Allylic oxidation method for cyclohexene derivative

A technology for allylic oxidation and cyclohexene, applied in chemical instruments and methods, physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problem of lengthy synthesis process and low yield Human satisfaction, unfriendly environment, etc.

Active Publication Date: 2008-03-19
CHINA TOBACCO HUNAN INDAL CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

There are quite a lot of reports about the method of allylic oxidation, but the yield of many synthetic methods is not satisfactory; or the synthetic process is lengthy and complicated; or use som

Method used

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  • Allylic oxidation method for cyclohexene derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1 Synthesis of oxyisophorone

[0031] α-isophorone 1.38g, VO(acac) 2 0.20g, 20ml of acetone, react with 15ml of tert-butyl hydroperoxide (70%) at 50℃, stir after 18h, remove the catalyst, rotary evaporate, evaporate the solvent and tert-butanol to dryness, extract with 2*20ml of ether, Na 2 SO 3 Solution 20ml for washing, water 20ml for washing, anhydrous Na 2 SO 4 Drying, rotary evaporation, petroleum ether: ethyl acetate = 8:1 as the eluent, column chromatography to obtain 0.6 g (40%) oxyisophorone.

[0032] NMR 1 H(CDCl 3 , 300MHz): 1.249(s, 6H), 2.014(s, 3H), 2.723(s, 2H). 6.555-6.571(m, 1H). MS: 152(M + , 66%), 137 (11%), 124 (4%), 109 (16%), 96 (96%), 81 (5%), 68 (100%).

Embodiment 2

[0033] Embodiment 2: Synthesis of theaspiranone

[0034] Theaspirane 1.94g, VO(acac) 2 0.266g, in 15ml of acetonitrile, react with 7ml of tert-butyl hydroperoxide (70%) at 40°C, stop the reaction after 6h, remove the catalyst, rotary evaporate, evaporate the solvent and tert-butanol to dryness, extract with 2*20ml of ether, Na 2 SO 3 Solution 20ml for washing, water 20ml for washing, anhydrous Na 2 SO 4 Drying, rotary evaporation, the peak area of ​​theaspiranone was 70% after GC-MS analysis. MS: 208(M + , <1%), 152 (100%), 110 (63%), 193 (1%), 165 (2%), 96 (9%), 82 (8%), 69 (7%).

Embodiment 3

[0035] Embodiment 3: Synthesis of α-pinenone

[0036] α-pinenone 1.36g, VO(acac) 2 0.266g, 20ml of acetone, react with 7ml of tert-butyl hydroperoxide (70%), stop the reaction for 10h, remove the catalyst, rotary evaporate, evaporate the solvent and tert-butanol to dryness, extract with 2*20ml of ether, Na 2 SO 3 Solution 20ml for washing, water 20ml for washing, anhydrous Na 2 SO 4 Drying, rotary evaporation, petroleum ether: ethyl acetate = 5:1 as eluent, column chromatography to obtain α-pinenone 0.93g (62%).

[0037] MS: 150(M + , 48%), 135 (79%), 122 (17%), 107 (100%), 95 (13%), 91 (59%), 79 (36%), 67 (15%).

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Abstract

The invention discloses a method of the allylic oxidation of a cyclohexenyl derivative. In organic solvent, the cyclohexenyl derivative reacts with vanadium compound and alkyl hydroperoxide at a temperature lower than 80 DEG C, so that Alpha, Beta-unsaturated carbonyl compound is composed. The invention has the advantages of simple method and high product yield, and the produced Alpha, Beta-unsaturated ketone can be widely applied to food additives, cosmetics, medicines, etc.

Description

technical field [0001] The invention relates to a method for allylic oxidation of cyclohexene derivatives. Background technique: [0002] Allylic oxygen is a very important organic reaction, and the synthesized α, β-unsaturated ketones are widely used in food additives, cosmetics, medicine and so on. There are quite a lot of reports about the method of allylic oxidation, but the yield of many synthetic methods is not satisfactory; or the synthetic process is lengthy and complicated; or use some precious metals and other reagents; or use unfriendly reagents, such as Chromium trioxide, chromium trioxide-pyridine, tert-butyl chromate, pyridinium dichromate, pyridinium chlorochromate, etc. [0003] Therefore, it is a great challenge to find a simple, efficient, safe, environmentally friendly, and low-consumption method for allylic oxidation. Invention content: [0004] The purpose of the present invention is to provide a method for allylic oxidation of cyclohexene derivative...

Claims

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Application Information

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IPC IPC(8): C07C45/87C07C49/603C07D307/12B01J23/22
Inventor 杨华武陈勇朱卓越赵瑜陈雄黎艳玲银董红刘建福
Owner CHINA TOBACCO HUNAN INDAL CORP
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