CN101665430A - Method for synthesizing tetradecene alcohol acetic ester in ostrinia nubilalis sex pheromone - Google Patents
Method for synthesizing tetradecene alcohol acetic ester in ostrinia nubilalis sex pheromone Download PDFInfo
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- CN101665430A CN101665430A CN200910152994A CN200910152994A CN101665430A CN 101665430 A CN101665430 A CN 101665430A CN 200910152994 A CN200910152994 A CN 200910152994A CN 200910152994 A CN200910152994 A CN 200910152994A CN 101665430 A CN101665430 A CN 101665430A
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Abstract
The invention discloses a method for synthesizing tetradecene alcohol acetic ester in ostrinia nubilalis sex pheromone, which takes ethyltriphenylphosphonium bromide and 1, 12-codlemone as starting materials. The method comprises the following steps: the 1, 12-codlemone is subjected to a unilateral transesterification reaction to obtain 12-hydroxy dodecanol acetic ester, and then subjected to an oxidation reaction to obtain 12-oxo dodecanol acetic ester which is in a Wittig reaction with the ethyltriphenylphosphonium bromide to obtain (Z/E)-12 tetradecenoic alcohol acetic ester of high cis-trans ratio in Asian ostrinia nubilalis sex pheromone. The invention has the advantages of simple and reasonable synthesis route, convenient and safe operation, high usage ratio of raw materials, short synthesis time and the like.
Description
Technical field
The present invention relates to a kind of chemical synthesis process of major ingredient compound (Z/E)-12-tetradecene alcohol acetic ester of sex pheromone of Ostrinia furnacalis.
Background technology
Ostrinia furnacalis (Ostrinia furnacalis Guenee) is the primary pest of the Far East Area's harm corn, the contour bar crop of Chinese sorghum, is widely distributed within the border in China.Corn is one of important farm crop of generally planting of China, and there is serious harm in Ostrinia furnacalis to China's maize yield and quality.The Pyrausta nubilalis (Hubern). feeding habits are very assorted, are the primary pests of corn, and the various piece outside the milpa of can causing harm during plague of insects generation is dug up the roots makes the afunction partly of being injured to significantly reduce corn kernel.General but the time corn underproduction 10% takes place, the outbreak year corn underproduction even can surpass can 30%.Pyrausta nubilalis (Hubern). pierces the stem stalk with larva causes harm, and more hidden, agricultural chemicals is difficult to tag; Simultaneously, this worm survives the winter in maize straw, cob or root stubble with mature larva; Maize straw can not all be handled in winter again, makes that the Pyrausta nubilalis (Hubern). hibernating base is huge; Therefore, difficulty of prevention and cure is very big.
The peasant abuses height poisons the medicine of learning to farm, severe contamination farmland, fruits and vegetables and surrounding environment, cause the pesticide residue severe overweight in the fruit and vegetable food, have a strong impact on the healthy of human consumer, bring obstruction also for simultaneously the outlet of fruits and vegetables, after especially states such as Japan, European Union have strengthened agricultural residual standard to agricultural products in China.This a series of problem has proposed new requirement and challenge for our pest control.Therefore, exploitation is new, effectively prediction and the method for preventing and treating seem very urgent.
Modal in the world at present pest control technology comprises natural enemy, microorganism, chemical pesticide and semiochemicals technology.Wherein, the semiochemicals technology has single-minded selectivity, low risk and advantages of environment protection, causes the attention of global various countries gradually and applies.
The evaluation of the pheromone compound of Pyrausta nubilalis (Hubern)., synthetic and applied research start from the seventies in last century.Synthetic method about compound in the sex pheromone of Ostrinia furnacalis (Z/E)-12-tetradecene alcohol acetic ester all has report: Klun both at home and abroad
1., Ando
2., Du Jiawei
3.Deng being intermediate with the long-chain alkynol, Li Zhengming
4.Deng the use organoboron reagent, finished this sex pheromone synthetic (respectively referring to 1., Klun J A, Bierl-Leonhardt B A, Schwarz M, et al.SexPheromone of the Asian Corn Borer Moth[J] .Life Science, 1980,27 (17): 1603-1606.; 2., Ando T, Saito C, Arai K, et al. (Z)-and (E)-12-Tetradecenyl Acetates:SexPheromone of Oriental Corn Borer (Lepidoptera:Pyralidae) [J] .Agric Biol Chem, 1980,44 (11): 2643-2649.; 3., Zhu Yuxin, Wang Meizhen, Du Jiawei. the improvement of sex pheromone of Ostrinia furnacalis is synthetic, entomology research collected papers [C]. the 7th collection, Shanghai: Shanghai science tech publishing house, 1987,13-17.), there are problems such as raw material costliness, severe reaction conditions, step length in above method; Chen Jiawei
5., Liu Fuchu
6., Li Jiuming
7.Deng with 1,12-12 carbon, two pure and mild 10-undecylenic alcohols or Z-15-tetracosenoic acid or 10-hydroxydecanoic acid are starting raw material, by polystep reaction obtain this pheromone (respectively referring to 5., Chen Jiawei, Jiang Jilong, Lu Jun. [J] synthesized in the improvement of sex pheromone of Ostrinia furnacalis. organic chemistry, 1989,9:80-83.; 6., Liu Fuchu, Lin Jun. easy to be synthetic [J] of sex pheromone of Ostrinia furnacalis. organic chemistry, 1995,15:546-549.; 7., Li Jiuming, Huang Guozheng, harmony is built equality. the new synthetic method of sex pheromone of Ostrinia furnacalis [J]. agricultural chemicals, 2007,46 (6): 388-389.), above method exists all that experimental procedure is tediously long, problem such as operation inconvenience etc.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect that prior art exists, and provide a kind of raw material cheap and easy to get, synthetic route advantages of simple of adopting, convenient and safe operation, the raw material availability height, the synthetic method of tetradecene alcohol acetic ester in the compound in the sex pheromone of Ostrinia furnacalis of generated time weak point.
For achieving the above object, technical scheme of the present invention is with ethyltriphenylphosphonium bromide and 1,12-12 carbon glycol are starting raw material, described 1,12-12 carbon glycol get 12-hydroxyl 12 carbon alcohol acetic esters through monolateral esterification, again through peroxidation, obtain 12-oxo 12 carbon alcohol acetic esters, described ethyltriphenylphosphonium bromide and 12-oxo 12 carbon alcohol acetic esters react through Wittig, obtain (the Z/E)-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis of high cis-to-trans ratio.The suitable inverse ratio of (the Z/E)-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis of the high cis-to-trans ratio that this step obtains is 90/10.
Further be provided be with (the Z/E)-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis of high cis-to-trans ratio through configuration conversion, obtain low (Z/E)-12-tetradecene alcohol acetic ester along inverse ratio.The suitable inverse ratio of (Z/E)-12-tetradecene alcohol acetic ester of the low suitable inverse ratio that this step obtains is 25/75.
Because (Z/E)-12-tetradecene alcohol acetic ester contained in the sex pheromone of each geographic Ostrinia furnacalis has nothing in common with each other along inverse ratio, therefore can be with the Z/E of the above-mentioned high remy hair ratio that makes)-12-tetradecene alcohol acetic ester and low (Z/E)-12-tetradecene alcohol acetic ester along inverse ratio mix (Z/E)-12-tetradecene alcohol acetic ester that can obtain multiple suitable inverse ratio, to adapt to each geographic actual needs.
Reaction synthetic route of the present invention is as follows
Further being provided with is described 1, the monolateral esterification of 12-12 carbon glycol is with 1,12-12 carbon glycol are dissolved in 60-80 ℃ the toluene, add the vitriol oil of 98% massfraction of catalytic amount and the Glacial acetic acid of 100% molecular fraction, stopped reaction after 120-125 ℃ of following backflow 12-36 hour, desolventize and dissolution residual substance through decompression, washing, drying is after concentrating, obtain 12-hydroxyl 12 carbon alcohol acetic esters through column chromatography, eluent is sherwood oil and ethyl acetate.
Further setting is that the oxidizing reaction of described 12-hydroxyl 12 carbon alcohol acetic esters is that 12-hydroxyl 12 carbon alcohol acetic esters are dissolved in the exsiccant methylene dichloride, the pyridinium chlorochromate that adds the 120-150% molecular fraction, stir after 3-5 hour under the room temperature, after filtration, decompression desolventizes and dissolution residual substance, washing, dry, after concentrating, obtain 12-oxo 12 carbon alcohol acetic esters through column chromatography, eluent is sherwood oil and ethyl acetate.
Further be provided with is that described Wittig reaction is that ethyltriphenylphosphonium bromide with the 120-140% molecular fraction is dissolved in the anhydrous tetrahydro furan; fully be cooled under the protection of inert gas-20-0 ℃ after; the potassium tert.-butoxide powder that in batches adds the 120-140% molecular fraction; the tetrahydrofuran solution that adds compound 12-oxo 12 carbon alcohol acetic esters after stirring reaction 30-60 minute; reacted 10-30 minute; through saturated ammonium chloride solution or the cancellation of 1-3mol/L dilute hydrochloric acid; the ether dilution; washing; dry; concentrate; rapid column chromatography obtains the thick product of (Z/E)-12-tetradecene alcohol acetic ester, obtains (Z/E)-12-tetradecene alcohol acetic ester of high cis-to-trans ratio again through underpressure distillation.
Further be provided with is that described configuration conversion reaction is heated to 70-75 ℃ with high cis-to-trans ratio (Z/E)-12-tetradecene alcohol acetic ester under protection of inert gas; add the sodium nitrite solution dilute nitric acid solution then successively; after stirring reaction 1-2 hour; be cooled to room temperature; through dilution, washing, drying; after concentrating, obtain low (Z/E)-12-tetradecene alcohol acetic ester along inverse ratio through column chromatography.
The invention has the advantages that: with inexpensive ethyltriphenylphosphonium bromide and 1,12-12 carbon glycol are starting raw material, can obtain target compound through the simple reaction operation of three steps; During preparation 12-hydroxyl 12 carbon alcohol acetic esters, avoid the organo-alkali compounds such as acetic anhydride, Acetyl Chloride 98Min. and pyridine that use price relatively costly, 1 of the bilateral esterification of unique by product of reaction, 12-12 carbon glycol can be converted into raw material and reuse; The preparation of 12-oxo 12 carbon alcohol acetic esters adopts PCC as oxygenant, the productive rate height, and side reaction is few, and crude product can not add and carries out next step Wittig reaction discretely; Ethyltriphenylphosphonium bromide and 12-oxo 12 carbon alcohol acetic esters carry out the crude product compound of Wittig reaction gained through rapid column chromatography, just can obtain (Z/E)-12-tetradecene alcohol acetic ester through underpressure distillation again, along inverse ratio is 90/10, and total recovery is 45%; Again will along inverse ratio be (Z/E)-12-tetradecene alcohol acetic ester of 90/10 through configuration conversion, must be (Z/E)-12-tetradecene alcohol acetic ester of 25/75 along inverse ratio.The relatively inexpensive raw material that is easy to get of whole process using, the experimental procedure advantages of simple, easy to operation, the raw material availability height, main compound (Z/E)-12-tetradecene alcohol acetic ester in synthetic sex pheromone of Ostrinia furnacalis within a short period of time is fit to suitability for industrialized production at lower cost.
Below in conjunction with embodiment the present invention is done further introduction.
Embodiment
Below by embodiment the present invention is carried out concrete description; only be used for the present invention is further specified; can not be interpreted as the qualification to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Synthesizing of 12-hydroxyl 12 carbon alcohol acetic esters: dropping funnel is being housed, is adding 1 in the 1L three-necked bottle of water trap and prolong, 12-12 carbon glycol 50.0g (0.24mol) and toluene (500mL), be heated to 70 ℃, be stirred to the solid dissolving, and dropping vitriol oil 0.65mL (1.2g, 12mmol); Be heated to backflow, slowly drip Glacial acetic acid 13.8mL (14.5g, toluene 0.24mol) (50mL) solution.Drip off and continue to reflux 20 hours.Cooling removes by filter precipitate, and (2 * 50mL), filtrate decompression concentrates precipitate, and resistates is dissolved in ethyl acetate, and combined ethyl acetate solution is used saturated sodium bicarbonate and saturated common salt water washing, anhydrous magnesium sulfate drying successively with the ethyl acetate washing.Concentrating under reduced pressure, crude product gets white powder solid 30.3g through column chromatography purification, reclaims unreacted glycol 10.2g, the glycol 13.5g of bilateral esterification, yield: 87%.
Synthesizing of Z/E-12-tetradecene alcohol acetic ester 1/2: in the exsiccant flask, add 12-hydroxyl 12 carbon alcohol acetic ester 30.3g (124mmol) and dry methylene chloride (400mL), after treating the solid dissolving, add pyridinium chlorochromate drone salt 35.3g (161mmol) under stirring in batches, add and continue to stir 4 hours.Filter, (2 * 50mL), filtrate decompression concentrates residue, and resistates is dissolved in ether, merges diethyl ether solution, uses dilute hydrochloric acid, saturated sodium bicarbonate and saturated common salt water washing successively, anhydrous magnesium sulfate drying with the ether washing.Concentrating under reduced pressure, crude product are directly used in next step reaction.
Ethyltriphenylphosphonium bromide 64.4g (174mmol) is dissolved in exsiccant tetrahydrofuran (THF) (350mL), under ice bath and argon shield, adds potassium tert.-butoxide pressed powder 18.0g (161mmol) in batches, stirred 30 minutes, get red solution.Slowly drip the tetrahydrofuran solution (slow as far as possible, the speed of dropping directly influences yield) of above-mentioned crude product.Stirred 10 minutes, and slowly added saturated ammonium chloride solution cancellation reaction, add the ether diluting reaction, use saturated ammonium chloride solution and saturated common salt water washing successively, anhydrous magnesium sulfate drying.Filter, concentrate, through the thick product of rapid column chromatography gained again through underpressure distillation (120-122 ℃/0.2mmHg) colourless liquid 16.4g, yield: 52%, Z/E=90/10.
The configuration conversion of Z/E-12-tetradecene alcohol acetic ester 1/2: get the said products 10.1g and place flask; under argon shield, be heated to 75 ℃; add sodium nitrite solution 2.5mL (2mol/L) and salpeter solution 1.7mL (2mol/L) then successively, continue reaction 1 hour.Be cooled to room temperature, add the normal hexane dilute reaction solution, use saturated sodium bicarbonate solution, distilled water and saturated common salt water washing successively, anhydrous magnesium sulfate drying.Filter, concentrate, through the colourless liquid 10.0g of column chromatography, yield is near 100%, Z/E=25/75.
Claims (6)
1. the synthetic method of tetradecene alcohol acetic ester in the nubilalis sex pheromone, it is characterized in that: with ethyltriphenylphosphonium bromide and 1,12-12 carbon glycol are starting raw material, described 1,12-12 carbon glycol get 12-hydroxyl 12 carbon alcohol acetic esters through monolateral esterification, again through peroxidation, obtain 12-oxo 12 carbon alcohol acetic esters, described ethyltriphenylphosphonium bromide and 12-oxo 12 carbon alcohol acetic esters react through Wittig, obtain (the Z/E)-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis of high cis-to-trans ratio.
2. the synthetic method of tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 1, it is characterized in that: (the Z/E)-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis of high cis-to-trans ratio through configuration conversion, must be hanged down (the Z/E)-12-tetradecene alcohol acetic ester along inverse ratio.
3. the synthetic method of tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 1 and 2, it is characterized in that: described 1, the monolateral esterification of 12-12 carbon glycol is with 1,12-12 carbon glycol are dissolved in the 60-80 ℃ of toluene, the vitriol oil of 98% massfraction of adding catalytic amount and the Glacial acetic acid of 100% molecular fraction, stopped reaction after 120-125 ℃ of following backflow 12-36 hour, desolventize and dissolution residual substance through decompression, washing, dry, after concentrating, obtain 12-hydroxyl 12 carbon alcohol acetic esters through column chromatography, eluent is sherwood oil and ethyl acetate.
4. the synthetic method of tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 3, it is characterized in that: the oxidizing reaction of described 12-hydroxyl 12 carbon alcohol acetic esters is that 12-hydroxyl 12 carbon alcohol acetic esters are dissolved in the exsiccant methylene dichloride, the pyridinium chlorochromate that adds the 120-150% molecular fraction, stir after 3-5 hour under the room temperature, after filtration, decompression desolventizes and dissolution residual substance, washing, dry, after concentrating, obtain 12-oxo 12 carbon alcohol acetic esters through column chromatography, eluent is sherwood oil and ethyl acetate.
5. according to the synthetic method of tetradecene alcohol acetic ester in claim 1 or the 2 or 4 described nubilalis sex pheromones, it is characterized in that: described Wittig reaction is that the ethyltriphenylphosphonium bromide with the 120-140% molecular fraction is dissolved in the anhydrous tetrahydro furan, rare gas element protects down fully and is cooled to-20-0 ℃ after, the potassium tert.-butoxide powder that in batches adds the 120-140% molecular fraction, the tetrahydrofuran solution that adds compound 12-oxo 12 carbon alcohol acetic esters after stirring reaction 30-60 minute, reacted 10-30 minute, through saturated ammonium chloride solution or the cancellation of 1-3mol/L dilute hydrochloric acid, the ether dilution, washing, dry, concentrate, rapid column chromatography obtains the thick product of (Z/E)-12-tetradecene alcohol acetic ester, obtains (Z/E)-12-tetradecene alcohol acetic ester of high cis-to-trans ratio again through underpressure distillation.
6. the synthetic method of tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 5; it is characterized in that: described configuration conversion reaction is heated to 70-75 ℃ with high cis-to-trans ratio (Z/E)-12-tetradecene alcohol acetic ester under protection of inert gas; add the sodium nitrite solution dilute nitric acid solution then successively; stirring reaction 1-2 hour; be cooled to room temperature; through dilution; washing; dry; after concentrating, obtain low (Z/E)-12-tetradecene alcohol acetic ester along inverse ratio through column chromatography.
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| CN101906034A (en) * | 2010-07-23 | 2010-12-08 | 北京中捷四方生物科技有限公司 | Synthesizing method of oriental fruit moth sex pheromone 8(Z/E)-dodecylene-1-alcohol acetate |
| CN102795998A (en) * | 2012-08-23 | 2012-11-28 | 昆明博鸿生物科技有限公司 | Method for synthesis of sex pheromone compound of grapholitha molesta |
| CN103288635A (en) * | 2013-06-24 | 2013-09-11 | 黑龙江省科学院微生物研究所 | Preparation method of 12-tetradecadienyl acetate of corn borer sex pheromone |
| 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 |
| CN103694117A (en) * | 2014-01-07 | 2014-04-02 | 吉林大学 | Novel method for preparing asiatic corn borer sex pheromone from tridecane compound |
| 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 |
| CN110028405A (en) * | 2019-04-30 | 2019-07-19 | 北京林业大学 | A method of synthesizing cis- 3- tetradecene alcohol acetic ester and trans- 3- tetradecene alcohol acetic ester |
| CN112574032A (en) * | 2020-12-29 | 2021-03-30 | 山东省农药科学研究院 | Improved method for preparing (Z, E) -12-tetradecene-1-alcohol acetate |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101906034A (en) * | 2010-07-23 | 2010-12-08 | 北京中捷四方生物科技有限公司 | Synthesizing method of oriental fruit moth sex pheromone 8(Z/E)-dodecylene-1-alcohol acetate |
| CN101906034B (en) * | 2010-07-23 | 2012-11-28 | 北京中捷四方生物科技有限公司 | Synthesizing method of oriental fruit moth sex pheromone 8(Z/E)-dodecylene-1-alcohol acetate |
| CN102795998A (en) * | 2012-08-23 | 2012-11-28 | 昆明博鸿生物科技有限公司 | Method for synthesis of sex pheromone compound of grapholitha molesta |
| 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 |
| CN103288635A (en) * | 2013-06-24 | 2013-09-11 | 黑龙江省科学院微生物研究所 | Preparation method of 12-tetradecadienyl acetate of corn borer sex pheromone |
| CN103694117A (en) * | 2014-01-07 | 2014-04-02 | 吉林大学 | Novel method for preparing asiatic corn borer sex pheromone from tridecane compound |
| CN103694117B (en) * | 2014-01-07 | 2015-03-25 | 吉林大学 | Method for preparing Asiatic corn borer sex pheromone from tridecane compound |
| 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 |
| CN110028405A (en) * | 2019-04-30 | 2019-07-19 | 北京林业大学 | A method of synthesizing cis- 3- tetradecene alcohol acetic ester and trans- 3- tetradecene alcohol acetic ester |
| CN112574032A (en) * | 2020-12-29 | 2021-03-30 | 山东省农药科学研究院 | Improved method for preparing (Z, E) -12-tetradecene-1-alcohol acetate |
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