CN103694117A - Novel method for preparing asiatic corn borer sex pheromone from tridecane compound - Google Patents
Novel method for preparing asiatic corn borer sex pheromone from tridecane compound Download PDFInfo
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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Abstract
The invention discloses a novel method for preparing asiatic corn borer sex pheromone from a tridecane compound which is taken as an initial raw material, and belongs to the technical field of agricultural plant protection. The invention provides a novel method for preparing asiatic corn borer sex pheromone from a tridecane compound which is taken as an initial raw material. In particular, the invention first proposes an innovative and unique '13C+1C' synthesis strategy for chemical synthesis of the asiatic corn borer sex pheromone. The method disclosed by the invention has the characteristics of low raw material cost, short synthesis route, simple synthesis condition, high total yield and the like, and is applicable to industrial production.
Description
Technical field
The invention belongs to agriculture plant protection technical field, be specifically related to a kind of sex pheromone of Ostrinia furnacalis novel preparation method of C13 compound as starting raw material of usining.
Background technology
Ostrinia furnacalis is the primary pest of China's corn field; in the method for various control Ostrinia furnacalis; insect sex pheromone biological control method is highly sensitive with it, selectivity is strong, nontoxic, free from environmental pollution, not killed natural enemies, the advantage such as be difficult for developing immunity to drugs; meet IPM(integrated pest management) strategy; it is current internationally recognized environment protective plant protecting technology; significant to protecting agriculture production, ecological safety and realizing agricultural sustainable development, and obtain wide popularization and application.
Because the sex pheromone content producing in female polypide is very micro-; average every female moth only contains 9.0 ± 7.7ng(Z:E=47:53); and insect sex pheromone technology prevention Ostrinia furnacalis need to be used relatively a large amount of sex pheromones; only adopt natural extract can not meet actual needs, be therefore emphasis and the focus of chemical preparation and plant protection subject to the preparation of sex pheromone of Ostrinia furnacalis always.People wish efficiently to prepare with simple, economic method, realize suitability for industrialized production, thereby promote better this technology.
The preparation method of sex pheromone of Ostrinia furnacalis, has been reported both at home and abroad, sums up and mainly contains carbon chain growth and shorten 2 preparation strategies, wherein with " 12C+2C ", prepares strategy study more.Mainly with 1,12-, 12 carbon glycol, as starting raw material, design syntheti c route, and then build 14 carbon backbone chains.
1 carbon chain growth preparation strategy
(the Suk-ku Kang such as Kang, Jung-Min Park, Kyung-Lan Hwang, Jeong-Uhn Lee, Hyun-Gwan Goh.Synthesis and Biological Test of the Pheromone of the Asian Corn Borer Moth (Ostrinia furnacalis) [J] .Bulletin of Korean Chemical Society.1985, 6 (1): 15-19) attempt with 1, 12-12 carbon glycol are raw material, two keys of 14 carbon backbone chains and 12 by wittig condensation reaction, have been formed with Ethyltriphenylphosphonium brimide, by controlling the condition of condensation reaction, prepare separately two kinds of configuration sex pheromone monomers, need after being mixed, for field, apply.
Chen Jia prestige (the Chen Jiawei of seminar; yellow rose-tinted clouds; Jiang Jilong. the synthetic and raw side effect [J] of expansion of sex pheromone of Ostrinia furnacalis. Hubei University's journal (natural science edition); 1991; 13 (2): old prestige of 140-146., yellow rose-tinted clouds, Xu Jing. apply the synthetic sex pheromone of Ostrinia furnacalis [J] of wittig reagent of different degree of crosslinking. SCI; 1993,14:653-655.) be engaged in for many years the research that using polymer wittig reagent is prepared sex pheromone of Ostrinia furnacalis.They equally with 1,12-, 12 carbon glycol for raw material, designed the wittig solid phase method that shows unique characteristics and conventional liquid phase method two lines and prepared sex pheromone of Ostrinia furnacalis.Solid phase is prepared overall yield and is reached 60% left and right, and conventional liquid phase method overall yield is 32%.
(the Chen Haibin such as Chen Haibin, Du Yongjun. the simple synthesis of sex pheromone of Ostrinia furnacalis [J]. Pesticide Science journal, 2010,12 (1): 90 – 92.) from 1,12-ten two carbon glycol set out, and through monolateral esterification and wittig reaction, with 45% total recovery, have prepared sex pheromone of Ostrinia furnacalis 1,2, along inverse ratio, be 9:1.Gained compound, through configuration conversion, is obtained to the mixture that suitable inverse ratio is 25:75.
(the Li Jiuming such as Li Jiuming; Yong Jianping; Huang Fenglan. easy synthetic [J] of sex pheromone of Ostrinia furnacalis. modern, 2011,10 (4): 35-37; 40.) with 1; 12-12 carbon glycol are starting raw material, through monolateral bromo, acetylize, pyridine oxide oxidation and Wittig reaction, it are prepared, and total recovery is 36.6%(Z:E=89:11); then cis-trans-isomer mixture is carried out in Sodium Nitrite and nitric acid system to configuration conversion, make to become 17:83 along reverse proportionality.
Except 1,12-, 12 carbon glycol, also there is other aliphatics alcohols material to be used as starting raw material and prepare sex pheromone of Ostrinia furnacalis.
(the J.A.Klun such as Klun, B.A.Bierl-Leonhardt, M.Schwarz.etc.Sex pheromone of the Asian Corn Borer[J] .Life Sciences, 1980,27 (17): 1603-1606.) after definite sex pheromone of Ostrinia furnacalis forms, first it has been realized to artificial preparation, it prepares strategy is mainly " 1+7+6 ".(the Li Zhengming such as Li Zhengming, the novel method [J] of a Meyer Schwarz. synthetic Ostrinia furnacalis sex pheromone. Chinese science, 1984,1:38-43.) taked the preparation strategy of " 11+3 ", utilize hydroboration, by borane reagent, through " one pot reaction ", prepare alkene, the advantage of this preparation method's maximum is " one kettle way " preparation, greatly shortened route, improved efficiency, but overall yield is lower, only 18% left and right, is unsuitable for scale operation.(the Li Jiuming such as Li Jiuming; Huang Guozheng; Yong Jianping. the new synthetic method of sex pheromone of Ostrinia furnacalis [J]. agricultural chemicals; 2007; 46(6): 388-389,400.) take 10-hydroxydecanoic acid as starting raw material, through Lithium Aluminium Hydride reduction, monolateral bromo, DCHP protection, Grignard reagent coupling, de-DHP and acetylize, ozonization and Wittig reaction, prepared target compound; total recovery is 17.9%, prepares strategy and remains " 12+2 ".
2. carbochain shortens preparation strategy
Wang has elementary (Wang Youchu, Liu Fuchu. the improvement synthetic [J] of sex pheromone of Ostrinia furnacalis. Kunming Journal of Teachers College (natural science edition), 1994,9 (1): 90-94.) from the natural cis-12-Decosahedaenoic acid being easy to get, (the erucic acid), through ozonize, NaBH
4(KBH
4) reduction preparation corresponding 13-hydroxyl-ficocerylic acid (" 22-9 " strategy); with obtain 13-acetoxyl group ficocerylic acid by acetylize; through bromo decarboxylic reaction, obtain 12-acetoxyl group bromo n-tridecane again; finally react with triphenyl phosphorus; then carrying out wittig with acetaldehyde reacts and has prepared target compound; total recovery is 15%, and the crucial preparation process of this route remains " 12+2 ".
Multiple elementary (the Liu Fuchu of Liu, Lin Jun. easy synthetic [J] of sex pheromone of Ostrinia furnacalis. organic chemistry, 1995,15:546-549.) reported the syntheti c route that unsaturated fatty acids Z-15-tetracosenoic acid that a kind of crude vegetal-Malania Oleifera Oil of take Yunnan high yield obtains through saponification is raw material, through three-step reaction, prepared intermediate 13-tetradecene-1-alcohol acetate, with CoCl
2-Ph
3p-NaBH
4for sex pheromone of Ostrinia furnacalis has been prepared in catalyst system isomerization, total recovery is 17.5%.The feature of this route maximum is that the product of migration of the double bond, isomerization gained is 46:54 along reverse proportionality, approaches along reverse proportionality with Ostrinia furnacalis virgin moth belly extract, can be directly used in field and use, and has saved loaded down with trivial details post-processed work.
Sum up above-mentioned existing preparation method, we find to exist following outstanding problem:
1. the expensive or severe reaction conditions of part route or starting raw material or syntheti c route is long or wayward along reverse proportionality, cannot meet the natural outstanding problem such as compare, and application and the large-scale production of restriction the method, affected the widespread use of this technology.
2. an other method is prepared separately along anti-two components, needs to be mixed and just to can be used for field application through the later stage, increases and uses difficulty.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, and a kind of novel preparation method of C13 compound as the sex pheromone of Ostrinia furnacalis of starting raw material of usining is provided.Particularly the present invention has proposed " 13C+1C " synthesis strategy of a kind of innovation, uniqueness first for the chemical preparation of sex pheromone of Ostrinia furnacalis, have that raw materials cost is cheap, synthetic route is short, synthesis condition is simple, total recovery high, applicable to suitability for industrialized production.
Sex pheromone of Ostrinia furnacalis of the present invention (Z, E)-12-tetradecene-1-alcohol acetate (1,2) structural formula is shown below, and the two proportion of composing is approximately 27:73(relative percentage).
Of the present inventionly a kind ofly using C13 compound as the sex pheromone of Ostrinia furnacalis novel preparation method of starting raw material, comprise following preparation process:
1) 1,13-undecane dicarboxylic acid is reduced to 1,13-tridecane glycol.
Get 1; 13-undecane dicarboxylic acid is (as round-bottomed flask) in reaction vessel; add anhydrous THF(tetrahydrofuran (THF)) dissolve; under ice bath and nitrogen protection, add lithium aluminum hydride, room temperature reaction 10～15 hours, after reaction finishes; under ice bath, dropwise add HCl solution to the gas of massfraction 10～20% no longer to overflow; suction filtration, divides washing leaching cake 3～5 times by 15～25ml ethyl acetate, and filtrate is used anhydrous MgSO
4dry, revolve after steaming to obtain white solid crude product, 1,13-tridecane glycol crude product; Wherein 1, the consumption mol ratio of 13-undecane dicarboxylic acid and lithium aluminum hydride is 1:3～5; In THF solution, the concentration of 1,13-undecane dicarboxylic acid is 20～30mg/mL.
2) 1, the monolateral esterification of 13-tridecane glycol generates 13-hydroxyl 13 carbon-1-alcohol acetic ester.
Get 1,13-tridecane glycol crude product is in reaction vessel, add hexanaphthene, 55～60 ℃ of stirring and dissolving dripped the aqueous solution containing Glacial acetic acid and the vitriol oil in 10～30 minutes in reaction vessel, wherein Glacial acetic acid concentration is 0.7～0.9mol/L, vitriol oil concentration is 0.002～0.003mol/L, and 55～60 ℃ are reacted 8～12 hours, are cooled to room temperature, separatory, organic phase is first used the saturated NaHCO of 15～25ml
3solution washing 2～3 times, rear use 15～25ml saturated common salt water washing 2～3 times, revolve and steam to obtain crude product, and column chromatography purification obtains white solid 13-hydroxyl 13 carbon-1-alcohol acetic ester; Wherein, in cyclohexane solution, the concentration of 1,13-tridecane glycol is 20～30mg/mL; The consumption mol ratio of 1,13-tridecane glycol and Glacial acetic acid is 1:80～90.
3) the monolateral 13-aldehyde radical 13 carbon-1-alcohol acetic ester that is oxidized to of 13-hydroxyl 13 carbon-1-alcohol acetic ester.
Get PCC(pyridinium chlorochromate) be placed in reaction vessel, under room temperature, add methylene dichloride to dissolve, in reaction vessel, add 13-hydroxyl 13 carbon-1-alcohol acetic ester, stirring at room, TLC monitors reaction process, after 3～5 hours, reaction finishes, suction filtration, 5～15ml anhydrous diethyl ether washing leaching cake 2～3 times, filtrate is revolved steaming, crude product, through column chromatography purification, obtains colourless oil liquid product 13-aldehyde radical 13 carbon-1-alcohol acetic ester; Wherein, in dichloromethane solution, the concentration of 13-hydroxyl 13 carbon-1-alcohol acetic ester is 30～40mg/mL; The consumption mol ratio of 13-hydroxyl 13 carbon-1-alcohol acetic ester and pyridinium chlorochromate is 1:1～3.
4) 13-aldehyde radical 13 carbon-1-alcohol acetic ester is reduced to 13-tetradecene-1-alcohol acetic ester.
Get methyltriphenylphospbromide bromide phosphorus and in reaction vessel, be dissolved in anhydrous THF(tetrahydrofuran (THF)), under nitrogen protection, add potassium tert.-butoxide, stirring at room 20～45min, obtains yellow solution; At-20～-30 ℃, to be dissolved in anhydrous THF(tetrahydrofuran (THF)) in 13-aldehyde radical 13 carbon-1-alcohol acetic ester, dropwise join in reaction flask, TLC monitoring, after after 8～12 hours, reaction finishes, add 10～20ml saturated ammonium chloride solution cancellation reaction, by 10～15ml anhydrous diethyl ether extracting twice, merge organic phase, concentrate to obtain crude product, column chromatography purification, obtains colourless oil liquid product 13-tetradecene-1-alcohol acetic ester; Wherein, in THF solution, the concentration of 13-aldehyde radical 13 carbon-1-alcohol acetic ester is 15～25mg/mL; The consumption mol ratio of 13-aldehyde radical 13 carbon-1-alcohol acetic ester and potassium tert.-butoxide is 1:1.5～2.5; The consumption mol ratio of potassium tert.-butoxide and methyltriphenylphospbromide bromide phosphorus is 1:1～1.2.
5) 13-tetradecene-1-alcohol acetic ester generates (Z, E)-12-tetradecene-1-alcohol acetic ester through migration of the double bond.
By waterless cobaltous chloride vacuum-drying 8～12 hours at 135～140 ℃, be cooled to after room temperature, in reaction vessel, be dissolved in anhydrous THF, under nitrogen protection, add triphenylphosphine, stir 20～45min, at-5～15 ℃, add sodium borohydride, stir 20～40min, by the 13-tetradecene-1-alcohol acetic ester being dissolved in THF, dropwise slowly add in reaction system, low temperature stirs, TLC monitoring, after 3～6 hours, reaction finishes, , add 5～10mL, 2mol/L HCl solution cancellation reaction, with 5～15ml anhydrous diethyl ether extraction 2 times, merge organic phase, concentrate to obtain crude product, 5～7ml n-hexane extraction crude product 2～3 times, suction filtration, concentrated filtrate, through column chromatography purification, obtain colourless oil liquid mix products (Z/E)-12-tetradecene-1-alcohol acetic ester, wherein, in THF solution, the concentration of 13-tetradecene-1-alcohol acetic ester is 90～100mg/mL, the consumption mol ratio of 13-tetradecene-1-alcohol acetic ester and sodium borohydride is 1:1.5～2, the consumption mol ratio of sodium borohydride and triphenylphosphine is 1:2.3～3, the consumption mol ratio of sodium borohydride and waterless cobaltous chloride is 1:1～1.3.
The present invention is a kind of usings C13 compound as the sex pheromone of Ostrinia furnacalis novel preparation method of starting raw material, and syntheti c route is as follows:
Accompanying drawing explanation
Fig. 1: (Z/E)-12-tetradecene-1-alcohol acetic ester proton nmr spectra (
1h-NMR) figure;
Fig. 2: (Z/E)-12-tetradecene-1-alcohol acetic ester carbon-13 nmr spectra (
13c-NMR) figure;
Fig. 3: (Z/E)-12-tetradecene-1-alcohol acetic ester mass spectrum (MS) figure;
Fig. 4: (Z/E)-12-tetradecene-1-alcohol acetic ester gas-chromatography (GC) figure.
From (Z/E)-12-tetradecene-1-alcohol acetic ester proton nmr spectra (Fig. 1) is analyzed, we are known:
1hNMR (500MHz, CDCl
3), δ: 5.38-5.41 (2H, m ,-CH=CH-), 4.02 (2H, t, J=6.6Hz, CH
2oAc), 2.03 (3H, s, COCH
3), 2.03 (3H, d, CH
3c=); 1.64 (4H, m, CH
2), 1.26-1.32 (16H, m, 8CH
2).
Carbon-13 nmr spectra (Fig. 2), each carbon geochemistry displacement:
13c NMR (125MHz, CDCl
3): δ=17.8,20.9,25.8,28.5,29.1,29.2,29.3,29.4,29.5 (2), 29.6,32.6,64.6,124.5,131.6,171.2.
Mass spectrum (Fig. 3) measurement result is: MS (ES): m/z=255.2[M+1]
+.
Gas-chromatography (Fig. 4) is measured known: t (Z-12-tetradecene-1-alcohol acetic ester)=21.056, t (E-12-tetradecene-1-alcohol acetic ester)=20.714, is Z:E=27:73 along reverse proportionality.
Above four kinds of signs all prove that we have synthesized (Z/E)-12-tetradecene-1-alcohol acetic ester compound.
Specific implementation method
In order to understand the present invention, spy enumerates following embodiment, and its effect is understood to explaination of the present invention, but not to any type of restriction of the present invention.
Embodiment 1:
Embodiment 2:
Get 1.0818g(5mmol) 1,13-tridecane glycol crude product is in 250ml round-bottomed flask, add hexanaphthene 40ml to dissolve, 55 ℃ of stirring and dissolving, in 10 minutes, in reaction flask, drip the aqueous solution that has dissolved 23ml Glacial acetic acid, the 0.08ml vitriol oil in 30ml water, 55 ℃ are reacted 10 hours, are cooled to room temperature, separatory, organic phase is first used the saturated NaHCO of 20ml
3solution washing 2 times, rear with 20ml saturated common salt water washing 2 times, revolves and steams to obtain crude product.Column chromatography (eluent is sherwood oil: ether=3:1, volume ratio) purifying, obtains white solid 13-hydroxyl 13 carbon-1-alcohol acetic ester 0.8398g, 1-2 two step overall yields 65%.
Embodiment 3:
Get 0.6466g(3mmol) PCC(pyridinium chlorochromate) be placed in 50ml round-bottomed flask, under room temperature, add 15ml methylene dichloride to dissolve, in reaction flask, add 0.5168g(2mmol) 13-hydroxyl 13 carbon-1-alcohol acetic ester, stirring at room, TLC monitoring, after 3 hours, reaction finishes, suction filtration, 10ml anhydrous diethyl ether washing leaching cake 2 times, filtrate is revolved steaming, and crude product is through column chromatography (eluent is sherwood oil: ether=8:1, volume ratio) purifying, obtain colourless oil liquid product 13-aldehyde radical 13 carbon-1-alcohol acetic ester 0.6466g, productive rate 95%.
Embodiment 4:
Get 0.7144g(2mmol) methyltriphenylphospbromide bromide phosphorus is dissolved in the anhydrous THF(tetrahydrofuran (THF) of 10ml in 50ml round-bottomed flask), under nitrogen protection, add 0.2244g(2mmol) potassium tert.-butoxide, stirring at room 30min, obtains yellow solution.At-20 ℃, to be dissolved in the anhydrous THF(tetrahydrofuran (THF) of 5ml) in 0.3076g(1.2mmol) 13-aldehyde radical 13 carbon-1-alcohol acetic ester, dropwise join in reaction flask, TLC monitoring, after after 10 hours, reaction finishes, add 10ml saturated ammonium chloride solution cancellation reaction, by 10ml anhydrous diethyl ether extracting twice, merge organic phase, concentrate to obtain crude product, column chromatography (eluent is sherwood oil: ether=10:1, volume ratio) purifying, obtain colourless oil liquid product 13-tetradecene-1-alcohol acetic ester 0.2626g, productive rate 86%.
Embodiment 5:
By 0.2855g(1.2mmol) waterless cobaltous chloride vacuum-drying 8 hours at 135 ℃, be cooled to after room temperature, in 50ml round-bottomed flask, be dissolved in the anhydrous THF of 10ml, under nitrogen protection, add 0.9442g(3.6mmol) triphenylphosphine, stir 30min, at-10 ℃, add 0.0454g(1.2mmol) sodium borohydride, stir 30min, by the 0.4681g(1.84mmol being dissolved in 5ml THF) 13-tetradecene-1-alcohol acetic ester, dropwise slowly add in reaction system, low temperature stirs, TLC monitoring, after 4 hours, reaction finishes, add 5ml2mol/L HCl solution cancellation reaction, with 10ml anhydrous diethyl ether extraction 2 times, merge organic phase, concentrate to obtain crude product, twice of 5ml n-hexane extraction crude product, suction filtration, concentrated filtrate, through column chromatography, (eluent is sherwood oil: ether=40:1, volume ratio) purifying, obtain colourless oil liquid mix products (Z/E)-12-tetradecene-1-alcohol acetic ester 0.3558g, productive rate 76%(Z:E=27:73, GC-MS determines along reverse proportionality), total recovery 40%.
Claims (6)
1. using C13 compound as the sex pheromone of Ostrinia furnacalis novel preparation method of starting raw material, its step is as follows:
1) 1,13-undecane dicarboxylic acid is reduced to 1,13-tridecane glycol
Get 1; 13-undecane dicarboxylic acid is in reaction vessel; add anhydrous THF to dissolve; under ice bath and nitrogen protection, add lithium aluminum hydride, room temperature reaction 10～15 hours, after reaction finishes; under ice bath, dropwise add HCl solution to the gas of massfraction 10～20% no longer to overflow; suction filtration, divides washing leaching cake 3～5 times by 15～25ml ethyl acetate, and filtrate is used anhydrous MgSO
4dry, revolve after steaming to obtain white solid crude product, 1,13-tridecane glycol crude product;
2) 1, the monolateral esterification of 13-tridecane glycol generates 13-hydroxyl 13 carbon-1-alcohol acetic ester
Get 1,13-tridecane glycol crude product is in reaction vessel, add hexanaphthene to dissolve, 55～60 ℃ of stirring and dissolving dripped the aqueous solution containing Glacial acetic acid and the vitriol oil in 10～30 minutes in reaction vessel, wherein Glacial acetic acid concentration is 0.7～0.9mol/L, vitriol oil concentration is 0.002～0.003mol/L, and 55～60 ℃ are reacted 8～12 hours, are cooled to room temperature, separatory, organic phase is first used the saturated NaHCO of 15～25ml
3solution washing 2～3 times, rear use 15～25ml saturated common salt water washing 2～3 times, revolve and steam to obtain crude product, and column chromatography purification obtains white solid 13-hydroxyl 13 carbon-1-alcohol acetic ester;
3) the monolateral 13-aldehyde radical 13 carbon-1-alcohol acetic ester that is oxidized to of 13-hydroxyl 13 carbon-1-alcohol acetic ester
Get pyridinium chlorochromate and be placed in reaction vessel, under room temperature, add methylene dichloride to dissolve, in reaction vessel, add 13-hydroxyl 13 carbon-1-alcohol acetic ester, stirring at room, TLC monitoring, after 3～5 hours, reaction finishes, suction filtration, 5～15ml anhydrous diethyl ether washing leaching cake 2～3 times, filtrate is revolved steaming, crude product, through column chromatography purification, obtains colourless oil liquid product 13-aldehyde radical 13 carbon-1-alcohol acetic ester;
4) 13-aldehyde radical 13 carbon-1-alcohol acetic ester is reduced to 13-tetradecene-1-alcohol acetic ester
Get methyltriphenylphospbromide bromide phosphorus and in reaction vessel, be dissolved in anhydrous THF, under nitrogen protection, add potassium tert.-butoxide, stirring at room 20～45min, obtains yellow solution; At-20～-30 ℃, by the 13-aldehyde radical 13 carbon-1-alcohol acetic ester being dissolved in anhydrous THF, dropwise join in reaction flask, TLC monitoring, after after 8～12 hours, reaction finishes, add 10～20ml saturated ammonium chloride solution cancellation reaction, by 10～15ml anhydrous diethyl ether extracting twice, merge organic phase, concentrate to obtain crude product, column chromatography purification, obtains colourless oil liquid product 13-tetradecene-1-alcohol acetic ester;
5) 13-tetradecene-1-alcohol acetic ester generates (Z, E)-12-tetradecene-1-alcohol acetic ester through migration of the double bond
By waterless cobaltous chloride vacuum-drying 8～12 hours at 135～140 ℃, be cooled to after room temperature, in reaction vessel, be dissolved in anhydrous THF, under nitrogen protection, add triphenylphosphine, stir 20～45min, at-5～15 ℃, add sodium borohydride, stir 20～40min, by the 13-tetradecene-1-alcohol acetic ester being dissolved in THF, dropwise slowly add in reaction system, low temperature stirs, TLC monitoring, after 3～6 hours, reaction finishes, , add 5～10mL, 2mol/L HCl solution cancellation reaction, with 5～15ml anhydrous diethyl ether extraction 2 times, merge organic phase, concentrate to obtain crude product, 5～7ml n-hexane extraction crude product 2～3 times, suction filtration, concentrated filtrate, through column chromatography purification, obtain colourless oil liquid mix products (Z/E)-12-tetradecene-1-alcohol acetic ester.
2. as claimed in claim 1ly a kind ofly using C13 compound as the sex pheromone of Ostrinia furnacalis novel preparation method of starting raw material, it is characterized in that: in step 1), the consumption mol ratio of 1,13-undecane dicarboxylic acid and lithium aluminum hydride is 1:3～5; In THF solution, the concentration of 1,13-undecane dicarboxylic acid is 20～30mg/mL.
3. as claimed in claim 1ly a kind ofly using C13 compound as the sex pheromone of Ostrinia furnacalis novel preparation method of starting raw material, it is characterized in that: step 2) in cyclohexane solution, the concentration of 1,13-tridecane glycol is 20～30mg/mL; The consumption mol ratio of 1,13-tridecane glycol and Glacial acetic acid is 1:80～90.
4. as claimed in claim 1ly a kind ofly using C13 compound as the sex pheromone of Ostrinia furnacalis novel preparation method of starting raw material, it is characterized in that: in step 3) dichloromethane solution, the concentration of 13-hydroxyl 13 carbon-1-alcohol acetic ester is 30～40mg/mL; The consumption mol ratio of 13-hydroxyl 13 carbon-1-alcohol acetic ester and pyridinium chlorochromate is 1:1～3.
5. as claimed in claim 1ly a kind ofly using C13 compound as the sex pheromone of Ostrinia furnacalis novel preparation method of starting raw material, it is characterized in that: in step 4) THF solution, the concentration of 13-aldehyde radical 13 carbon-1-alcohol acetic ester is 15～25mg/mL; The consumption mol ratio of 13-aldehyde radical 13 carbon-1-alcohol acetic ester and potassium tert.-butoxide is 1:1.5～2.5; The consumption mol ratio of potassium tert.-butoxide and methyltriphenylphospbromide bromide phosphorus is 1:1～1.2.
6. as claimed in claim 1ly a kind ofly using C13 compound as the sex pheromone of Ostrinia furnacalis novel preparation method of starting raw material, it is characterized in that: in step 5) THF solution, the concentration of 13-tetradecene-1-alcohol acetic ester is 90～100mg/mL; The consumption mol ratio of 13-tetradecene-1-alcohol acetic ester and sodium borohydride is 1:1.5～2; The consumption mol ratio of sodium borohydride and triphenylphosphine is 1:2.3～3; The consumption mol ratio of sodium borohydride and waterless cobaltous chloride is 1:1～1.3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299195A (en) * | 2018-02-02 | 2018-07-20 | 山东省农药科学研究院 | A kind of synthetic method of sex pheromone of Ostrinia furnacalis |
| CN108300396A (en) * | 2018-04-08 | 2018-07-20 | 赵顺全 | A kind of preparation method of viscous snout moth's larva glue |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101665430A (en) * | 2009-09-22 | 2010-03-10 | 温州医学院 | Method for synthesizing tetradecene alcohol acetic ester in ostrinia nubilalis sex pheromone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101665430A (en) * | 2009-09-22 | 2010-03-10 | 温州医学院 | Method for synthesizing tetradecene alcohol acetic ester in ostrinia nubilalis sex pheromone |
Non-Patent Citations (3)
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| J.A.KLUN ET AL: "Sex pheromone of the Asian Corn Borer", 《LIFE SCIENCES》 * |
| SUK-KU KANG ET AL: "Synthesis and Biological Test of the Pheromone of the Asian Corn Borer Moth(Ostrinia furnacalis)", 《BULLETIN OF KOREAN CHEMICAL SOCIETY》 * |
| 刘伟 等: "亚洲玉米螟性信息素合成研究进展", 《安徽农业科学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299195A (en) * | 2018-02-02 | 2018-07-20 | 山东省农药科学研究院 | A kind of synthetic method of sex pheromone of Ostrinia furnacalis |
| CN108300396A (en) * | 2018-04-08 | 2018-07-20 | 赵顺全 | A kind of preparation method of viscous snout moth's larva glue |
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