CN103694117B - Method for preparing Asiatic corn borer sex pheromone from tridecane compound - Google Patents
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
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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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 preparation method using C13 compound as starting raw material.
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, not easily the advantage such as to develop immunity to drugs; meet IPM (integrated pest management) strategy; it is current internationally recognized environment protective plant protecting technology; protecting agriculture is produced, ecological safety and to realize agricultural sustainable development significant, and obtain wide popularization and application.
Because the sex pheromone content produced in female polypide is very micro-; on average every female moth is only containing 9.0 ± 7.7ng (Z:E=47:53); and insect sex pheromone technology prevention Ostrinia furnacalis needs to use relatively a large amount of sex pheromones; only adopt natural extract 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, thus promote this technology better.
The preparation method of sex pheromone of Ostrinia furnacalis, has been reported both at home and abroad, sums up and mainly contains carbochain growth and shorten 2 preparation strategies, wherein prepare strategy study with " 12C+2C " more.Mainly design syntheti c route with 1,12-12 carbon glycol as starting raw material, and then build 14 carbon backbone chains.
1 carbochain increases 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 is raw material, the double bond of 14 carbon backbone chains and 12 is defined by wittig condensation reaction with Ethyltriphenylphosphonium brimide, two kinds of configuration sex pheromone monomers are prepared separately by the condition controlling condensation reaction, need for Field information after mixture.
Chen Jia prestige seminar (Chen Jiawei; yellow rose-tinted clouds; Jiang Jilong. the expansion synthesis of sex pheromone of Ostrinia furnacalis and raw side effect [J]. Hubei University's journal (natural science edition); 1991; 13 (2): 140-146. old prestige; yellow rose-tinted clouds; Xu Jing. apply the wittig tube-nursery sex pheromone of Ostrinia furnacalis [J] of different degree of crosslinking. SCI; 1993,14:653-655.) be engaged in the research that using polymer wittig reagent prepares sex pheromone of Ostrinia furnacalis for many years.They equally with 1,12-12 carbon glycol for raw material, devise the wittig solid phase method that shows unique characteristics and conventional liquid phase method two lines have prepared sex pheromone of Ostrinia furnacalis.Solid phase is prepared overall yield and is reached about 60%, and conventional liquid phase method overall yield is 32%.
(the Chen Haibin such as Chen Haibin, Du Yongjun. the simple synthesis [J] of sex pheromone of Ostrinia furnacalis. Pesticide Science journal, 2010,12 (1): 90 – 92.) from 1,12-ten two carbon glycol set out, and through monolateral esterification and wittig reaction, the total recovery with 45% has prepared sex pheromone of Ostrinia furnacalis 1,2, be 9:1 along inverse ratio.By gained compound through configuration conversion, obtaining along inverse ratio is the mixture of 25:75.
(the Li Jiuming such as Li Jiuming; Yong Jianping; Huang Fenglan. the easy synthesis [J] of sex pheromone of Ostrinia furnacalis. modern; 2011; 10 (4): 35-37; 40.) with 1; 12-12 carbon glycol is starting raw material; through monolateral bromo, acetylize, pyridine oxide oxidation and Wittig reaction, it is prepared; total recovery is 36.6% (Z:E=89:11); then cis-trans-isomer mixture is carried out configuration conversion in Sodium Nitrite and nitric acid system, 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 determining sex pheromone of Ostrinia furnacalis composition, achieve artificial preparation to it first, it prepares strategy mainly " 1+7+6 ".(the Li Zhengming such as Li Zhengming, Meyer Schwarz. mono-kind synthesizes the novel method [J] of Ostrinia furnacalis sex pheromone. Chinese science, 1984,1:38-43.) take the preparation strategy of " 11+3 ", utilize hydroboration, alkene is prepared through " one pot reaction " by borane reagent, the maximum advantage of this preparation method is prepared by " one kettle way ", substantially reduce route, improve efficiency, but overall yield is lower, only about 18%, be unsuitable for scale operation.(the Li Jiuming such as Li Jiuming; Huang Guozheng; Yong Jianping. the new synthetic method [J] of sex pheromone of Ostrinia furnacalis. agricultural chemicals; 2007; 46 (6): 388-389,400.) with 10-hydroxydecanoic acid for starting raw material, prepared target compound through Lithium Aluminium Hydride reduction, the protection of monolateral bromo, DCHP, Grignard reagent coupling, de-DHP and acetylize, ozonization and Wittig reaction; total recovery is 17.9%, prepares strategy and remains " 12+2 ".
2. carbochain shortens preparation strategy
Wang has elementary (Wang Youchu, Liu Fuchu. improvement synthesis [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 be easy to get, (the erucic acid), through ozonize, NaBH
4(KBH
4) the corresponding 13-hydroxyl-ficocerylic acid of reduction preparation (" 22-9 " strategy); with after obtain 13-acetoxyl group ficocerylic acid through acetylize; 12-acetoxyl group bromo n-tridecane is obtained again through bromo decarboxylic reaction; last and triphenyl phosphorus reacts; then carry out wittig to react prepared target compound with acetaldehyde; total recovery is 15%, and the crucial preparation process of this route remains " 12+2 ".
Multiple elementary (the Liu Fuchu of Liu, Lin Jun. the easy synthesis [J] of sex pheromone of Ostrinia furnacalis. organic chemistry, 1995,15:546-549.) report a kind of syntheti c route being raw material through the unsaturated fatty acids Z-15-tetracosenoic acid that saponification obtains with the crude vegetal-Malania Oleifera Oil of Yunnan high yield, intermediate 13-tetradecene-1-alcohol acetate has been prepared, with CoCl through three-step reaction
2-Ph
3p-NaBH
4for sex pheromone of Ostrinia furnacalis has been prepared in catalyst system isomerization, total recovery is 17.5%.The maximum feature of this route is that the product of migration of the double bond, isomerization gained is 46:54 along reverse proportionality, close along reverse proportionality with Ostrinia furnacalis virgin moth belly extract, can be directly used in field and use, eliminate loaded down with trivial details post-processed work.
Sum up above-mentioned existing preparation method, we find to there is following outstanding problem:
1. Some routes or starting raw material is expensive or severe reaction conditions or syntheti c route is long or wayward along reverse proportionality, cannot meet the outstanding problems such as natural ratio, the restriction application of the method and large-scale production, have impact on the widespread use of this technology.
2. individual method is prepared separately along anti-two components, just need can be used for Field information through later stage mixture, increases and uses difficulty.
Summary of the invention
The object of the invention is the shortcoming overcoming above-mentioned prior art, provides a kind of preparation method of the sex pheromone of Ostrinia furnacalis using C13 compound as starting raw material.Particularly the present invention be propose a kind of innovation first, uniqueness " 13C+1C " synthesis strategy is used for the chemical preparation of sex pheromone of Ostrinia furnacalis, there is low raw-material cost, synthetic route be short, synthesis condition is simple, total recovery high, be applicable to suitability for industrialized production.
Sex pheromone of Ostrinia furnacalis (Z, E)-12-tetradecene-1-alcohol acetate (1,2) structural formula of the present invention is shown below, and the two proportion of composing is approximately 27:73 (relative percentage).
A kind of sex pheromone of Ostrinia furnacalis novel preparation method using C13 compound as starting raw material of the present invention, comprises following preparation process:
1) 1,13-undecane dicarboxylic acid is reduced to 1,13-tridecane diols.
Get 1; 13-undecane dicarboxylic acid is (as round-bottomed flask) in reaction vessel; add anhydrous THF (tetrahydrofuran (THF)) to dissolve; lithium aluminum hydride is added, room temperature reaction 10 ~ 15 hours, after reaction terminates under ice bath and nitrogen protection; the HCl solution dropwise adding massfraction 10 ~ 20% under ice bath is no longer overflowed to gas; suction filtration, divide 3 ~ 5 washing leaching cakes by 15 ~ 25ml ethyl acetate, filtrate uses anhydrous MgSO
4drying, obtains white solid crude product, i.e. 1,13-tridecane diols crude product after revolving steaming; Wherein 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.
2) the monolateral esterification of 1,13-tridecane diols generates 13-hydroxyl 13 carbon-1-alcohol acetic ester.
Get 1,13-tridecane diols crude product is in reaction vessel, add hexanaphthene, 55 ~ 60 DEG C of stirring and dissolving, in 10 ~ 30 minutes, in reaction vessel, drip the aqueous solution containing Glacial acetic acid and the vitriol oil, wherein Glacial acetic acid concentration is 0.7 ~ 0.9mol/L, vitriol oil concentration is 0.002 ~ 0.003mol/L, and 55 ~ 60 DEG C are reacted 8 ~ 12 hours, are cooled to room temperature, separatory, organic phase first uses 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, column chromatography purification, obtains white solid 13-hydroxyl 13 carbon-1-alcohol acetic ester; Wherein in cyclohexane solution, the concentration of 1,13-tridecane diols is 20 ~ 30mg/mL; The consumption mol ratio of 1,13-tridecane diols and Glacial acetic acid is 1:80 ~ 90.
3) 13-hydroxyl 13 carbon-1-alcohol acetic ester is monolateral is oxidized to 13-aldehyde radical 13 carbon-1-alcohol acetic ester.
Get PCC (pyridinium chlorochromate) and be placed in reaction vessel, add methylene dichloride under room temperature to dissolve, in reaction vessel, add 13-hydroxyl 13 carbon-1-alcohol acetic ester, stirring at room temperature, TLC monitors reaction process, after 3 ~ 5 hours, reaction terminates, suction filtration, 5 ~ 15ml anhydrous diethyl ether washing leaching cake 2 ~ 3 times, filtrate revolves steaming, crude by column chromatography purifying, 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 in reaction vessel, be dissolved in anhydrous THF (tetrahydrofuran (THF)), add potassium tert.-butoxide under nitrogen protection, stirring at room temperature 20 ~ 45min, obtains yellow solution; At-20 ~-30 DEG C, to be dissolved in the 13-aldehyde radical 13 carbon-1-alcohol acetic ester in anhydrous THF (tetrahydrofuran (THF)), dropwise join in reaction flask, TLC monitors, after after 8 ~ 12 hours, reaction terminates, 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 DEG C, after being cooled to room temperature, anhydrous THF is dissolved in reaction vessel, triphenylphosphine is added under nitrogen protection, stir 20 ~ 45min, sodium borohydride is added at-5 ~ 15 DEG C, stir 20 ~ 40min, to be dissolved in the 13-tetradecene-1-alcohol acetic ester in THF, dropwise slowly add in reaction system, low temperature stirs, TLC monitors, after 3 ~ 6 hours, reaction terminates, , add 5 ~ 10mL, the cancellation of 2mol/L HCl solution is reacted, 2 times are extracted with 5 ~ 15ml anhydrous diethyl ether, 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.
A kind of sex pheromone of Ostrinia furnacalis novel preparation method using C13 compound as starting raw material of the present invention, 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) analyzes, 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 chemical shifts:
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) measures 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:
Get 1; 13-undecane dicarboxylic acid 1.2210g (5mmol) is in the 150ml round-bottomed flask of drying; add anhydrous THF (tetrahydrofuran (THF)) 50ml to dissolve, add lithium aluminum hydride 0.5690g (15mmol) under ice bath and nitrogen protection, room temperature reaction 12 hours.After reaction terminates, dropwise add 10% (mass ratio) HCl solution under ice bath and no longer overflow to gas, suction filtration, divide 3 washing leaching cakes by 20ml ethyl acetate, filtrate uses anhydrous MgSO
4dry.White solid crude product 1.0824g, i.e. 1,13-tridecane diols crude product, productive rate and lower step joint account is obtained after revolving steaming.
Embodiment 2:
Get 1.0818g (5mmol) 1,13-tridecane diols crude product is in 250ml round-bottomed flask, add hexanaphthene 40ml to dissolve, 55 DEG C of stirring and dissolving, in 10 minutes, drip the aqueous solution having dissolved 23ml Glacial acetic acid, the 0.08ml vitriol oil in 30ml water in reaction flask, 55 DEG C are reacted 10 hours, are cooled to room temperature, separatory, organic phase first uses the saturated NaHCO of 20ml
3solution washing 2 times, rear 20ml saturated common salt water washing 2 times, revolve and steam 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 yield 65%.
Embodiment 3:
Get 0.6466g (3mmol) PCC (pyridinium chlorochromate) and be placed in 50ml round-bottomed flask, add 15ml methylene dichloride under room temperature to dissolve, 0.5168g (2mmol) 13-hydroxyl 13 carbon-1-alcohol acetic ester is added in reaction flask, stirring at room temperature, TLC monitors, after 3 hours, reaction terminates, suction filtration, 10ml anhydrous diethyl ether washing leaching cake 2 times, filtrate revolves steaming, crude by 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 in 50ml round-bottomed flask, be dissolved in the anhydrous THF of 10ml (tetrahydrofuran (THF)); 0.2244g (2mmol) potassium tert.-butoxide is added under nitrogen protection; stirring at room temperature 30min, obtains yellow solution.At-20 DEG C, to be dissolved in 0.3076g (1.2mmol) the 13-aldehyde radical 13 carbon-1-alcohol acetic ester in the anhydrous THF of 5ml (tetrahydrofuran (THF)), dropwise join in reaction flask, TLC monitors, after after 10 hours, reaction terminates, 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 the vacuum-drying 8 hours at 135 DEG C of 0.2855g (1.2mmol) waterless cobaltous chloride, after being cooled to room temperature, the anhydrous THF of 10ml is dissolved in 50ml round-bottomed flask, 0.9442g (3.6mmol) triphenylphosphine is added under nitrogen protection, stir 30min, 0.0454g (1.2mmol) sodium borohydride is added at-10 DEG C, stir 30min, by 0.4681g (1.84mmol) 13-tetradecene-1-alcohol acetic ester be dissolved in 5ml THF, dropwise slowly add in reaction system, low temperature stirs, TLC monitors, after 4 hours, reaction terminates, add 5ml 2mol/L HCl solution cancellation reaction, 2 times are extracted with 10ml anhydrous diethyl ether, merge organic phase, concentrate to obtain crude product, 5ml n-hexane extraction crude product twice, 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. take C13 compound as the method that sex pheromone of Ostrinia furnacalis prepared by raw material, its step is as follows:
1) 1,13-undecane dicarboxylic acid is reduced to 1,13-tridecane diols
Get 1; 13-undecane dicarboxylic acid is in reaction vessel; add anhydrous THF to dissolve; lithium aluminum hydride is added, room temperature reaction 10 ~ 15 hours, after reaction terminates under ice bath and nitrogen protection; the HCl solution dropwise adding massfraction 10 ~ 20% under ice bath is no longer overflowed to gas; suction filtration, divide 3 ~ 5 washing leaching cakes by 15 ~ 25ml ethyl acetate, filtrate uses anhydrous MgSO
4drying, obtains white solid crude product, i.e. 1,13-tridecane diols crude product after revolving steaming;
2) the monolateral esterification of 1,13-tridecane diols generates 13-hydroxyl 13 carbon-1-alcohol acetic ester
Get 1,13-tridecane diols crude product is in reaction vessel, add hexanaphthene to dissolve, 55 ~ 60 DEG C of stirring and dissolving, in 10 ~ 30 minutes, in reaction vessel, drip the aqueous solution containing Glacial acetic acid and the vitriol oil, wherein Glacial acetic acid concentration is 0.7 ~ 0.9mol/L, vitriol oil concentration is 0.002 ~ 0.003mol/L, and 55 ~ 60 DEG C are reacted 8 ~ 12 hours, are cooled to room temperature, separatory, organic phase first uses 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, column chromatography purification, obtains white solid 13-hydroxyl 13 carbon-1-alcohol acetic ester;
3) 13-hydroxyl 13 carbon-1-alcohol acetic ester is monolateral is oxidized to 13-aldehyde radical 13 carbon-1-alcohol acetic ester
Get pyridinium chlorochromate and be placed in reaction vessel, add methylene dichloride under room temperature to dissolve, in reaction vessel, add 13-hydroxyl 13 carbon-1-alcohol acetic ester, stirring at room temperature, TLC monitors, after 3 ~ 5 hours, reaction terminates, suction filtration, 5 ~ 15ml anhydrous diethyl ether washing leaching cake 2 ~ 3 times, filtrate revolves steaming, crude by column chromatography purifying, 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 in reaction vessel, be dissolved in anhydrous THF, add potassium tert.-butoxide under nitrogen protection, stirring at room temperature 20 ~ 45min, obtains yellow solution; At-20 ~-30 DEG C, to be dissolved in the 13-aldehyde radical 13 carbon-1-alcohol acetic ester in anhydrous THF, dropwise join in reaction flask, TLC monitors, after after 8 ~ 12 hours, reaction terminates, 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 DEG C, after being cooled to room temperature, anhydrous THF is dissolved in reaction vessel, triphenylphosphine is added under nitrogen protection, stir 20 ~ 45min, sodium borohydride is added at-5 ~ 15 DEG C, stir 20 ~ 40min, to be dissolved in the 13-tetradecene-1-alcohol acetic ester in THF, dropwise slowly add in reaction system, low temperature stirs, TLC monitors, after 3 ~ 6 hours, reaction terminates, add 5 ~ 10mL, the cancellation of 2mol/L HCl solution is reacted, 2 times are extracted with 5 ~ 15ml anhydrous diethyl ether, 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. a kind of is as claimed in claim 1 the method that sex pheromone of Ostrinia furnacalis prepared by raw material with C13 compound, it is characterized in that: step 1) in, 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. a kind of is as claimed in claim 1 the method that sex pheromone of Ostrinia furnacalis prepared by raw material with C13 compound, it is characterized in that: step 2) in cyclohexane solution, the concentration of 1,13-tridecane diols is 20 ~ 30mg/mL; The consumption mol ratio of 1,13-tridecane diols and Glacial acetic acid is 1:80 ~ 90.
4. a kind of is as claimed in claim 1 the method that sex pheromone of Ostrinia furnacalis prepared by raw material with C13 compound, it is characterized in that: step 3) 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.
5. a kind of is as claimed in claim 1 the method that sex pheromone of Ostrinia furnacalis prepared by raw material with C13 compound, it is characterized in that: step 4) 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.
6. a kind of is as claimed in claim 1 the method that sex pheromone of Ostrinia furnacalis prepared by raw material with C13 compound, it is characterized in that: step 5) 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.
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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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| 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)
| Title |
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| Sex pheromone of the Asian Corn Borer;J.A.Klun et al;《Life Sciences》;19801231;第27卷(第17期);第1603-1606页 * |
| Synthesis and Biological Test of the Pheromone of the Asian Corn Borer Moth(Ostrinia furnacalis);Suk-ku Kang et al;《Bulletin of Korean Chemical Society》;19851231;第6卷(第1期);第15-19页 * |
| 亚洲玉米螟性信息素合成研究进展;刘伟 等;《安徽农业科学》;20131231;第41卷(第20期);第8531-8535页 * |
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