 (m, 9H), 6.94 (1H, d, J=15.8Hz), 4.40 (s, 2H); MS (70ev) m / z: 286 (M + , 7).

Embodiment 2

[0031] Example 2: 4-p-methoxyphenyl-1-benzenesulfonyl-3-buten-2-one

[0032]

[0033] In a 500ml three-necked flask equipped with a mechanical stirring device, add 1.2 g (6.8 mmol) of 4-p-methoxyphenyl-3-buten-2-one, 2,4,4,6-tetrabromo-2, 5.6 g (13.6 mmol) of 5-cyclohexadien-1-one was added, and then 100 ml of acetonitrile dissolved in 5% (g / ml) HCl was added, and stirred at 60° C. for 5 hours. Stop the reaction and saturate with NaHCO 3 Neutralize, CH 2 Cl 2 It was extracted and dried, concentrated, dissolved in 100ml of ethanol, reacted with sodium benzenesulfinate dihydrate, post-treated, and recrystallized from ethanol to obtain 1.7g of the product with a yield of 78%, m.p.142-144°C. 1 H-NMR (CDCl 3 ): δ7.90-7.92(m, 2H), 7.52-7.67(m, 6H), 6.92-6.94(d, J=8.8Hz, 2H), 6.79-6.83(d, J=15.7Hz, 1H), 4.37(s, 2H), 3.86(s, 3H); MS(70ev) m / z(rel.intensity,%) 316(M + ,twenty four).

Embodiment 3

[0034] Example 3: 4-(4'-N, N-dimethylamino)phenyl-1-benzenesulfonyl-3-butene-2-one

[0035]

[0036]In a 500ml three-necked flask equipped with a mechanical stirring device, add 1.3g (6.8mmol) of 4-p-dimethylaminophenyl-3-buten-2-one, 2,4,4,6-tetrabromo-2 , 2.8g (6.8mmol) of 5-cyclohexadien-1-one, and then add 100ml of 1,4-dioxane dissolved in 0.1% (g / ml) HBr, and stir at 100°C for 1 hour. Stop the reaction and saturate with NaHCO 3 Neutralize, CH 2 Cl 2 It was extracted and dried, concentrated, dissolved in 100ml of ethanol, reacted with sodium benzenesulfinate dihydrate, post-treated, and recrystallized from ethanol to obtain 1.0 g of the product with a yield of 54%, m.p.157-159°C. 1 H-NMR (CDCl 3 ): δ7.92-7.90 (m, 2H), 7.44-7.65 (m, 6H), 6.69-6.67 (m, 3H), 4.35 (s, 2H), 3.06 (s, 3H).

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Abstract

The invention discloses a chemical synthesizing method of alpha, beta-unsaturated ketone substituted by sulfonyl as formula (I), which comprises the following steps: adding unsaturated ketone as formula (III) and 2,4,4,6-tetrabromine-2, 5-cyclohexadiene-1-ketone as bromide agent as formula (II); disposing to obtain the rough product of bromide; proceeding nucleophilic reaction for rough bromide product and RSO2Na as formula (IV); making R and R1 in the formula (I) as alkyl or aryl with random carbon number; setting the molar rate of unsaturated ketone and bromide agent at 1:1-2; setting the bulk rate of each molar of unsaturated ketone and aprotic polar solvent at 1:5-50; obtaining the density of inorganic acid in the aprotic solvent at 0. 1%-5%(g / ml).

Description

(1) Technical field [0001] The invention relates to a chemical synthesis method for sulfonyl-substituted α, β unsaturated ketones. (2) Background technology [0002] Sulfonyl-substituted α, β unsaturated ketones are a kind of prochiral bidentate coordination substrates in the Diels-Alder reaction, and can be used as dienophiles in the asymmetric catalytic Diels-Alder reaction we studied. In the Hetero Diels-Alder reaction, it can be used as a diene, and in the Michael reaction, it can be used as both an acceptor and a donor. The reported research results have proved that in the above reaction, as a new type of reaction substrate, it can be effectively matched with the chiral catalyst to achieve the ideal stereo control effect, and a chiral compound with high enantioselectivity has been synthesized. It has broad application prospects in the synthesis of chiral drugs and natural products. [0003] Two methods have been reported for the synthesis of sulfonyl-substituted α, β-...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C317/24C07C315/00
Inventor 裴文王永江孙莉拜堃张徐飞
Owner ZHEJIANG UNIV OF TECH
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