Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature

A technology of verbenone and verbenol, applied in the field of preparation of verbenol and verbenone, can solve the problem that the yield of verbenone is less than 20%, the yield of verbenol is less than 12%, and the yield is less than 20%. % and other problems, to achieve the effect of short reaction time, cheap and easy-to-obtain catalyst, and simple operation

Inactive Publication Date: 2011-03-16
JIANGNAN UNIV
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  • Abstract
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  • Claims
  • Application Information

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Problems solved by technology

[0003] (1) Using cobalt chloride as a catalyst, Journal of Molecular Catalysis A: Chemical 201 (2003) 71–77, the yield of verbenol is about 10%, the yield of verbenone is about 10%, the disadvantage is that the yield is too low
[0004] (2) Using cobalt-containing complexes as catalysts, Journal of Molecular Catalysis A: Chemical 198 (2003) 223–229, the disadvantage is that the yield is low, and the yields of verbenol and verbenone are both less than 20%, and oxygen oxidation is required , the reaction time is about 7h
[0005] (3) Combined catalysis of silica and titanium dioxide, Catalysis Letters 67 (2000) 203–206, the disadvantage is low yield, the yield of verbenol is less than 12%, and the yield of verbenone is less than 20%

Method used

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  • Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] 0.994g (7.3mmol) a- Add pinene to 10 mL of acetonitrile solvent, add 0.185 g (1.46 mmol) of catalyst ferric dichloride, add 0.263 g (1.46 mmol) of 1,10-phenanthroline, then add 22 mmol of hydrogen peroxide, and stir at 15 °C. The reaction was stopped after 2h. Centrifuge or filter to remove catalyst, dry with anhydrous sodium sulfate, and rotary evaporate to remove acetonitrile and hydrogen peroxide. With petroleum ether: a mixed solvent of ethyl acetate volume ratio of 5:1 was used as an eluent, and cocatalyst 1 (1,10-phenanthroline) and by-products were removed by column chromatography to obtain 0.078g verbenol (produced The rate is 7%), 0.941g verbenone (yield rate is 85.9%).

[0019] Verbenol: CDCl 3 , δ (ppm); NMR 1 H: 0.85 (3H,s,CH 3 , 8-H); 1.31 (3H, s, CH 3 , 10-H); 1.71 (t, J =1.59 Hz, CH 3 , 9-H); 2.00 (m, 1H, 4-H); 2.17 (m, 1H,5-H); 2.26 (m, 1H, 6-H); 4.43 (m, 1H, 1-H); 5.32 (m,1H, 2-H).

[0020] Verbolenone: CDCl 3 , δ (ppm); NMR 1 H: 0.98 (3H,...

Embodiment 2

[0022] 0.994g (7.3mmol) a- Add pinene to 10 mL of dichloromethane solvent, add 0.277g (1.46mmol) tin dichloride, add 0.263g (1.46mmol) 1,10-phenanthroline, then add 29.2mmol peracetic acid, at 25°C After stirring, stop the reaction after 3h. Remove the catalyst by centrifugation or filtration, dry with anhydrous sodium sulfate, and rotary evaporate to remove dichloromethane and peracetic acid. With sherwood oil: the mixed solvent that ethyl acetate volume ratio is 5: 1 is eluent, removes cocatalyst 1 (1,10-phenanthroline) and by-product through column chromatography, obtains 0.973g verbenol (product The yield was 87.6%), 0.035g verbenone (the yield was 3.2%).

Embodiment 3

[0024] 0.994g (7.3mmol) a- Add pinene to 10mL acetic acid solvent, add 0.098 g (0.73mmol) copper dichloride, add 0.114g (0.73mmol) 2,2'-bipyridine, then add 14.6mmol tert-butyl hydroperoxide, at 40°C After stirring, stop the reaction after 1h. The catalyst was removed by centrifugation and filtration, dried over anhydrous sodium sulfate, and rotary evaporated to remove acetic acid and tert-butyl hydroperoxide. With sherwood oil: the mixed solvent that ethyl acetate volume ratio is 5: 1 is eluent, removes 2,2'-dipyridine and by-product through column chromatography, separates and obtains 0.087g verbenol (yield rate 7.8% ), 0.902g verbenone (82.3% yield).

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Abstract

The invention discloses a preparation method of verbenol and verbenone through the air oxidation of a-pinene at room temperature, belonging to the technical field of the preparation of the verbenol and the verbenone. In the method disclosed by the invention, a catalyst, a co-catalyst 1 and a co-catalyst 2 are added in the a-pinene as a raw material to prepare the verbenol and the verbenone through the catalytic oxidation at the room temperature in the presence of the air. The preparation method of the verbenol and the verbenone has moderate reaction condition and short reaction time and is simple to operate, catalysts are cheap and available, and the prepared verbenol and verbenone are high in yield and have the characteristic of higher industrial production value.

Description

technical field [0001] An air oxidation at room temperature a- The method for preparing verbenol and verbenone from pinene belongs to the technical field of verbenol and verbenone preparation. Background technique [0002] Verpenol (4,6,6-trimethylbicyclo[3.1.1]-3-hepten-2-ol), verbenone (4,6,6-trimethylbicyclo[3.1.1]- 3-hepten-2-one) is an oxygen-containing derivative of monoterpene, which has important applications in organic synthesis and chemical industry. Verbeenol and verbenone have a verbena-like aroma and can be used in food additives, cosmetics, flavors and fragrances. Verpenol and verbenone are natural components of plants and also pheromones for insects. It plays an important role in the prevention and control of the stem pests of pine species, which seriously damages pine species - pine scorpion. At present, there are not many methods for chemically synthesizing verbenol and verbenone, and the yields are not high. For example: [0003] (1) Using cobalt chlo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/627C07C45/34C07C35/28C07C29/50
Inventor 郑昌戈刘煊业喻晓蔚徐岩
Owner JIANGNAN UNIV
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