Preparation method of (8E, 10E)-8, 10-dodecadienol-1-alcohol

A technology of dodecadiene and 10- is applied in the field of preparation of (8E,10E)-8,10-dodecadien-1-ol, and can solve the problem of poor purity of chlorohexyloxytrimethylsilane. High, easy to produce impurities, low success rate and other problems, to achieve the effect of improving the success rate of triggering, avoiding the generation of impurities, and reducing the generation of impurities

Active Publication Date: 2012-10-10
常州胜杰生命科技股份有限公司
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AI Technical Summary

Problems solved by technology

[0004] The disadvantages of this method are: (1) The temperature of the hydroxyl protection reaction in step ① is 25°C to 35°C, which is easy to produce impurities, and finally leads to the low purity of the product chlorohexyloxytrimethylsilane (only 96%)
In addition, due to the hydrolysis reaction of trimethylchlorosilane in sodium carbonate solution, part of trimethylchlorosilane cannot react with chlorohexanol, resulting in low yield of this step (according to the embodiment with the largest yield 1 calculation, the actual yield is only 88%)
(2) The Grignard reaction in step ② uses iodine as the initiator, and directly uses chlorohexyloxytrimethylsilane to react and add it at one time. Since the Grignard reaction is very violent, this reaction method leads to the success of the Grignard reaction. Very small rate
In terms of reaction kinetics, this feeding method will make the catalytic ability very strong, which will lead to the formation of more impurities
In addition, higher dropping temperature and higher catalyst concentration (above 0.2mol / L) also easily lead to the formation of more impurities
The generated impurities are difficult to remove, so the purity of the product of the coupling reaction is not high, which in turn affects the purity of the final product (8E,10E)-8,10-dodecadien-1-ol

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1）

[0012] The preparation method of (8E,10E)-8,10-dodecadien-1-ol of the present embodiment has the following steps:

[0013] ① Under nitrogen protection, add 340 g of 6-chlorohexanol (2.49 mol), 300 g of triethylamine (2.97 mol) and 900 mL of methyl tert-butyl ether into a 1.5 L four-necked flask. The temperature was lowered to 2 °C with an ice bath, and 300 g of trimethylchlorosilane (2.76 mol) was added dropwise, and the dropwise temperature was controlled at 2 °C. After dripping, the stirring reaction was continued at a temperature of 2 °C until the content of 6-chlorohexanol in GC analysis was less than or equal to 1 wt%.

[0014] After the reaction, 400 mL of water was added to the four-necked flask, stirred for 5 min, and the phases were separated. The aqueous phase was extracted with methyl tert-butyl ether (1×100 mL), the organic phases were combined, and the solvent was evaporated under reduced pressure. And collect the fraction of (60~70) ℃ / 4mmHg, obtain 489g of chlor...

Embodiment 2～ Embodiment 4）

[0027] Each embodiment is basically the same as embodiment 1, and the differences are shown in Table 1 to Table 4.

[0028] Example 1 Example 2 Example 3 Example 4 Four-necked flask 1.5L 1.5L 1.5L 1.5L 6-Chlorohexanol 340g (2.49mol) 340g (2.49mol) 340g (2.49mol) 410g (3.0mol) Trimethylchlorosilane 300g (2.76mol) 300g (2.76mol) 300g (2.76mol) 358g (3.3mol) triethylamine 300g (2.97mol) 300g (2.97mol) 300g (2.97mol) 353g (3.5mol) Methyl tert-butyl ether 900mL 900mL 900mL 1L Dropping temperature and reaction temperature 2℃ 5℃ 0℃ 2℃ Product A weight 491g 489g 488g 589g Product A Purity 99.5% 99.3% 99.2% 99.3% yield 94.1% 93.5% 93.2% 93.5%

[0029] Note: Table 1 is the reaction conditions and results of step ① of the present invention, wherein product A is chlorohexyloxytrimethylsilane.

[0030] Example 1 Example 2 Example 3 Example 4 product A ...

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Abstract

The invention discloses a preparation method of (8E, 10E)-8, 10-dodecadienol-1-alcohol. The method comprises the steps of: reacting 6-chlorohexanol with trimethylchlorosilane in the presence of methyl tertiary butyl ether and triethylamine at 0 to 5 DEG C to obtain chloride trimethylethoxysilane; then performing the Grignard reaction on the chloride trimethylethoxysilane to obtain a Grignard agent; and reacting (2E, 4E)-2, 4-hexadiene-1-dryocrassyl acetate with the Grignard agent to obtain (8E, 10E)-8, 10-dodecadienol-1-triethoxysilane; and finally hydrolyzing the (8E, 10E)-8, 10-dodecadienol-1-triethoxysilane to obtain (8E, 10E)-8, 10-dodecadienol-1-alcohol. According to the preparation method, both the purity and the yield of hydroxy-protecting reaction product are relatively high; and the initiating success rate of the Grignard reaction is relatively high, the purity of the coupling reaction product is high.

Description

technical field [0001] The present invention relates to a preparation method of sex pheromone, in particular to a preparation method of (8E,10E)-8,10-dodecadien-1-ol. Background technique [0002] (8E,10E)-8,10-dodecadien-1-ol is the chemical name for the codling moth sex pheromone. [0003] Chinese patent document CN101440020A discloses a preparation method of (8E,10E)-8,10-dodecadien-1-ol, the method has the following steps: 1. Mix chlorohexanol and trimethylchlorosilane in alkali; The reaction time is 3h~9h, the reaction temperature is 25℃~35℃, and then post-treatment is carried out to obtain chlorohexyloxytrimethylsilane; ②The post-treated chlorohexyloxytrimethylsilane obtained in step ① Methylsilane obtains Grignard reagent through Grignard reaction; ③ in Li 2 CuCl 4 In the presence of a catalyst, (2E,4E)-2,4-hexadien-1-ol acetate is coupled with the Grignard reagent obtained in step ②, and the temperature of the catalytic reaction is controlled by ice brine to -15°C...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C33/02C07C29/09
Inventor 苏衡王加高李海燕申传伟
Owner 常州胜杰生命科技股份有限公司
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