CN111116360A - Method for synthesizing sex pheromone of peach-strip wheat moth - Google Patents
Method for synthesizing sex pheromone of peach-strip wheat moth Download PDFInfo
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Abstract
The invention belongs to the technical field of synthesis of green pesticides, and discloses a novel method for synthesizing sex pheromone of peach-streak wheat moth. The method comprises the steps of taking 5-hexyne-1-alcohol as a raw material, carrying out nucleophilic substitution reaction with 1-bromobutane in the presence of n-butyllithium and HMPA to generate 5-decyne-1-alcohol, then reducing the 5-decyne-1-alcohol by lithium aluminum hydride to obtain (E) -5-decyne-1-alcohol, and finally carrying out acetylation reaction to obtain (E) -5-decyne-1-alcohol acetate. The invention utilizes lithium aluminum hydride to reduce triple bonds of alkyne into E-type double bonds, and has the advantages of simple synthetic route, mild reaction condition, good environmental compatibility and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis of green pesticides, and particularly relates to a novel method for synthesizing sex pheromone of peach-streak wheat moth.
Background
The peach-stripe wheat moth (Anarsia linetella Zeller) is distributed in east and middle parts of asia, middle and south parts of europe, north america, and the like. Mainly harms various fruit trees such as peaches, apricots, apples, pears, persimmons, narrow-leaved oleaster, plums and the like (Baijiuwei; Zhao Jianxia; Maranglian forestry science 1980, 127-. Sex pheromones of the peach-stripe wheat moth have biological activity of attracting male moths (Roelofs, w.; Kochansky, j.; antton, e.; Rice, r.; carre, r. environ. entomol.1975,4, 580-one 582.), can be used for population monitoring of peach-stripe wheat moths (Hart, m.; Takacs, s.; Gries, g. wo2007053926a1), trapping and interfering mating, and the like (Becker, r.; bushmann, e.; Mackenroth, w.; Schuermann, g.; Seufert, w.; Seppelt, w.; Krieg, w.; neutann 033n, u.ep 0160a1). The sex pheromone of the peach fruit moth has the advantages of high biological activity, low using amount, no harm to natural enemies and the like, and has an important function in green prevention and control of the peach fruit moth.
The sex pheromone of the peach strips and wheat moths is firstly separated by Carde and the like, and is identified to be (E) -5-decen-1-alcohol acetate as a main component and (E) -5-decen-1-alcohol (formula 1) as a secondary component (Roelofs, W.; Kochansky, J.; Anthon, E.; Rice, R.; Carde, R.environ.Entomol.1975,4, 580-Bull.). although the sex pheromone of the peach strips and wheat moths has the advantages of high biological activity, no harm to natural enemies and the like, the content of the sex pheromone of the peach strips and wheat moths is extremely low in female insects, the sex pheromone of the peach strips and wheat moths is difficult to extract, and the application research of the sex pheromone of the peach strips and wheat moths in pest control is seriously hindered.
(1) α, the omega-bifunctional raw material method is to take α omega-bifunctional compound 2, 3-dichloro hexahydropyran as a starting material, generate E-type enol through Kumada coupling and alkaline ring opening elimination, and generate (E) -5-decene-1-alcohol acetate through multiple reactions such as oxidation, Wittig reaction, hydroboration redox, acetylation and the like (Bestmann, H.J.; Koschatzky, K.H.; Schaetzke, W.; Suess, J.; Vorowsky, O.Liebigs ann.chem.1981, 1705-1720.).
(2) The acetylene coupling method is characterized in that under the catalysis of metal palladium and in the presence of lithium bromide, acrolein and acetylene are coupled to obtain (E) -5-bromo-4-pentenal, and then Kumada coupling, Wittig reaction, acetylation and other multi-step reactions are carried out to obtain (E) -5-decene-1-alcohol acetate (Huangfei; Yanwangqiu; Zhangshun; Yao 36191; Tayun organic chemistry 2017,37, 1046-.
(3) The triple bond reduction method uses 1-hexyne as a raw material, firstly reacts with 1-dimethyl tert-butylsiloxy-3-iodopropane to generate alkynyl silyl ether, and then is reduced by using sodium metal/liquid ammonia to obtain (E) -5-decene-1-alcohol (Poleschner, H.; Heydereich, M.; Martin, D.Synthesis 1991, 1231-Si-1235.).
(4) The iodohydrocarbon elimination method is characterized in that 1-hexene is used as a starting material and reacts with chloroiodomethane to generate 1-chloro-3-iodoheptane, then the 1-chloro-3-iodoheptane reacts with dimethyl malonate to obtain iodomalonic acid derivatives, the iodomalonic acid derivatives are subjected to elimination reaction to obtain E-type alkenyl substituted malonic acid, and finally the iodomalonic acid derivatives are heated to decarboxylate and are reduced by lithium aluminum hydride to obtain (E) -5-decene-1-ol. (Miyano, S.; Hokari, H.; Umeda, Y.; Hashimoto, H.Bull.Chem.Soc.Jpn.1980,53,770-774.)
Although the synthesis research of sex pheromone of the peach-streak wheat moth achieves certain results, the problems of harsh reaction conditions, long reaction route, high reagent toxicity and the like still exist. Therefore, the research on the novel method for synthesizing the sex pheromone of the peach-strip wheat moth, which has mild reaction conditions and good environmental compatibility, has important theoretical significance and application value.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing sex pheromone of peach strips and wheat moths. The method comprises the steps of taking 5-hexyne-1-alcohol 1 as a raw material, carrying out nucleophilic substitution reaction with 1-bromobutane 2 in the presence of n-butyllithium and HMPA to generate alkynol 3, then reducing the alkynol by lithium aluminum hydride to obtain (E) -5-decene-1-alcohol, and finally carrying out acetylation reaction to obtain (E) -5-decene-1-alcohol acetate. The synthesis route of the sex pheromone of the peach-strip wheat moth is shown in a formula 2.
The method for synthesizing the sex pheromone of the peach strip wheat moth comprises the following steps.
(1) Synthesis of 5-decyn-1-ol 3
Under the protection of argon, the tetrahydrofuran solution of 5-hexyne-1-ol 1 and HMPA is cooled to-78 ℃, and n-butyl lithium is dropwise added. Heating to-30 ℃, and stirring for reaction for 1 h. Then 1-bromobutane 2 is added dropwise, and the temperature is raised to room temperature and the reaction is stirred for 10 hours. After the reaction was completed, the reaction was quenched with a saturated aqueous ammonium chloride solution. Separating, extracting the water phase with diethyl ether, combining the organic phases, washing with saturated sodium chloride aqueous solution, drying, concentrating under reduced pressure, and purifying by silica gel column chromatography to obtain alkynol 3.
(2) Synthesis of (E) -5-decen-1-ol
Under the protection of argon, the mixture of lithium aluminum hydride, alkynol 3 and diethylene glycol dimethyl ether is heated to reflux reaction for 14 hours. After the reaction was completed, the reaction was quenched with an aqueous sodium hydroxide solution. Filtering with diatomite, washing the filter cake with diethyl ether, washing the filtrate with water and saturated sodium chloride solution, drying, and concentrating under reduced pressure to obtain (E) -5-decene-1-alcohol.
(3) Synthesis of (E) -5-decen-1-ol acetate
Under the protection of argon, acetic anhydride is dripped into the mixed solution of (E) -5-decene-1-alcohol, dichloromethane and triethylamine, the temperature is raised to the room temperature, and the reaction is carried out for 8 hours. After the reaction was completed, water was added to quench, the mixture was separated, the aqueous phase was extracted with dichloromethane, and the organic phases were combined. Washing with water and saturated aqueous solution of sodium chloride, drying, concentrating under reduced pressure, and purifying by silica gel column chromatography to obtain (E) -5-decene-1-alcohol acetate.
Detailed Description
Examples 1
Synthesis of 5-decyne-1-ol 2
5-hexyn-1-ol 1(0.20g,2mmol), HMPA (1mL, 6mmol) and tetrahydrofuran (10mL) were added sequentially under argon protection to a 50mL Schlenk tube and stirred well. The mixture was allowed to warm to-78 deg.C and n-butyllithium (1.7mL,2.4M,4mmol) was slowly added dropwise. After the dripping is finished, slowly heating the mixed solution to-30 ℃, and stirring for reacting for 1 h. Then slowly dropwise adding1-bromobutane 2(0.27g,2mmol) was added dropwise, the reaction mixture was slowly warmed to room temperature and stirred for 10 h. After the reaction was completed, the reaction was quenched by dropwise addition of saturated aqueous ammonium chloride (10mL) under cooling in an ice bath. The layers were separated, the aqueous layer was extracted with ether (3X 10mL), and the organic layers were combined. The organic phase was washed with water (20mL) and saturated aqueous sodium chloride (20mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the crude product. The crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate 5:1) to give alkynol 3(0.15g, 48% yield) as a pale yellow liquid compound.1H NMR(300MHz,CDCl3)δ3.67(t,J＝6.2Hz,2H),2.22–2.11(m,4H),1.68–1.43(m,9H),0.90(t,J＝7.2Hz,3H).13C NMR(75MHz,CDCl3)δ80.54,79.64,62.27,31.75,31.14,25.31,21.83,18.44,18.31,13.48.
EXAMPLES example 2
(E) Synthesis of (E) -5-decen-1-ol
Under the protection of argon, lithium aluminum hydride (1.48g,38.88mmol), diethylene glycol dimethyl ether (40mL) and alkynol 3(0.93g,6.48mmol) were added to a 100mL three-necked reaction flask equipped with a reflux condenser, the reaction mixture was heated to reflux, and the reaction was continued for 14h with stirring. After the reaction was completed, the reaction mixture was cooled to room temperature. The reaction was quenched by dropping aqueous sodium hydroxide (5mL) under ice-bath cooling. The reaction mixture was filtered with suction through celite, and the filter cake was washed with diethyl ether (500 mL). The filtrate was washed with water (3X 100mL) and saturated aqueous sodium chloride (2X 100mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the compound (E) -5-decen-1-ol (0.94g, 93% yield) as a pale yellow liquid.1H NMR(300MHz,CDCl3)δ5.42–5.38(m,2H),3.64(t,J＝6.5Hz,2H),2.05–1.97(m,4H),1.63–1.52(m,2H),1.34–1.26(m,7H),0.93–0.89(t,J＝6.9Hz,3H).13C NMR(75MHz,CDCl3)δ130.80,129.75,62.79,32.23,32.19,31.75,25.69,22.14,13.87.
EXAMPLE 3
(E) Synthesis of (E) -5-decen-1-ol acetate
Under argon protection, (E) -5-decen-1-ol (0.90g,5.75mmol), dichloromethane (15mL) and triethylamine (3.49g,34.5mmol) were added to a 50mL Schlenk tube, and acetic anhydride (1.76g,17.25 mmol) was slowly added dropwise with cooling on an ice bath). The reaction solution is heated to room temperature and stirred for reaction for 8 hours. After the reaction was complete, the reaction was quenched by addition of water (10 mL). The layers were separated, the aqueous layer was extracted with dichloromethane (3X 15mL), and the organic layers were combined. The organic phase was washed with water (3X 20mL) and saturated aqueous sodium chloride (30mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the crude product. The crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate 80:1) to give the compound (E) -5-decen-1-ol acetate (0.97g, 85% yield) as a pale yellow liquid.1H NMR(300MHz,CDCl3)δ5.42–5.36(m,2H),4.05(t,J＝6.7Hz,2H),2.04–1.95(m,7H),1.63–1.60(m,2H),1.41–1.29(m,6H),0.89(t,J＝6.9Hz,3H).13C NMR(75MHz,CDCl3)δ170.98,130.96,129.41,64.37,32.15,32.02,31.68,27.98,25.80,22.09,20.83,13.82.
Claims (5)
1. A method for synthesizing sex pheromone of peach streak wheat moth is characterized by comprising the following steps: taking 5-hexyne-1-alcohol as a raw material, carrying out nucleophilic substitution reaction with 1-bromobutane in the presence of n-butyllithium and HMPA to generate 5-decyne-1-alcohol, then reducing the 5-decyne-1-alcohol by lithium aluminum hydride to obtain (E) -5-decyne-1-alcohol, and finally carrying out acetylation reaction to obtain (E) -5-decyne-1-alcohol acetate.
2. The method for synthesizing grapholitha molesta sex pheromone according to claim 1, wherein the method for synthesizing (E) -5-decen-1-ol comprises the following steps: under the protection of argon, heating a mixture of lithium aluminum hydride, 5-decyne-1-alcohol and diethylene glycol dimethyl ether to reflux reaction; after the reaction is finished, quenching the reaction by using a sodium hydroxide aqueous solution; filtering with diatomite, washing the filter cake with diethyl ether, washing the filtrate with water and saturated sodium chloride solution, drying, and concentrating under reduced pressure to obtain (E) -5-decene-1-alcohol.
3. The synthesis according to claim 2, characterized in that the reaction solvent used for the synthesis of (E) -5-decen-1-ol is tetrahydrofuran, dichloromethane, diethylene glycol dimethyl ether and hexahydropyran, preferably diethylene glycol dimethyl ether.
4. The synthesis process according to claim 2, characterized in that the reaction temperature for the synthesis of (E) -5-decen-1-ol ranges from 25 to 160 ℃, preferably 160 ℃.
5. The synthesis process according to claim 2, characterized in that the molar equivalent ratio of lithium aluminum hydride to 5-decyn-1-ol in the reaction for the synthesis of (E) -5-decen-1-ol is from 1:3 to 1:8, preferably 1: 6.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093166A (en) * | 2010-11-18 | 2011-06-15 | 中国农业大学 | Method for synthesizing marine natural product by using high optical activity enantiomer |
| CN106431831A (en) * | 2016-09-18 | 2017-02-22 | 昆明博鸿生物科技有限公司 | Synthesizing method for 5E-decene-1-alcohol and acetic acid 5E-decenoate |
| CN109020937A (en) * | 2018-08-20 | 2018-12-18 | 中国农业大学 | The synthetic method of one kind (E) -7- dodecylene -1- alcohol acetic ester |
| CN109456182A (en) * | 2018-11-16 | 2019-03-12 | 中国农业大学 | The synthesis of (5Z, 7E)-ten two carbon -5,7- diene -1- alcohol and its acetic acid esters and propionic ester |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093166A (en) * | 2010-11-18 | 2011-06-15 | 中国农业大学 | Method for synthesizing marine natural product by using high optical activity enantiomer |
| CN106431831A (en) * | 2016-09-18 | 2017-02-22 | 昆明博鸿生物科技有限公司 | Synthesizing method for 5E-decene-1-alcohol and acetic acid 5E-decenoate |
| CN109020937A (en) * | 2018-08-20 | 2018-12-18 | 中国农业大学 | The synthetic method of one kind (E) -7- dodecylene -1- alcohol acetic ester |
| CN109456182A (en) * | 2018-11-16 | 2019-03-12 | 中国农业大学 | The synthesis of (5Z, 7E)-ten two carbon -5,7- diene -1- alcohol and its acetic acid esters and propionic ester |
Non-Patent Citations (1)
| Title |
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| PALAKODETY R. K., ET AL.: "First Stereoselective Total Synthesis of Gallicynoic Acids G and H", 《HELVETICA CHIMICA ACTA》 * |
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Application publication date: 20200508 |