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Synthesis method of oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol

A technology of verbenone and verbenol, which is applied to the preparation of oxygen-containing compounds, chemical instruments and methods, and the preparation of carbonyl compounds by oxidation, etc. It can solve the problems of unsatisfactory selectivity, difficulties in separation and purification, and conversion of α-pinene The problem of low conversion rate and other problems, to achieve the effect of high selectivity and high conversion rate

Inactive Publication Date: 2010-10-20
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Abstract
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AI Technical Summary

Problems solved by technology

[0006] Above-mentioned method, generally speaking, the conversion rate of α-pinene conversion rate is not high, and total selectivity is also unsatisfactory, and what obtain mostly is the mixture of verbenone and verbenol
This brings certain difficulties to separation and purification, especially in the preparation of optically pure verbenone and verbenol

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Example 1 Synthesis of (-)-verbelenone

[0025] Dissolve 25g or 184mmol of (-)-α-pinene in a mixture of 500mL of acetone and 80mL of water, under stirring, add 18.4g or 184mmol of CrO 3 , 25 ℃ reaction for 10 hours. After filtration, the acetone was evaporated, and the resulting mixture was dissolved in CH 2 Cl 2 , this organic phase was separately washed with saturated NaCO 3 , washed with NaCl aqueous solution and then washed with anhydrous Na 2 SO 4 Dry, filter and evaporate the solvent, and the obtained crude product is subjected to column chromatography, eluted with ethyl acetate: petroleum ether=1:5, to obtain 157 g of (-)-verbelenone as a light yellow liquid with a yield of 57%. 1 HNMR (300MHz, CDCl 3 ): δ=1.01[s, 3H, C(6)-CH 3 ], 1.50[s, 3H, C(6)-CH 3 ], 2.01[s, 3H, C(4)-CH 3 ], 2.06[d, 1H, 3 J H，H =9.6Hz, C(7)-H], 2.42[1H, C(7)-H], 2.64[1H, C(1)-H], 2.81[1H, C(5)-H], 5.71[ 1H, C(3)-H].

Embodiment 2

[0026] Example 2 Synthesis of (+)-verbelenone

[0027] Dissolve 15.6g (+)-α-pinene 114mmol in a mixture of 300mL acetone and 48mL water, add CrO under stirring 3 11.4 g (114 mmol) were reacted at 25°C for 10 hours. The acetone was filtered and evaporated, and the resulting mixture was dissolved in CH 2 Cl 2 , and used saturated NaCO 3 , washed with NaCl aqueous solution, washed with anhydrous Na 2 SO 4 Dry; filter and evaporate the solvent, the crude product obtained is subjected to column chromatography, eluted with ethyl acetate: petroleum ether=1:5, to obtain 9 g of (+)-verbelenone as a pale yellow liquid with a yield of 60%. 1 H NMR (300MHz, CDCl 3 ): δ=0.95[s, 3H, C(6)-CH 3 ], 1.44[s, 3H, C(6)-CH 3 ], 1.96[3H,C(4)-CH 3 ], 2.02[d, 1H, 3 JH, H=9.1Hz, C(7)-H], 237[1H, C(7)-H], 2.58[1H, C(1)-H], 2.75[1H, C(5)-H] , 5.67[1H, C(3)-H]. 13 C NMR (75MHz, CDCl 3 ): δ=21.9, 23.4, 26.4, 40.7, 49.5, 539, 57.4, 121.0, 170.0, 203.8.

Embodiment 3

[0028] Example 3 Synthesis of (-)-cis verbenol

[0029] At -20 °C, to a stirred mixture containing 0.56 g, or 1.5 mmol NaBH 4 22g, namely 1.5mmol (-)-verbelenone, was added dropwise to the mixed solution of propanol and water with a volume ratio of 5:12 in 60mL, and after the reaction was monitored by thin layer chromatography (TLC), excess NaBH 4 Neutralize with 6% hydrochloric acid solution. The reaction mixture was diluted with water and extracted three times with 10 mL of ether. The organic phases were combined, and the organic phases were washed with saturated aqueous NaCl solution and anhydrous MgSO. 4 Dry, filter, and evaporate the solvent to obtain a light yellow solid. The crude product is recrystallized from n-hexane to obtain 1.97 g of (-)-cis-verbeenol as a white crystal, with a yield of 89%. 1 H NMR (300MHz, CDCl 3 ): δ=1.08[s, 3H, C(6)-CH 3 ], 1.29[1H,C(7)-H], 1.35[3H,C(6)-CH 3 ], 1.61[1H, CHO H ], 1.73[3H,C(4)-CH 3 ], 1.97[1H, C(1)-H], 2.29[1H, C(5)-H], 2...

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Abstract

The invention provides a synthesis method of an oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol, which is a synthesis method of the verbena ketene and the verbenol with high conversion rate, wherein the conversion rate of the alpha-pinene is nearly 100 percent; the yield of (-) -verbena ketene is 57 percent, the yield of (+)-verbena ketene is 60 percent, the yield of (-)-cis verbenol is 89 percent, the yield of (+)-cis verbenol is 79 percent, the yield of (-) -trans verbenol is 51 percent, and the yield of (+)-trans verbenol is 49 percent. The obtained products oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol can be used for preventing pinaceae plant pests.

Description

technical field [0001] The invention belongs to a method for synthesizing oxygen-containing derivatives of α-pinene, and relates to a method for synthesizing the oxygen-containing derivatives of α-pinene, the beetle pheromone verbenone and verbenol. Background technique [0002] Tomicus piniperda L is the main pest of pinaceae and one of the common forest pests in the world. In foreign countries, the insect mainly harms the European red pine Pinus sylverstris, the coastal pine P.pinaster, the European black pine P.nigra and the red pine P.densiflora and other pine trees. In China, P. yunnanensis, P. massolangbianensis and P. densata are mainly harmful to P. yunnanensis. At the end of the 1970s, the vertical pit cut-tip beetle occurred on a large scale in Yunnan, resulting in the death of a large area of ​​Yunnan pine. In recent years, the pest has been seriously harmful in Northeast my country, causing huge losses to forestry production and ecological environment construct...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/627C07C45/28C07C35/28C07C29/143C07C27/02A01P7/04
Inventor 刘志强段海峰林英杰宋凤瑞郑重
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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