CN101434521A - Method for synthesizing compound E10, E12-hexadecadienal in sex pheromone of legume pod borer - Google Patents
Method for synthesizing compound E10, E12-hexadecadienal in sex pheromone of legume pod borer Download PDFInfo
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Abstract
A synthetic method of compound E10, E12-hiago dienal in maruca testulalis geyer sex pheromone is characterized in that the compound adopts trans-2-hexenol and 1, 10-decanediol as the substrate; after halogenating reaction, bromide can be obtained from the trans-2-hexenol which is then reacted with phosphorus tribromide to obtain triphenylphosphine ylide salt; after the esterification reaction of the 1, 10-decanediol, the 1, 10-decanediol protected by acetic ester can be obtained, and then after oxidation reaction, 10-oxo decyl acetate can be obtained; after Witting reaction and then quenching reaction of the triphenylphosphine ylide salt and the 10-oxo decyl acetate, 10, 12-hiago dienal can obtained by separation; after the process of recrystal, trans 10, 12-hiago dienal with transverse structure can be obtained, and then after the oxidation reaction, E10, E12-hiago dienal is obtained. The method of the invention adopts materials which are cheap and easy to be obtained and uses simple and reasonable syntheticroute, the operation is simple and safe, the utilization rate of the materials is high and the main ingredient compound of the maruca testulalils geyer sex pheromone can be synthesized with low cost in a short time.
Description
Technical field
The present invention relates to the wild snout moth's larva insect sex pheromone of beans major ingredient (E10, E12)-hexadecadienoic aldehyde with and the chemical synthesis process of analogue and intermediate.
Background technology
The wild snout moth's larva Maruca of beans testulalis Geyer is the important pests of present legume crop, bores moth property cause harm leaf, flower and beanpod.Because the leguminous crop harvest time is short, adopt the wild snout moth's larva of chemical pesticide control bean-pod borer and beans, residual quantity is big, can pollute beanpod.This worm eats into larva gets food in the beanpod, more hidden, agricultural chemicals is difficult for tagging, and simultaneously, mature larva is to take off to pupate after pod buries, and certain protection is also arranged, and therefore, difficulty of prevention and cure is very big.In the high-incidence season, the peasant adopts methods such as improving spraying medicine concentration, increase access times, use riskiest pesticide to prevent and treat usually, the result had had both killed and wounded natural enemy in a large number, destroyed the eubiosis in vegetable garden, cause insect rampant again, cause pesticide residue severe overweight in the vegetables again, influenced ediblely, bring out the resistance of vegetables pest simultaneously various conventional chemical agricultural chemicals.Legume crop is plucked in batches, and the collecting period is separated by closely, will pluck once in 2-3 days receipts phases of Sheng, after a lot of peasant households have executed agricultural chemicals, does not reach the just listing of fate of personal distance.
The unreasonable use agriculture chemical of vegetable grower, the abuse height poisons the medicine of learning to farm, severe contamination farmland, commodity vegetables and context, cause the content severe overweight of the pesticide residue in the vegetable products, have a strong impact on the healthy of people, bring difficulty for Vegetables Exportation, especially states such as Japan, European Union have strengthened the agricultural residual standard to agricultural products in China.This a series of problem has proposed new requirement and challenge to our pest control.Therefore, exploitation is new, effectively prediction and the method for preventing and treating seem very urgent.
More common in the world pest control technology comprises natural enemy, microorganism and semiochemicals technology at present.The semiochemicals technology has then that selectivity is strong, low risk and compatibility, causes the attention of various countries just day by day and applies.
Evaluation, the applied research work of the pheromone compound of the wild snout moth's larva of beans start from the nineties, all so far research work very limited (Adati, T.﹠amp; Tatsuki, 1999; Downham etc., 2003).Domestic only have observed to some biological habits and description (seeing following reference).The major ingredient that we have identified the wild snout moth's larva insect sex pheromones of China's beans for (E10, E12)-hexadecadienoic aldehyde.
Huang Qizhong, (the lepidopteran: the Pyralidae) group of larva change of bean-pod borer (Marucavitrata) on the sesbania of vegetables farm, Peng Wu health .2002 platform South Asia.Taiwan insect 22:271-278.
Huang Qizhong, Peng Wu health .2003 bean-pod borer (Marucavitrata) (lepidopteran: Pyralidae) the cause harm characteristic of sesbania (Sesbaniacannabina).Taiwan insect 23:1-11.
Ke Lidao etc., 1985 insect journals 28 (1), 51
Song Guochun, Peng Yuanfu, Yang Zhenxia, generation and the control of the Hou Su tinkling of pieces of jade 1994 Shandong Province soybean moth pod insects.The Laiyang Agricultural College journal, 11 (supplementary issues) 125-127.
The gentle Zhang Rongzong of Wang Zhi, occurrence characteristic of 1999 bean-pod borers and prophylactico-therapeutic measures.Fujian agriculture science and technology 1999 (1), 35-36
Wen Lizhang, Xiao Xinping, the biological characteristics and the Study of Prevention Technology of Deng Pei cloud .2000 bean pod borer.Insect knowledge 37 (5) 274-278
Yang Zhihua, Lv Xilin, Zhou Guihua.1991 bean-pod borer pests occurrence rule researchs.Insect knowledge, 28 (6) 341-344.
A spot of (Z10, E12)-hexadecadienoic aldehyde, (E10, Z12)-hexadecadienoic aldehyde and (Z10, Z12)-hexadecadienoic aldehyde impurity severe inhibition allure.Therefore, (E10, E12)-the decisive pheromone of purity of hexadecadienoic aldehyde lures the activity of core.And because this compound accounts for absolute content in the wild snout moth's larva sex pheromone of beans mixture, so its synthetic cost is very crucial for applying of final product.
Summary of the invention
Technical problem to be solved by this invention provide a kind of adopt the relatively inexpensive raw material that is easy to get, through compound in the wild snout moth's larva sex pheromone of synthetic beans in the synthetic route of advantages of simple, lower cost short period (E10, E12)-synthetic method of hexadecadienoic aldehyde.
The technical scheme that the present invention solves the problems of the technologies described above is such: compd E 10 in the wild snout moth's larva sex pheromone of a kind of beans, the synthetic method of E12-hexadecadienoic aldehyde, it is characterized in that compound with instead-2-hexenol and two kinds of raw materials of decamethylene-glycol are substrate; Instead-the 2-hexenol obtains bromide through halogenating reaction, obtains triphenylphosphine ylide salt with the phosphorus tribromide reaction again; The esterification of decamethylene-glycol has obtained the decamethylene-glycol of acetic ester list protection; again through peroxidation; obtain 10-oxo acetic ester in the last of the ten Heavenly stems, triphenylphosphine ylide salt and 10-oxo acetic ester in the last of the ten Heavenly stems are through the Wittig reaction, and cancellation is reacted again; separate and obtain 10; 12-n-Hexadecane dienol obtains the anti-10 of transconfiguration, 12-n-Hexadecane dienol through recrystallization; oxidizing reaction has obtained E10 then, the E12-hexadecadienoic aldehyde.
The preparation of described compound triphenyl phosphine ylide salt be with instead-the 2-hexenol is dissolved in the dry methylene chloride; be cooled to-8～12 ℃ under the nitrogen protection; slowly drip the phosphorus tribromide of 0.31～0.35% (molar percentage); the phosphorus tribromide of preferred 0.33% (molar percentage); dropwise and continue to stir; saturated sodium bicarbonate solution cancellation reaction with ice; add bulk petroleum ether as diluting more than 5～10 times; the saturated common salt water washing; collect the organic phase anhydrous sodium sulfate drying then; cross and filter out sodium sulfate; remove sherwood oil with Rotary Evaporators more just to obtain instead-the thick product of 1-bromo-2-hexene; do not need to be further purified it is dissolved in the dry toluene; the triphenyl phosphorus that adds 1.1～1.3% (molar percentages); the triphenyl phosphorus of preferred 1.2% (molar percentage) after lucifuge stirs, filters and obtains white solid triphenylphosphine ylide salt.
Described 3,1; the esterification of 10-decanediol is with 1; the 10-decanediol is dissolved in the toluene; add the Glacial acetic acid of 0.9～1% (molar percentage) and the vitriol oil of catalytic amount 80～90% (wt), 99～101 ℃ refluxed 1～2 hour after stopped reaction, preferably 100 ℃ refluxed 1～2 hour down after stopped reaction; through the dry aftertreatment of conventional washing; column chromatography obtains the decamethylene-glycol of compound acetic ester list protection, and eluent is ethyl acetate and sherwood oil.
1 of described acetic ester list protection; the oxidizing reaction of 10-decanediol is with 1 of compound acetic ester list protection; the 10-decanediol is dissolved in the dry methylene chloride; add 1.2～1.4% (molar percentage) PCC; stirring at room reaction under the nitrogen protection; cross and filter out solid impurity, column chromatography obtains 10-oxo acetic ester in the last of the ten Heavenly stems, and eluent is ethyl acetate and sherwood oil.
Described Wittig reaction is that 1.2～1.4% (molar percentage) compound triphenyl phosphine ylide salt is dissolved in the dry tetrahydrofuran; be cooled to-18～-22 ℃ under the nitrogen protection; drip the hexane solution of 1.2～1.4% (molar percentage) n-Butyl Lithium; behind the stirring reaction; cool to-68～-72 ℃ of tetrahydrofuran solutions that add compound 10-oxo acetic ester in the last of the ten Heavenly stems; after the stirring; controlled temperature is at-20 ℃--and 30 ℃; drip the hexane solution of 1.2～1.3% (molar percentage) n-Butyl Lithium again; after the stirring at room, dehydrated alcohol cancellation reaction is through the dry aftertreatment of conventional washing; column chromatography purification obtains compound 10,12-n-Hexadecane dienol.
Described trans-10, the preparation of 12-n-Hexadecane dienol are with compound 10, and 12-n-Hexadecane dienol is dissolved in the dry normal hexane, and recrystallization under-18～-22 ℃ of conditions obtains white pure solid chemical compound trans-10,12-n-Hexadecane dienol.
Described E10; the preparation of E12-hexadecadienoic aldehyde is with the compound trans-10; 12-n-Hexadecane dienol is dissolved in the dry methylene chloride; the PCC that adds 1.2～1.4% (molar percentages); the stirring at room reaction is crossed and is filtered out solid impurity under the nitrogen protection, and column chromatography obtains target compound E10; E12-hexadecadienoic aldehyde, eluent are ethyl acetate and sherwood oil.
Compared with prior art, the invention has the advantages that: the synthetic route of compound with instead-2-hexenol and two kinds of raw materials of decamethylene-glycol are that substrate reacts in two steps, can obtain target compound through the simple reactions operation of seven steps; When preparing the decamethylene-glycol of acetic ester list protection, simple to operate, avoid using relatively costly acetic anhydride, carboxylic acid halides and pyridine or other organic basic compound, unique by product of generation can be converted into raw material (4) not to be needed to be further purified, and can directly reuse; Can improve the content of trans olefins in the product by dripping the hexane solution of 1.3% (molar percentage) n-Butyl Lithium again during the Wittig reaction.After dehydrated alcohol cancellation reaction, directly obtain 10, the thick product of 12-n-Hexadecane dienol does not need further hydrolysis acetic ester.The relatively inexpensive raw material that is easy to get of whole process using, through the synthetic route of advantages of simple, safety simple to operate, raw material availability height, the wild snout moth's larva sex pheromone of synthetic beans major ingredient compound in the lower cost short period.
Description of drawings
Fig. 1 process flow diagram.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
1. the preparation of compound (3) triphenylphosphine ylide salt: with compound (1) anti--the 2-hexenol is dissolved in the dry methylene chloride; be cooled to-10 ℃ under the nitrogen protection; slowly drip the phosphorus tribromide of 0.33% (molar percentage); dropwise and continue to stir after 30 minutes; saturated sodium bicarbonate solution cancellation reaction with ice; add the dilution of bulk petroleum ether; as 5; or 10 more than the multiple; use the saturated common salt water washing again; collect organic phase then and use anhydrous sodium sulfate drying half an hour; cross and filter out sodium sulfate; again with Rotary Evaporators remove sherwood oil just can obtain compound (2) anti--the thick product of 1-bromo-2-hexene; do not need to be further purified it is dissolved in the dry toluene; the triphenyl phosphorus that adds 1.2% (molar percentage); lucifuge stirs two days later, and filtering and obtaining white solid is exactly target compound (3) triphenylphosphine ylide salt.
2.1; the esterification of 10-decanediol: with 1; the 10-decanediol is dissolved in the toluene; add the Glacial acetic acid of 0.9～1% (molar percentage) and the vitriol oil of catalytic amount 80～90% (wt), 100 ℃ refluxed one hour after stopped reaction, through the dry aftertreatment of conventional washing; column chromatography obtains 1 of target compound acetic ester list protection; 10-decanediol, chromatography column model are 30*300/24 (19), and eluent is ethyl acetate and sherwood oil.
3. 1 of compound (5) acetic ester list protection; the oxidizing reaction of 10-decanediol: with 1 of compound (5) acetic ester list protection; the 10-decanediol is dissolved in the dry methylene chloride; add 1.3% (molar percentage) PCC; stirring at room is two hours under the nitrogen protection, crosses and filters out solid impurity, and column chromatography obtains the target compound (6) of 10-oxo acetic ester in the last of the ten Heavenly stems; the chromatography column model is 30*300/24 (19), and eluent is ethyl acetate and sherwood oil.
4.Wittig reaction: 1.3% (molar percentage) compound (3) triphenylphosphine ylide salt is dissolved in the dry tetrahydrofuran; be cooled to-20 ℃ under the nitrogen protection; drip the hexane solution of 1.3% (molar percentage) n-Butyl Lithium; behind the stirring reaction one hour; cool to-70 ℃ of tetrahydrofuran solutions that add compound (6) 10-oxo acetic ester in the last of the ten Heavenly stems; stir after one hour; controlled temperature is at-20 ℃--and 30 ℃; drip the hexane solution of 1.3% (molar percentage) n-Butyl Lithium again; stirring at room is dehydrated alcohol cancellation reaction after one hour; through the dry aftertreatment of conventional washing; column chromatography purification obtains compound (7) 10; 12-n-Hexadecane dienol, chromatography column model are 30*300/24 (19), and eluent is ethyl acetate and sherwood oil.
5. compound (8) trans-10, the preparation of 12-n-Hexadecane dienol: compound (7) 10,12-n-Hexadecane dienols are dissolved in the dry normal hexane, and recrystallization under-20 ℃ of conditions obtains white pure solid chemical compound (8) trans-10,12-n-Hexadecane dienol.
6. compound (9) (E10; E12)-preparation of hexadecadienoic aldehyde: with compound (8) trans-10; 12-n-Hexadecane dienol is dissolved in the dry methylene chloride; add the PCC of 1.3% (molar percentage), stirring at room is two hours under the nitrogen protection, crosses to filter out solid impurity; column chromatography obtains target compound (E10; E12)-and hexadecadienoic aldehyde, the chromatography column model is 22*300/24 (19), eluent is ethyl acetate and sherwood oil.
Flow process of the present invention is referring to Fig. 1.
Claims (7)
1, compd E 10 in the wild snout moth's larva sex pheromone of a kind of beans, the synthetic method of E12-hexadecadienoic aldehyde, it is characterized in that compound with instead-2-hexenol and two kinds of raw materials of decamethylene-glycol are substrate; Instead-the 2-hexenol obtains bromide through halogenating reaction, obtains triphenylphosphine ylide salt with the phosphorus tribromide reaction again; The esterification of decamethylene-glycol has obtained the decamethylene-glycol of acetic ester list protection; again through peroxidation; obtain 10-oxo acetic ester in the last of the ten Heavenly stems, triphenylphosphine ylide salt and 10-oxo acetic ester in the last of the ten Heavenly stems are through the Wittig reaction, and cancellation is reacted again; separate and obtain 10; 12-n-Hexadecane dienol obtains the anti-10 of transconfiguration, 12-n-Hexadecane dienol through recrystallization; oxidizing reaction has obtained E10 then, the E12-hexadecadienoic aldehyde.
2; synthetic method according to claim 1; the preparation that it is characterized in that described compound triphenyl phosphine ylide salt be with instead-the 2-hexenol is dissolved in the dry methylene chloride; be cooled to-8～12 ℃ under the nitrogen protection; slowly drip the phosphorus tribromide of 0.31～0.35% (molar percentage); dropwise and continue to stir; saturated sodium bicarbonate solution cancellation reaction with ice; add the dilution of bulk petroleum ether; the saturated common salt water washing; collect the organic phase anhydrous sodium sulfate drying then; cross and filter out sodium sulfate; remove sherwood oil with Rotary Evaporators more just to obtain instead-the thick product of 1-bromo-2-hexene, do not need to be further purified directly it is dissolved in the dry toluene, add the triphenyl phosphorus of 1.1～1.3% (molar percentages); after lucifuge stirs, filter and obtain white solid triphenylphosphine ylide salt.
3, synthetic method according to claim 1; it is characterized in that described 3,1; the esterification of 10-decanediol is with 1; the 10-decanediol is dissolved in the toluene, adds the Glacial acetic acid of 0.9～1.0% (molar percentage) and the vitriol oil of catalytic amount 80～90% (wt), 99～101 ℃ refluxed 1～2 hour after stopped reaction; through the dry aftertreatment of conventional washing; column chromatography obtains the decamethylene-glycol of compound acetic ester list protection, and eluent is ethyl acetate and sherwood oil.
4, synthetic method according to claim 1; it is characterized in that 1 of described acetic ester list protection; the oxidizing reaction of 10-decanediol is with 1 of compound acetic ester list protection; the 10-decanediol is dissolved in the dry methylene chloride; the PCC that adds 1.2～1.4% (molar percentages), stirring at room reaction under the nitrogen protection is crossed and is filtered out solid impurity; column chromatography obtains 10-oxo acetic ester in the last of the ten Heavenly stems, and eluent is ethyl acetate and sherwood oil.
5; synthetic method according to claim 1; it is characterized in that described Wittig reaction is that 1.2～1.4% (molar percentage) compound triphenyl phosphine ylide salt is dissolved in the dry tetrahydrofuran; be cooled to-18～-22 ℃ under the nitrogen protection; drip the hexane solution of 1.2～1.4% (molar percentage) n-Butyl Lithium; behind the stirring reaction; cool to-68～-72 ℃ of tetrahydrofuran solutions that add compound 10-oxo acetic ester in the last of the ten Heavenly stems; after the stirring; controlled temperature is at-20 ℃--and 30 ℃; drip the hexane solution of 1.2～1.3% (molar percentage) n-Butyl Lithium again; after the stirring at room; dehydrated alcohol cancellation reaction; through the dry aftertreatment of conventional washing, column chromatography purification obtains compound 10,12-n-Hexadecane dienol.
6, synthetic method according to claim 1, it is characterized in that described trans-10, the preparation of 12-n-Hexadecane dienol is with compound 10,12-n-Hexadecane dienol is dissolved in the dry normal hexane, recrystallization under-18～-22 ℃ of conditions, obtain white pure solid chemical compound trans-10,12-n-Hexadecane dienol.
7, synthetic method according to claim 1; it is characterized in that described E10; the preparation of E12-hexadecadienoic aldehyde is with the compound trans-10; 12-n-Hexadecane dienol is dissolved in the dry methylene chloride, adds the PCC of 1.2～1.4% (molar percentages), stirring at room reaction under the nitrogen protection; cross and filter out solid impurity; column chromatography obtains target compound E10, and E12-hexadecadienoic aldehyde, eluent are ethyl acetate and sherwood oil.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101891593A (en) * | 2010-07-23 | 2010-11-24 | 河北科技大学 | Method for preparing sex pheromone of carpocapsa pomonella |
| CN102617343A (en) * | 2012-02-22 | 2012-08-01 | 石家庄维奥化工有限公司 | Adsorption chromatography purification method for 8-acetoxy caprylic aldehyde |
| CN103626657A (en) * | 2012-08-23 | 2014-03-12 | 昆明博鸿生物科技有限公司 | Synthesis of plodia interpunctella sex pheromone 9Z, 12E-tetradecadiene-1-acetate |
| CN110724042A (en) * | 2019-12-09 | 2020-01-24 | 中国林业科学研究院森林生态环境与保护研究所 | Method for synthesizing sex pheromone active ingredient of populus canula |
| CN111253228A (en) * | 2020-03-02 | 2020-06-09 | 常州大学 | Industrial synthesis method of dichocrocis punctiferalis sex pheromone |
| CN112409148A (en) * | 2020-11-23 | 2021-02-26 | 昆明悦馨生物科技有限公司 | Preparation method of 2 trans, 6 cis-nonadienal and 2 trans, 6 cis-nonadienol |
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2007
- 2007-11-13 CN CN200710156845A patent/CN101434521B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101891593A (en) * | 2010-07-23 | 2010-11-24 | 河北科技大学 | Method for preparing sex pheromone of carpocapsa pomonella |
| CN101891593B (en) * | 2010-07-23 | 2013-04-10 | 河北科技大学 | Method for preparing sex pheromone of carpocapsa pomonella |
| CN102617343A (en) * | 2012-02-22 | 2012-08-01 | 石家庄维奥化工有限公司 | Adsorption chromatography purification method for 8-acetoxy caprylic aldehyde |
| CN102617343B (en) * | 2012-02-22 | 2014-04-02 | 石家庄维奥化工有限公司 | Adsorption chromatography purification method for 8-acetoxy caprylic aldehyde |
| CN103626657A (en) * | 2012-08-23 | 2014-03-12 | 昆明博鸿生物科技有限公司 | Synthesis of plodia interpunctella sex pheromone 9Z, 12E-tetradecadiene-1-acetate |
| CN110724042A (en) * | 2019-12-09 | 2020-01-24 | 中国林业科学研究院森林生态环境与保护研究所 | Method for synthesizing sex pheromone active ingredient of populus canula |
| CN111253228A (en) * | 2020-03-02 | 2020-06-09 | 常州大学 | Industrial synthesis method of dichocrocis punctiferalis sex pheromone |
| CN111253228B (en) * | 2020-03-02 | 2023-01-17 | 常州大学 | Industrial synthesis method of dichocrocis punctiferalis sex pheromone |
| CN112409148A (en) * | 2020-11-23 | 2021-02-26 | 昆明悦馨生物科技有限公司 | Preparation method of 2 trans, 6 cis-nonadienal and 2 trans, 6 cis-nonadienol |
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