Synthesis of (5Z,7E)-dodecane-5,7-diene-1-alcohol as well as acetate and propionate thereof

A technology of ethyl dienoate and dodecane, applied in the field of insect pheromone synthesis, can solve problems such as harsh reaction conditions and lengthy steps

Active Publication Date: 2019-03-12
CHINA AGRI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] Although there have been some reports in the literature on the synthesis of (5Z,7E)-dodeca-5,7-dien-1-ol and its

Method used

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  • Synthesis of (5Z,7E)-dodecane-5,7-diene-1-alcohol as well as acetate and propionate thereof
  • Synthesis of (5Z,7E)-dodecane-5,7-diene-1-alcohol as well as acetate and propionate thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0027] Synthesis of 2-heptyn-1-ol (3)

[0028] Under the protection of argon, propynyl alcohol (20mmol, 1.12g) was dissolved in dry tetrahydrofuran (20mL), and HMPA (60mmol, 10.75g) was added at room temperature, and stirred evenly. Then the temperature of the mixture was lowered to -78°C, and n-butyllithium (40mmol, 2.4M in n-hexane, 16.7mL) was slowly added dropwise. After the dropwise addition was completed, the temperature was slowly raised to -30°C, and the reaction was stirred for 1 h, then n-bromobutane (10 mmol, 1.37 g) was added, the temperature of the reaction mixture was raised to room temperature, and the reaction was stirred for 9 h. After the reaction is complete, use saturated NH 4 The reaction was quenched with aqueous Cl solution, the layers were separated, the aqueous phase was extracted with diethyl ether (3×20 mL), and the organic phases were combined. Anhydrous Na for organic phase 2 SO 4 Drying and concentration under reduced pressure gave the crude p...

Embodiment 2

[0030] Synthesis of (E)-2-hepten-1-ol (4)

[0031] Under the protection of argon, weigh lithium aluminum tetrahydrogen (2mmol, 76mg) into the Shrek bottle, lower the temperature of the system to 0°C, and slowly add (E)-2-hepten-1-ol (4) (1mmol , 114mg) in THF (4mL). The reaction was stirred at 0° C. for 1 h, then the temperature was naturally raised to room temperature, and the stirring reaction was continued for 9 h. After the reaction was completed, methanol and ammonium chloride were added to quench the reaction at 0°C. Suction filtration, the solid was washed with ether, the filtrate was extracted with ether (3×10 mL), the layers were separated, and the organic phases were combined. Anhydrous Na for organic phase 2 SO 4 Drying, concentration under reduced pressure, and finally purification by silica gel column chromatography (petroleum ether / ethyl acetate 5:1) gave (E)-2-hepten-1-ol (4) (91.8mg, yield 82%), as colorless liquid. 1 H NMR (300MHz, CDCl 3 )δ5.70-5.53(m,...

Embodiment 3

[0033] Synthesis of (5Z,7E)-dodeca-5,7-dienoic acid ethyl ester (5)

[0034] Under the protection of argon, 4A molecular sieve (0.2g) and PDC oxidant (1.3mmol, 489mg) were added into the Shrek bottle, and (E)-2-hepten-1-ol (4) (1mmol, 114mg) was added dropwise Dichloromethane (5 mL) solution was stirred at room temperature for 9 h. After the completion of the reaction, filter with suction, wash the solid with dichloromethane, wash the filtrate with saturated aqueous sodium chloride (5 mL), separate the layers, and combine the organic phases. Anhydrous Na for organic phase 2 SO 4 Dry and concentrate under reduced pressure to obtain the crude product of (E)-2-heptenal as a pale yellow liquid.

[0035] Under the protection of argon, weigh (5-ethoxy-5-oxopentyl)triphenylphosphine bromide (2 mmol, 940 mg) into a Shrek bottle, add THF (5 mL), and stir well. The temperature of the mixture was lowered to -78°C, sodium bistrimethyldisilazide (1.8mmol, 2M in THF, 0.9mL) was added sl...

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Abstract

The invention belongs to the technical field of insect pheromone synthesis, and discloses a new method for synthesizing (5Z,7E)-dodecane-5,7-diene-1-alcohol as well as acetate and propionate thereof.The method takes propynol as an initial raw material to be subjected to coupling with 1-bromobutane to generate 2-heptyne-1-alcohol, triple bond is reduced to be E-type double bond through LiAlH4, 2-heptyne-1-alcohol is oxidized to be olefine aldehyde through PDC, olefine aldehyde reacts with a Wittig reagent (5-ethyoxyl-5-oxopentyl)triphenyl phosphonium bromide to produce (5Z,7E)-dodecane-5,7-dienoic acid ethyl ester which is reduced by LiAlH4 to obtain (5Z,7E)-dodecane-5,7-diene-1-alcohol, (5Z,7E)-dodecane-5,7-diene-1-alcohol reacts with acetyl chloride and propionyl chloride finally to obtain (5Z,7E)-dodecane-5,7-diene-1-alcohol acetate and (5Z,7E)-dodecane-5,7-diene-1-alcohol propionate. The method utilizes LiAlH4 to reduce the triple bond to be the E-type double bond, and utilizes theWittig reaction of the Wittig reagent with the tail end provided with ester group and aldehyde to directly build the Z-type double bond, the synthesis route is simple, convenient and efficient, and the reaction condition is moderate and environmentally friendly.

Description

technical field [0001] The invention belongs to the technical field of insect pheromone synthesis, and in particular relates to a new method for synthesizing (5Z,7E)-dodeca-5,7-dien-1-ol and its acetate and propionate. Background technique [0002] (5Z,7E)-Dodeca-5,7-dien-1-ol and its acetate and propionate (Formula 1) are the active components of the sex pheromone of Dendrolimus punctatus (Walker) (Science Bulletin 1979, 1004-1008. Zhao Chenghua; Li Qun; Guo Xingyu; Wang Xuying Acta Entomology 1993, 247-250.), is also the active ingredient of the sex pheromone of the red pine caterpillar Dendrolimus spectabilis Butler (Lepidoptera: Lasiocampidae) (Ando, ​​T.; Vu, M.H.; Yoshida, S.; Takahashi, N.; Tatsuki, S.; Katagiri, K.; Yamane, A.; , H.; Ando, ​​T.; Takahashi, N.; Tatsuki, S.; Yamane, A.; Ikeda, T.; Yamazaki, S.Agric.Biol.Chem.1980,44,231-233. Sun Yongping; Feng Shiqiang; Wu Haishan Entomology Acta 2003,131-137.), or the active ingredient of the sex pheromone of Dendro...

Claims

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Application Information

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IPC IPC(8): C07C67/08C07C69/24C07C69/145
CPCC07C29/17C07C29/58C07C67/08C07C33/042C07C33/03C07C69/145C07C69/24
Inventor 钟江春马思捷边庆花王敏刘飞鹏孙效杨森
Owner CHINA AGRI UNIV
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