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Method for synthesizing high antimer pure pine needle bee sex pharomone (2S, 3S, 7S)-3,7-dimethyl-2-pentadeca alcohol ester

An enantiomer, dimethyl technology, applied in the synthesis of high-enantiomer pure pine sawfly sex pheromone (2S, which can solve the problem of low activity and achieve short steps, good application prospects, and high enantiomeric purity Effect

Inactive Publication Date: 2004-01-28
XIAMEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] In addition, many other research groups have reported the synthesis of 3,7-dimethyl-2-pentadecanol and its carboxylate, but many are racemates, or other less active isomers

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Step 1 Synthesis of (S)-dimethyl malate 2a

[0033] Add 200 mL of methanol to a single-necked bottle containing (S)-malic acid 1 (12.0 g, 89.6 mmol). Thionyl chloride (14mL, 197mmol) was added dropwise in an ice bath, then raised to room temperature and reacted for 15h, the solvent was concentrated and drained, 50mL of dichloromethane was added in an ice bath, neutralized with 11mL of saturated sodium bicarbonate solution, and separated The organic phase was taken out, the aqueous phase was extracted with dichloromethane (3×10mL), the combined organic phase was washed with 5mL saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure and then flash column chromatography (ethyl acetate: Petroleum ether = 1:1) to obtain compound 2a, 13.4 g, a colorless liquid, with a yield of 93%.

[0034] Step 2 Synthesis of (S)-2-dimethyl 2-toluenesulfonyloxymalate 3a

[0035] Under a nitrogen atmosphere, in an ice bath, the compound 2a (9.6g,...

Embodiment 2

[0064] Step 1 According to the method of Example 1, compound 2a was prepared from compound 1.

[0065] Step 2 Prepare compound 3a from compound 2a according to Example 1, using triethylamine as the base, and the rest of the operations are the same, with a yield of 88%.

[0066] Step 3 Compound 4 was prepared from compound 3a according to Example 1, using diethyl ether as a solvent, and the rest of the operations were the same, with a yield of 41%.

[0067]Step 4 To a solution of compound 4 (136mg, 1.5mmol), triethylamine (0.42mL, 3.0mmol) and a catalytic amount of DMAP in anhydrous dichloromethane (1.5mL), add tert-butyl dichloromethane dropwise under ice-cooling. Methylchlorosilane (271mg, 1.2mmol) in dichloromethane (1.5mL) was reacted for 24h, then 5mL of saturated sodium bicarbonate solution was added, extracted with ether (3×5mL), and the combined organic phases were washed with 0.5mL of saturated brine Washed, dried with anhydrous sodium sulfate, filtered, concentrated ...

Embodiment 3

[0080] Step 1 Add 90 mL of ethanol to a single-necked bottle containing (S)-malic acid 1 (4.81 g, 35.8 mmol). Add thionyl chloride (5.7mL, 78.7mmol) dropwise under ice-bath, rise to room temperature and react for 14h, concentrate and drain the solvent, add 25mL of dichloromethane in ice-bath, and neutralize with 11mL saturated sodium bicarbonate solution , separate the organic phase, extract the aqueous phase with dichloromethane (3 × 10mL), wash the combined organic phase with 5mL saturated brine, dry with anhydrous sodium sulfate, filter, concentrate under reduced pressure and flash column chromatography (ethyl acetate Ester: petroleum ether = 1:1) to obtain compound (S)-diethyl malate 2b, 6.53 g, a colorless liquid, with a yield of 96%.

[0081] Step 2 Under a nitrogen atmosphere, in an ice bath, dissolve (S)-diethyl malate 2b (5.18g, 27.2mmol) in 50mL of dry dichloromethane, add pyridine (3.3mL, 40.8mmol) and catalyze DMAP was measured and a solution of p-toluenesulfonyl ...

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Abstract

The method for synthesizing high-antimer pure pine sawfly sex pheromone (2S, 3S, 7S)-3,7-dimethyl-2- pentadecyl alcohol ester is characterized by that it uses cheap easily-evailable natural (S)-malicacid with high-antimer purity as raw material, and can high-stereoselectively synthesize a series of important intermediate compounds of (S)-1,3- butanediol 4, (2S, 3S-2-methyl-1,3-butanediol 12, (S)-3-methyl-hendecyl alcohol 8 and (2S,3S,7S)-3,7- dimethyl-2-pentadecyl alcohol 15 of the pine sawfly sex pheromone, then makes the (2S,3S,7S)-3,7- dimethyl-2-pentadecyl alcohol 15 undergo the process of acrylation reaction to obtain the pine sawfly sex pheromone (2S,3S,7S)-3,7-dimethyl-2-pentadecyl alcohol carboxylic ester 16 and 17 with high antimer purity.

Description

(1) Technical field [0001] The present invention relates to an optically active high-enantiomer pure pine sawfly sex pheromone (2S, 3S, 7S)-3,7-dimethyl-2-pentadecanol acetate and propionate and its important The synthetic method of intermediate chiral diol. (2) Background technology [0002] Insect pheromones are the main way of information exchange, population identification, sex attraction or offensive defense among insects. The use of insect sex pheromones to control pests has the advantages of being economical and effective, not polluting the environment, protecting natural enemies, convenient and safe to use, and having no resistance. . However, the amount of semiochemical substances secreted by insects is very low. Thousands or even millions of insects are needed to obtain insect sex pheromones in milligram quantities. Therefore, in order to obtain sufficient amounts of sex pheromones for necessary biological research and successful pest control, it is necessary to...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/00C07C31/18C07C31/20C07C67/08C07C69/675
Inventor 黄培强蓝洪桥郑啸
Owner XIAMEN UNIV
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