CN103288635A - Preparation method of 12-tetradecadienyl acetate of corn borer sex pheromone - Google Patents
Preparation method of 12-tetradecadienyl acetate of corn borer sex pheromone Download PDFInfo
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Abstract
The invention belongs to the field of corn borer sex pheromone, and discloses a preparation method of 12-tetradecadienyl acetate of the corn borer sex pheromone. Raw materials of the method are cheap and easily available. A stereochemical structure of a Grignard reagent which is used in the method enables that the stereoisomerism of a double bond is not encountered in reaction processes, product is single, operation is convenient and safe, raw material utilization ratio is high, synthetic route is simple and reasonable, and two main components of cis(trans)-12-tetradecadienyl acetate are synthesized. Cis-4-hexen-1-ol and 1,8-octanediol are taken as the initial raw materials of Z-12-tetradecadienyl acetate; the Grignard reagent is produced from 1,8-octanediol; cis-4-hexen-1-ol reacts with 4-toluene sulfonyl chloride and then the product and 8-magnesium bromide-1-octanol tetrahydropyran are subjected to Grignard coupling reaction; the product is subjected to deprotection and esterification; and then Z-12-tetradecadienyl acetate is obtained. E-12-tetradecadienyl acetate is obtained by subjecting crotonyl alcohol and 1, 10-decanediol to the reaction processes listed above. The 12-fourteen carbon enol acetate of the invention is used as sex pheromone for corn borer control.
Description
Technical field
The invention belongs to the nubilalis sex pheromone field; Anti--12-tetradecene alcohol acetic ester method in suitable in the synthetic nubilalis sex pheromone-12-tetradecene alcohol acetic ester and the nubilalis sex pheromone is specifically disclosed.
Background technology
Ostrinia furnacalis (Ostrinia fumacalis Guenee) is the primary pest of crops such as harm corn, Chinese sorghum, is widely distributed within the border in China.General but the time corn underproduction 10% takes place, serious year corn underproduction takes place 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, and difficulty of prevention and cure is very big.For a long time, the main chemical pesticide that relies on of Pyrausta nubilalis (Hubern). control, but because some habits of Pyrausta nubilalis (Hubern). itself, as the feeding habits complexity, the harm of larva moth food, the moth emergence period is long etc., has brought certain difficulty to chemical prevention.The life-time service agricultural chemicals, the Pyrausta nubilalis (Hubern). resistance increases, and preventive effect obviously descends, and natural enemy quantity reduces, and ecotope is fragile day by day.This a series of problem has proposed new requirement and challenge for our pest control.At present modal pest control technology comprises natural enemy, microorganism, chemical pesticide and based on the gyplure technology of insect sex pheromone in the world.Wherein, the insect sex pheromone technology has single-minded selectivity, low risk and advantages of environment protection, causes the attention of global various countries gradually and applies.China classifies gyplure control of maize snout moth's larva technology as the green prevention and control technology.
Sex pheromone of Ostrinia furnacalis is discharged by the female moth of Ostrinia furnacalis, can lure the sex pheromone of male moth mating of the same race, and main component is suitable-12-tetradecene yl acetate and anti--12-tetradecene yl acetate.
Following several route of synthesis is arranged at present:
A kind of approach is to be that intermediate synthesizes sex pheromone of Ostrinia furnacalis with the long-chain alkynol, all on the books in following document: KLUN J A, BIERL-LEONHARDT B A, SCHWARZ M Sex pheromone of the Asian corn borer moth1980,27 (17); ANDO T.SAITO C.ARAI K (Z)-and (E)-12-tetradecenyl acetates:sex pheromone of oriental corn borer (Lepidoptera:Pyratidae) 1980 (11); Zhu Yuxin, Wang Meizhen. the improvement of the tame latitude sex pheromone of Ostrinia furnacalis of shutting out synthetic 1987.
Another kind of approach is Li Zhengming, and is disclosed in novel method 1984 (1) documents of a SCHW ARZ M synthetic Ostrinia furnacalis sex pheromone: as to be to use organoboron reagent to finish sex pheromone of Ostrinia furnacalis.
It is problems such as Z/E body mixture that above-mentioned two methods exist raw material costliness, severe reaction conditions, synthetic route length, reactant.
Also having a kind of approach is 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, obtain this pheromone by polystep reaction, be recorded in the following document: Chen Jiawei, Jiang Jilong. the improvement of Lu Jun sex pheromone of Ostrinia furnacalis synthetic 1989 (9); Liu Fuchu, easy synthetic 1995 of woods army sex pheromone of Ostrinia furnacalis; Li Jiuming, Huang Guozheng, Yong Jianping, A Jiaike Baeyer. the new synthetic method agricultural chemicals 2007 (6) of Chinese mugwort Sa sex pheromone of Ostrinia furnacalis; Chen Haibin, the simple and easy synthesis method agricultural chemicals journal 2012 (12) of the equal sex pheromone of Ostrinia furnacalis of Du Yong.
Aforesaid method exists that severe reaction conditions, reaction preference are not high, reactant is problems such as Z/E body mixture.
Summary of the invention
In order to overcome the shortcoming and defect that prior art exists, the present invention adopts raw material cheap and easy to get, utilizes the original three-dimensional arrangement of Grignard reagent, reaction process not to relate to three-dimensional arrangement variation, single, the convenient and safe operation of product of two keys, the raw material availability height, generated time is short, the synthetic route advantages of simple has been synthesized anti--two kinds of main components of 12-tetradecene alcohol acetic ester in suitable in the nubilalis sex pheromone-12-tetradecene alcohol acetic ester and the nubilalis sex pheromone.
Among the present invention in the nubilalis sex pheromone Z-12-tetradecene alcohol acetic ester be to be starting raw material with suitable-4-hexen-1-ol and 1,8-ethohexadiol; Raw material 1, the 8-ethohexadiol obtains 8-bromo-1-octanol through monolateral bromination, obtains 8-bromo-1-octanol tetrahydropyrans through the protection of 3,4-dihydropyrane again, gets 8-magnesium bromide-1-octanol tetrahydropyrans with reactive magnesium again; Raw material is suitable-and the 4-hexen-1-ol is through obtaining suitable-4-hexene-1-P-TOLUENE SULFO ACID 99 ester with the reaction of tosic acid chlorine; suitable-4-hexene-1-p-toluenesulfonic esters and 8-magnesium bromide-1-octanol tetrahydropyrans carries out the form linked reaction and obtains Z-12-tetradecene tetrahydropyrans, obtains Z-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis through deprotection, esterification again.
The preparation method of described 8-bromo-1-octanol adds 0.1mol1 in the three-necked bottle that dropping funnel, water trap and prolong are housed, 8-ethohexadiol, 300mL benzene and 0.1mol Hydrogen bromide, add 0.001mol iodine again, oil bath heating stirring and refluxing 30h under 100 ℃ of conditions, use dilute hydrochloric acid and the saturated common salt water washing of the aqueous sodium hydroxide solution, 10% (mass percent concentration) of 5% (mass percent concentration) successively, anhydrous magnesium sulfate drying filters, evaporation concentration is again through SiO
2Column chromatography purification gets 8-bromo-1-octanol;
The preparation method of described 8-bromo-1-octanol tetrahydropyrans is dissolved in 0.09mol8-bromo-1-octanol in the 100mL methylene dichloride, be cooled to 0 ℃ then, add the 0.018mol tosic acid, the speed of dividing with 5mL/ drips 0.109mol2, the 3-dihydropyrane, stir then and rise to room temperature, stir 10h under the room temperature, with 10mL～20mL saturated sodium bicarbonate aqueous solution termination reaction, use the extracted with diethyl ether after washing, with the saturated brine washing, use dried over mgso more again, evaporation concentration gets 8-bromo-1-octanol tetrahydropyrans;
The preparation method of described 8-magnesium bromide-1-octanol tetrahydropyrans is dissolved in the THF solution that obtains 8-bromo-1-octanol tetrahydrochysene pyrrole among the 100mLTHF with 0.09mol8-bromo-1-octanol tetrahydropyrans; under nitrogen protection; with magnesium powder 0.095mol; 0.01g iodine and 50mLTHF place three-necked bottle; under the magnetic agitation; THF solution to the iodine color that the speed of dividing with 5mL/ splashes into 8-bromo-1-octanol tetrahydropyrans disappears; the speed of dividing with 3mL/ drips the THF solution of remaining 8-bromo-1-octanol tetrahydropyrans then; stir 10h under the room temperature again, obtain 8-magnesium bromide-1-octanol tetrahydropyrans.
Described suitable-preparation method of 4-hexene-1-P-TOLUENE SULFO ACID 99 ester is as follows; With 0.1mol suitable-the 4-hexen-1-ol is dissolved in the 50mL pyridine, is cooled to 0 ℃, adds the 0.12mol Tosyl chloride, stirs and rises to room temperature after one hour, continues to be stirred to react completely, and adds 5mL water, stirs adding 50mL water after 20 minutes, with ether extraction three times; Ether extract with 2mol/L hydrochloric acid, saturated sodium bicarbonate aqueous solution and saturated brine washing, concentrates after the dried over mgso successively, obtains suitable-4-hexene-1-P-TOLUENE SULFO ACID 99 ester.
The preparation method of described Z-12-tetradecene tetrahydropyrans is as follows: under nitrogen protection ,-78 ℃ of conditions; with 0.095mol suitable-4-hexene-1-P-TOLUENE SULFO ACID 99 ester is dissolved among the anhydrous THF of 400mL; the speed of dividing with 5mL/ splashes into 8-magnesium bromide-1-octanol tetrahydropyrans; add 0.003mol four cupric chloride lithiums then; stir and rise to room temperature after one hour; stir and be warmed up to 45 degree continuation stirrings 1 hour after 14 hours; add 100mL saturated aqueous ammonium chloride termination reaction then; the extracted with diethyl ether after washing; wash with saturated salt again; concentrate SiO after the dried over mgso
2Column chromatography obtains Z-12-tetradecene tetrahydropyrans.
Described Z-12-tetradecene tetrahydropyrans deprotection, esterification process are as follows: 1.0g tosic acid and 22.5g Z-12-tetradecene tetrahydropyrans are dissolved among the THF of 200mL drying; add the 16.8g diacetyl oxide again; heating reflux reaction 8 hours; be chilled to room temperature then; add saturated sodium bicarbonate aqueous solution to pH value=7; use dichloromethane extraction again three times, then with concentrating SiO after the dried over mgso
2The post separation obtains Z-12-tetradecene acetic ester.
The route that Z-12-tetradecene alcohol acetic ester of the present invention synthesizes is as follows:
With inexpensive suitable-4-hexen-1-ol and 1, the 8-ethohexadiol is starting raw material, can obtain target compound (Z-12-tetradecene acetic ester) through the simple reaction operation of 6 steps, utilize the form linked reaction to import two keys and prepare the three-dimensional arrangement variation that 12-tetradecene alcohol acetic ester reaction process does not relate to two keys, can utilize the original three-dimensional arrangement synthesizing cis of small molecules enol 12-tetradecene alcohol acetic ester, the productive rate height, side reaction is few.The crude product compound of reaction gained just can obtain Z-12-tetradecene alcohol acetic ester, total recovery 63.01% (with 1,8-ethohexadiol meter) through underpressure distillation again through rapid column chromatography.Needn't pass through configuration conversion, the relatively inexpensive raw material that is easy to get of whole process using, simple and reasonable steps, easy to operation, the raw material availability height, product is unique, main compound Z-12 one tetradecene alcohol acetic ester in the synthetic sex pheromone of Ostrinia furnacalis is fit to suitability for industrialized production at lower cost.
Among the present invention in the nubilalis sex pheromone E-12-tetradecene alcohol acetic ester be with crotons pure and mild 1,10-certain herbaceous plants with big flowers glycol is starting raw material, wherein raw material 1,10-certain herbaceous plants with big flowers glycol obtains 10-bromo-1-certain herbaceous plants with big flowers alcohol through monolateral bromination, again through 2, the protection of 3-dihydropyrane obtains 10-bromo-1-octanol tetrahydropyrans, gets 10-bromo magnesium-1-octanol tetrahydropyrans with reactive magnesium again; Reaction obtains crotyl alcohol P-TOLUENE SULFO ACID 99 ester to the raw material crotyl alcohol through tosic acid chlorine; crotyl alcohol P-TOLUENE SULFO ACID 99 ester and 10-bromo magnesium-1-octanol tetrahydropyrans is E-12-tetradecene tetrahydropyrans after the form linked reaction again, again the E-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis that deprotection, esterification obtain.
The preparation method of described 10-bromo-1-certain herbaceous plants with big flowers alcohol is as follows: add 0.1mol1 in the three-necked bottle that dropping funnel, water trap and prolong are housed, 10-decanediol, 300ml toluene and 0.1mol Hydrogen bromide, add 0.001mol iodine again, oil bath heating stirring and refluxing 30h under 110 ℃ of conditions, stop heating, use dilute hydrochloric acid and the saturated common salt water washing of the aqueous sodium hydroxide solution, 10% (mass percent concentration) of 5% (mass percent concentration) successively, anhydrous magnesium sulfate drying then, filter, evaporation concentration is at SiO
2Column chromatography purification gets 10-bromo-1-certain herbaceous plants with big flowers alcohol;
The preparation method of described 10-bromo-1-octanol tetrahydropyrans is as follows: under nitrogen protection, 0.09mol10-bromo-1-certain herbaceous plants with big flowers alcohol is dissolved among the 200mL THF, be cooled to 0 ℃ then, add the 0.018mol tosic acid, the speed of dividing with 5mL/ drips 0.109mol2, the 3-dihydropyrane, stir then and rise to room temperature, continue to stir 10 hours, use the saturated sodium bicarbonate aqueous solution termination reaction, the extracted with diethyl ether after washing is washed with saturated salt again, dried over mgso, evaporation concentration obtain 10-bromo-1-octanol tetrahydropyrans;
The method of the preparation of described E-12-tetradecene tetrahydropyrans is as follows: 0.09mol10-bromo-1-octanol tetrahydropyrans is dissolved in the THF solution that obtains 10-bromo-1-octanol tetrahydropyrans among the 200mLTHF; under nitrogen protection; with 0.095mol magnesium powder; 0.01g iodine and 50mLTHF place three-necked bottle; under the magnetic agitation; splashing into THF solution to the iodine color that the 10-bromo-1-certain herbaceous plants with big flowers alcohol tetrahydrochysene is muttered with the 5mL/ component velocity disappears; drip the THF solution of remaining 10-bromo-1-certain herbaceous plants with big flowers alcohol tetrahydropyrans with the 3mL/ component velocity; stirred 10 hours under the room temperature, obtain 10-bromo magnesium-1-octanol tetrahydropyrans.
The preparation method of described crotyl alcohol P-TOLUENE SULFO ACID 99 ester is as follows: crotyl alcohol 0.01mol is dissolved in the 50ml pyridine, be cooled to 0 ℃ then, add the 0.012mol Tosyl chloride again, stir and rise to room temperature after one hour, continue to stir 10h, add 5mL water again, stir adding 50mL water after 20 minutes, with after the extracted with diethyl ether three times successively with 10% hydrochloric acid, saturated sodium bicarbonate aqueous solution and saturated brine washing, concentrate after the dried over mgso then and obtain crotyl alcohol P-TOLUENE SULFO ACID 99 ester.
The preparation method of described E-12-tetradecene tetrahydropyrans is as follows: under nitrogen protection ,-78 ℃ of conditions; 0.095mol crotyl alcohol P-TOLUENE SULFO ACID 99 ester is dissolved among the anhydrous THF of 400mL; the speed of dividing with 5mL/ splashes into 10-bromo magnesium-1-octanol tetrahydropyrans; add 0.003mol four cupric chloride lithiums then; stir and rise to room temperature after one hour; continue to stir 14h; being warmed up to 45 ℃ then continues to stir one hour; add 100ml saturated aqueous ammonium chloride termination reaction again; extracted with diethyl ether, washing, saturated salt washing; concentrate after the dried over mgso, again SiO
2Column chromatography obtains E-12-tetradecene tetrahydropyrans.
Described E-12-tetradecene tetrahydropyrans deprotection, esterification process are as follows: 1.0g tosic acid and 0.081mol E-12-tetradecene tetrahydropyrans are dissolved among the THF of 200mL drying; add the 16.8g diacetyl oxide again; reflux 8 hours; be chilled to room temperature then; speed adding saturated sodium bicarbonate aqueous solution to the pH value of dividing with 10mL/ is 7; use dried over mgso behind the dichloromethane extraction 3 times, concentrate back SiO
2Post separates, and obtains E-12-tetradecene acetic ester.
The route that E-12-tetradecene alcohol acetic ester of the present invention synthesizes is as follows:
With inexpensive crotyl alcohol and 1,10-certain herbaceous plants with big flowers glycol is starting raw material, can obtain target compound through the simple reaction operation of 6 steps, utilize the form linked reaction to import two keys and prepare the three-dimensional arrangement variation that 12-tetradecene alcohol acetic ester reaction process does not relate to two keys, can utilize the original three-dimensional arrangement synthesis of trans of small molecules enol 12-tetradecene alcohol acetic ester to adapt to different application needs, the productive rate height, side reaction is few.The crude product compound of reaction gained just can obtain E-12-tetradecene alcohol acetic ester through underpressure distillation again through rapid column chromatography, and total recovery is 62.80% (in decamethylene-glycol).Needn't pass through configuration conversion.The relatively inexpensive raw material that is easy to get of whole process using, simple and reasonable steps, easy to operation, the raw material availability height, product is unique, and main compd E-12-tetradecene alcohol acetic ester in the synthetic sex pheromone of Ostrinia furnacalis is fit to suitability for industrialized production at lower cost.
Because (Z/E) 12-tetradecene alcohol acetic ester contained in the sex pheromone of each regional Ostrinia furnacalis has nothing in common with each other along inverse ratio, therefore above-mentioned (the Z)-12-tetradecene alcohol acetic acid vinegar that makes and anti-(E)-12-tetradecene alcohol acetic acid vinegar can be mixed to obtain multiple (Z/E)-12-tetradecene alcohol acetic acid vinegar along inverse ratio, to adapt to each regional actual needs.
Embodiment
Embodiment one: in the present embodiment in the nubilalis sex pheromone Z-12-tetradecene alcohol acetic ester be to be starting raw material with suitable-4-hexen-1-ol and 1,8-ethohexadiol; Raw material 1, the 8-ethohexadiol obtains 8-bromo-1-octanol through monolateral bromination, obtains 8-bromo-1-octanol tetrahydropyrans through the protection of 3,4-dihydropyrane again, gets 8-magnesium bromide-1-octanol tetrahydropyrans with reactive magnesium again; Raw material is suitable-and the 4-hexen-1-ol is through obtaining suitable-4-hexene-1-P-TOLUENE SULFO ACID 99 ester with the reaction of tosic acid chlorine, suitable-4-hexene-1-p-toluenesulfonic esters and 8-magnesium bromide-1-octanol tetrahydropyrans carries out the form linked reaction and obtains Z-12-tetradecene tetrahydropyrans, obtains Z-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis through deprotection, esterification again; Concrete operations are as follows:
The first step: the preparation method of 8-bromo-1-octanol is: add 0.1mol (14.6g) 1 in the three-necked bottle that dropping funnel, water trap and prolong are housed, 8-ethohexadiol, 300mL benzene and 0.1mol Hydrogen bromide (12mL48% Hydrogen bromide), add 0.001mol (0.126g) iodine again, oil bath heating stirring and refluxing 30h under 100 ℃ of conditions, stop heating, be that 5% aqueous sodium hydroxide solution, mass percent concentration are 10% dilute hydrochloric acid and saturated common salt water washing with mass percent concentration successively, anhydrous magnesium sulfate drying again, filter, evaporation concentration is again through SiO
2Column chromatography purification gets 8-bromo-1-octanol (yellow oil), yield 90%;
Second step: the preparation method of 8-bromo-1-octanol tetrahydropyrans is dissolved in 0.09mol8-bromo-1-octanol in the 100mL methylene dichloride, be cooled to 0 ℃ then, add 0.018mol tosic acid (PPTS), the speed of dividing with 5mL/ drips 0.109mol2, the 3-dihydropyrane, stir then and rise to room temperature, stir 10h under the room temperature, with 10～20mL saturated sodium bicarbonate aqueous solution termination reaction, use the extracted with diethyl ether after washing, with the saturated brine washing, use dried over mgso more again, evaporation concentration gets 8-bromo-1-octanol tetrahydropyrans, yield 95%;
The 3rd step: the preparation method of 8-magnesium bromide-1-octanol tetrahydropyrans (grignard reagent) is dissolved in the THF solution that obtains 8-bromo-1-octanol tetrahydrochysene pyrrole among the 100mLTHF with 0.09mol8-bromo-1-octanol tetrahydropyrans; under nitrogen protection; with magnesium powder 0.095mol; 0.01g iodine and 50mLTHF place three-necked bottle; under the magnetic agitation; THF solution to the iodine color that the speed of dividing with 5mL/ splashes into 8-bromo-1-octanol tetrahydropyrans disappears; the speed of dividing with 3mL/ drips the THF solution of remaining 8-bromo-1-octanol tetrahydropyrans then; stir 10h under the room temperature again, obtain 8-magnesium bromide-1-octanol tetrahydropyrans.
The 4th step: the preparation method of suitable-the 4-hexene-1-P-TOLUENE SULFO ACID 99 ester is as follows; With 0.1mol suitable-the 4-hexen-1-ol is dissolved in the 50mL pyridine, is cooled to 0 ℃, adds 0.12mol Tosyl chloride (TsCl), stir and rise to room temperature after one hour, continue to be stirred to and react completely, add 5mL water, stir adding 50mL water after 20 minutes, extract three times with ether; Ether extract with 2mol/L hydrochloric acid, saturated sodium bicarbonate aqueous solution and saturated brine washing, concentrates after the dried over mgso successively, obtains suitable-4-hexene-1-P-TOLUENE SULFO ACID 99 ester.Because this matter-pole instability is directly used in the reaction in the 5th step without purification.
The 5th step: the preparation method of Z-12-tetradecene tetrahydropyrans is as follows: under nitrogen protection ,-78 ℃ of conditions; with 0.095mol suitable-4-hexene-1-P-TOLUENE SULFO ACID 99 ester is dissolved among the anhydrous THF of 400mL; the speed of dividing with 5mL/ splashes into 8-magnesium bromide-1-octanol tetrahydropyrans; add 0.003mol four cupric chloride lithiums then; stir and rise to room temperature after one hour; continue to stir after 14 hours and be warmed up to 45 ℃; continue to stir one hour; add 100mL saturated aqueous ammonium chloride termination reaction then; the extracted with diethyl ether after washing; with the saturated salt washing, concentrate SiO after the dried over mgso again
2Column chromatography (ethyl acetate: normal hexane=1: 4) obtain 22.68g Z-12-tetradecene tetrahydropyrans, yield 85.2%.
The 6th step: Z-12-tetradecene tetrahydropyrans deprotection, esterification process are as follows: 1.0g tosic acid (PPTS) and 22.5g Z-12-tetradecene tetrahydropyrans are dissolved among the THF (tetrahydrofuran (THF)) of 200mL drying; add the 16.8g diacetyl oxide again; heating reflux reaction (temperature of reaction? ℃; please replenish) 8 hours; be chilled to room temperature then; add saturated sodium bicarbonate aqueous solution to pH value=7; use dichloromethane extraction again three times (each methylene dichloride consumption is 40mL); then with concentrating SiO after the dried over mgso
2Post separates (ethyl acetate: normal hexane=1: 4) obtain 16.87g Z-12-tetradecene acetic ester, yield 86.5%, total recovery 63.01% (in the 1.8-ethohexadiol).
Embodiment two: in the present embodiment in the nubilalis sex pheromone E-12-tetradecene alcohol acetic ester be with crotons pure and mild 1,10-certain herbaceous plants with big flowers glycol is starting raw material, wherein raw material 1,10-certain herbaceous plants with big flowers glycol obtains 10-bromo-1-certain herbaceous plants with big flowers alcohol through monolateral bromination, again through 2, the protection of 3-dihydropyrane obtains 10-bromo-1-octanol tetrahydropyrans, gets 10-bromo magnesium-1-octanol tetrahydropyrans with reactive magnesium again; Reaction obtains crotyl alcohol P-TOLUENE SULFO ACID 99 ester to the raw material crotyl alcohol through tosic acid chlorine, crotyl alcohol P-TOLUENE SULFO ACID 99 ester and 10-bromo magnesium-1-octanol tetrahydropyrans is E-12-tetradecene tetrahydropyrans after the form linked reaction again, again the E-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis that deprotection, esterification obtain; Specifically undertaken by following step:
The preparation method of step 1, described 10-bromo-1-certain herbaceous plants with big flowers alcohol is as follows: add 0.1mol (16.6g) 1 in the three-necked bottle that dropping funnel, water trap and prolong are housed, 10-decanediol, 300ml toluene and 0.1mol Hydrogen bromide (12mL48% Hydrogen bromide), add 0.001mol iodine again, oil bath heating stirring and refluxing 30h under 110 ℃ of conditions, stop heating, use dilute hydrochloric acid and the saturated common salt water washing of the aqueous sodium hydroxide solution, 10% (mass percent concentration) of 5% (mass percent concentration) successively, anhydrous magnesium sulfate drying then, filter, evaporation concentration is at SiO
2Column chromatography purification gets 21.35g10-bromo-1-certain herbaceous plants with big flowers alcohol, productive rate 90%;
Step 2, the preparation method of described 10-bromo-1-octanol tetrahydropyrans is as follows: under nitrogen protection, 0.09mol (21.35g) 10-bromo-1-certain herbaceous plants with big flowers alcohol is dissolved among the 200mL THF, be cooled to 0 ℃ then, add 0.018mol (4.46g) tosic acid (PPTS), the speed of dividing with 5mL/ drips 0.109mol2, the 3-dihydropyrane, stir then and rise to room temperature, continue to stir 10 hours, use the saturated sodium bicarbonate aqueous solution termination reaction, the extracted with diethyl ether after washing, wash with saturated salt again, dried over mgso, evaporation concentration obtain 27.47g10-bromo-1-octanol tetrahydropyrans, yield 95%;
Step 3; the method of the preparation of described E-12-tetradecene tetrahydropyrans is as follows: 0.09mol10-bromo-1-octanol tetrahydropyrans is dissolved in the THF solution that obtains 10-bromo-1-octanol tetrahydropyrans among the 200mLTHF; under nitrogen protection; with 0.095mol magnesium powder; 0.01g iodine and 50mLTHF place three-necked bottle; under the magnetic agitation; the speed of dividing with 5ml/ splashes into THF solution to the iodine color that the 10-bromo-1-certain herbaceous plants with big flowers alcohol tetrahydrochysene is muttered and disappears; drip the THF solution of remaining 10-bromo-1-certain herbaceous plants with big flowers alcohol tetrahydropyrans with the 3mL/ component velocity; stirred 10 hours under the room temperature, obtain 10-bromo magnesium-1-octanol tetrahydropyrans.The grignard reagent that obtains is not purified directly to carry out following reaction.
The preparation method of step 4, described crotyl alcohol P-TOLUENE SULFO ACID 99 ester is as follows: crotyl alcohol 0.01mol is dissolved in the 50ml pyridine, be cooled to 0 ℃ then, add 0.012mol Tosyl chloride (TsCl) again, stir and rise to room temperature after one hour, continue to stir 10h, add 5mL water again, stir and add 50mL water after 20 minutes, with the dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution and the saturated brine washing that after the extracted with diethyl ether three times with mass percent concentration are 10% successively, concentrate after the dried over mgso then and obtain 21.95g crotyl alcohol P-TOLUENE SULFO ACID 99 ester, yield 97%.
The preparation method of step 5, described E-12-tetradecene tetrahydropyrans is as follows: under nitrogen protection ,-78 ℃ of conditions; 0.095mol crotyl alcohol P-TOLUENE SULFO ACID 99 ester is dissolved among the anhydrous THF of 400mL; the speed of dividing with 5mL/ splashes into 10-bromo magnesium-1-octanol tetrahydropyrans; add 0.003mol four cupric chloride lithiums then; stir and rise to room temperature after one hour; continue to stir 14h; being warmed up to 45 ℃ then continues to stir one hour; add 100ml saturated aqueous ammonium chloride termination reaction again; extracted with diethyl ether, washing, saturated salt washing; concentrate after the dried over mgso, again SiO
2Column chromatography obtains 25.98g E-12-tetradecene tetrahydropyrans, yield 85.0%.
Step 6, described E-12-tetradecene acetic ester deprotection, esterification process are as follows: 1.0g tosic acid and 0.081mol E-12-tetradecene tetrahydropyrans are dissolved among the THF of 200mL drying; add the 16.8g diacetyl oxide again; reflux 8 hours; be chilled to room temperature then; speed adding saturated sodium bicarbonate aqueous solution to the pH value of dividing with 10mL/ is 7; use dried over mgso behind the dichloromethane extraction 3 times, concentrate back SiO
2Post separates, and obtains E-12-tetradecene acetic ester, yield 86.5%, total recovery 63% (in decamethylene-glycol).
Claims (10)
1. the preparation method of 12-tetradecene alcohol acetic ester in the nubilalis sex pheromone is characterized in that in the nubilalis sex pheromone that Z-12-tetradecene alcohol acetic ester is is starting raw material with suitable-4-hexen-1-ol and 1,8-ethohexadiol; Raw material 1, the 8-ethohexadiol obtains 8-bromo-1-octanol through monolateral bromination, obtains 8-bromo-1-octanol tetrahydropyrans through the protection of 3,4-dihydropyrane again, gets 8-magnesium bromide-1-octanol tetrahydropyrans with reactive magnesium again; Raw material is suitable-and the 4-hexen-1-ol is through obtaining suitable-4-hexene-1-P-TOLUENE SULFO ACID 99 ester with the reaction of tosic acid chlorine; suitable-4-hexene-1-p-toluenesulfonic esters and 8-magnesium bromide-1-octanol tetrahydropyrans carries out the form linked reaction and obtains Z-12-tetradecene tetrahydropyrans, obtains Z-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis through deprotection, esterification again.
2. the preparation method of 12-tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 1, the preparation method who it is characterized in that described 8-bromo-1-octanol is to dropping funnel is housed, add 0.1mol1 in the three-necked bottle of water trap and prolong, the 8-ethohexadiol, 300mL benzene and 0.1mol Hydrogen bromide, add 0.001mol iodine again, oil bath heating stirring and refluxing 30h under 100 ℃ of conditions, be 5% aqueous sodium hydroxide solution successively with mass percent concentration, mass percent concentration is 10% dilute hydrochloric acid and saturated common salt water washing, anhydrous magnesium sulfate drying, filter, evaporation concentration is again through SiO
2Column chromatography purification gets 8-bromo-1-octanol;
The preparation method of described 8-bromo-1-octanol tetrahydropyrans is dissolved in 0.09mol8-bromo-1-octanol in the 100mL methylene dichloride, be cooled to 0 ℃ then, add the 0.018mol tosic acid, the speed of dividing with 5mL/ drips 0.109mol2, the 3-dihydropyrane, stir then and rise to room temperature, stir 10h under the room temperature, with 10mL～20mL saturated sodium bicarbonate aqueous solution termination reaction, use the extracted with diethyl ether after washing, with the saturated brine washing, use dried over mgso more again, evaporation concentration gets 8-bromo-1-octanol tetrahydropyrans;
The preparation method of described 8-magnesium bromide-1-octanol tetrahydropyrans is dissolved in the THF solution that obtains 8-bromo-1-octanol tetrahydrochysene pyrrole among the 100mLTHF with 0.09mol8-bromo-1-octanol tetrahydropyrans; under nitrogen protection; with magnesium powder 0.095mol; 0.01g iodine and 50mLTHF place three-necked bottle; under the magnetic agitation; THF solution to the iodine color that the speed of dividing with 5mL/ splashes into 8-bromo-1-octanol tetrahydropyrans disappears; the speed of dividing with 3mL/ drips the THF solution of remaining 8-bromo-1-octanol tetrahydropyrans then; stir 10h under the room temperature again, obtain 8-magnesium bromide-1-octanol tetrahydropyrans.
3. the preparation method of 12-tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 2, it is characterized in that described suitable-preparation method of 4-hexene-1-P-TOLUENE SULFO ACID 99 ester is as follows; With 0.1mol suitable-the 4-hexen-1-ol is dissolved in the 50mL pyridine, is cooled to 0 ℃, adds the 0.12mol Tosyl chloride, stirs and rises to room temperature after one hour, continues to be stirred to react completely, and adds 5mL water, stirs adding 50ml water after 20 minutes, with ether extraction three times; Ether extract with 2mol/L hydrochloric acid, saturated sodium bicarbonate aqueous solution and saturated brine washing, concentrates after the dried over mgso successively, obtains suitable-4-hexene-1-P-TOLUENE SULFO ACID 99 ester.
4. the preparation method of 12-tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 3; the preparation method who it is characterized in that Z-12-tetradecene tetrahydropyrans is as follows: in nitrogen protection; under-78 ℃ of conditions; with 0.095mol suitable-4-hexene-1-P-TOLUENE SULFO ACID 99 ester is dissolved among the anhydrous THF of 400mL; the speed of dividing with 5mL/ splashes into 8-magnesium bromide-1-octanol tetrahydropyrans; add 0.003mol four cupric chloride lithiums then; stir and rise to room temperature after one hour; stir and be warmed up to 45 degree continuation stirrings 1 hour after 14 hours; add 100mL saturated aqueous ammonium chloride termination reaction then; the extracted with diethyl ether after washing; wash with saturated salt again; concentrate SiO after the dried over mgso
2Column chromatography obtains Z-12-tetradecene tetrahydropyrans.
5. according to the preparation method of 12-tetradecene alcohol acetic ester in claim 1,2, the 3 or 4 described nubilalis sex pheromones; it is characterized in that Z-12-tetradecene tetrahydropyrans deprotection, esterification process are as follows: 1.0g tosic acid and 22.5g Z-12-tetradecene tetrahydropyrans are dissolved among the THF of 200mL drying; add the 16.8g diacetyl oxide again; heating reflux reaction 8 hours; be chilled to room temperature then; add saturated sodium bicarbonate aqueous solution to pH value=7; use dichloromethane extraction again three times; then with concentrating SiO after the dried over mgso
2The post separation obtains Z-12-tetradecene acetic ester.
6. the preparation method of 12-tetradecene alcohol acetic ester in the nubilalis sex pheromone, it is characterized in that in the nubilalis sex pheromone anti--12-tetradecene alcohol acetic ester is with crotons pure and mild 1,10-certain herbaceous plants with big flowers glycol is starting raw material, wherein raw material 1,10-certain herbaceous plants with big flowers glycol obtains 10-bromo-1-certain herbaceous plants with big flowers alcohol through monolateral bromination, obtain 10-bromo-1-octanol tetrahydropyrans through the protection of 2,3-dihydropyrane again, get 10-bromo magnesium-1-octanol tetrahydropyrans with reactive magnesium again; Reaction obtains crotyl alcohol P-TOLUENE SULFO ACID 99 ester to the raw material crotyl alcohol through tosic acid chlorine; crotyl alcohol P-TOLUENE SULFO ACID 99 ester and 10-bromo magnesium-1-octanol tetrahydropyrans is E-12-tetradecene tetrahydropyrans after the form linked reaction again, again the E-12-tetradecene alcohol acetic ester in the sex pheromone of Ostrinia furnacalis that deprotection, esterification obtain.
7. the preparation method of 12-tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 6, the preparation method who it is characterized in that described 10-bromo-1-certain herbaceous plants with big flowers alcohol is as follows: to dropping funnel is housed, add 0.1mol1 in the three-necked bottle of water trap and prolong, the 10-decanediol, 300ml toluene and 0.1mol Hydrogen bromide, add 0.001mol iodine again, oil bath heating stirring and refluxing 30h under 110 ℃ of conditions, stop heating, be 5% aqueous sodium hydroxide solution successively with mass percent concentration, mass percent concentration is 10% dilute hydrochloric acid and saturated common salt water washing, anhydrous magnesium sulfate drying then, filter, evaporation concentration is at SiO
2Column chromatography purification gets 10-bromo-1-certain herbaceous plants with big flowers alcohol;
The preparation method of described 10-bromo-1-octanol tetrahydropyrans is as follows: 0.09mol10-bromo-1-certain herbaceous plants with big flowers alcohol is dissolved among the 100mL THF, be cooled to 0 ℃ then, add the 0.018mol tosic acid, the speed of dividing with 5mL/ drips 0.109mol2, the 3-dihydropyrane, stir then and rise to room temperature, continue to stir 10 hours, use the saturated sodium bicarbonate aqueous solution termination reaction, the extracted with diethyl ether after washing, with the saturated salt washing, dried over mgso, evaporation concentration obtain 10-bromo-1-octanol tetrahydropyrans again;
The method of the preparation of described E-12-tetradecene tetrahydropyrans is as follows: 0.09mol10-bromo-1-octanol tetrahydropyrans is dissolved in the THF solution that obtains 10-bromo-1-octanol tetrahydropyrans among the 200mLTHF; under nitrogen protection; with 0.095mol magnesium powder; 0.01g iodine and 50mLTHF place three-necked bottle; under the magnetic agitation; the speed of dividing with 5ml/ splashes into THF solution to the iodine color that the 10-bromo-1-certain herbaceous plants with big flowers alcohol tetrahydrochysene is muttered and disappears; drip the THF solution of remaining 10-bromo-1-certain herbaceous plants with big flowers alcohol tetrahydropyrans with the 3mL/ component velocity; stirred 10 hours under the room temperature, obtain 10-bromo magnesium-1-octanol tetrahydropyrans.
8. the preparation method of 12-tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 7, the preparation method who it is characterized in that described crotyl alcohol P-TOLUENE SULFO ACID 99 ester is as follows: crotyl alcohol 0.01mol is dissolved in the 50ml pyridine, be cooled to 0 ℃ then, add the 0.012mol Tosyl chloride again, stir and rise to room temperature after one hour, continue to stir 10h, add 5mL water again, stir and add 50mL water after 20 minutes, with the hydrochloric acid that after the extracted with diethyl ether three times with mass percent concentration is 10% successively, saturated sodium bicarbonate aqueous solution and saturated brine washing concentrate after the dried over mgso then and obtain crotyl alcohol P-TOLUENE SULFO ACID 99 ester.
9. the preparation method of 12-tetradecene alcohol acetic ester in the nubilalis sex pheromone according to claim 8; the preparation method who it is characterized in that described E-12-tetradecene tetrahydropyrans is as follows: in nitrogen protection; under-78 ℃ of conditions; 0.095mol crotyl alcohol P-TOLUENE SULFO ACID 99 ester is dissolved among the anhydrous THF of 400mL; the speed of dividing with 5mL/ splashes into 10-bromo magnesium-1-octanol tetrahydropyrans; add 0.003mol four cupric chloride lithiums then; stir and rise to room temperature after 1 hour; continue to stir 14h; being warmed up to 45 ℃ then continues to stir one hour; add 100ml saturated aqueous ammonium chloride termination reaction again; extracted with diethyl ether; washing; the saturated salt washing concentrates after the dried over mgso, SiO again
2Column chromatography obtains E-12-tetradecene tetrahydropyrans.
10. according to claim 6; 7; the preparation method of 12-tetradecene alcohol acetic ester in the 8 or 9 described nubilalis sex pheromones; it is characterized in that described E-12-tetradecene tetrahydropyrans deprotection; esterification process is as follows: the preparation method as follows: 1.0g tosic acid and 0.081mol E-12-tetradecene tetrahydropyrans are dissolved among the THF of 200mL drying; add the 16.8g diacetyl oxide again; reflux 8 hours; be chilled to room temperature then; speed adding saturated sodium bicarbonate aqueous solution to the pH value of dividing with 10mL/ is 7; use dried over mgso behind the dichloromethane extraction 3 times, concentrate back SiO
2Post separates, and obtains E-12-tetradecene acetic ester.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104974027A (en) * | 2015-07-30 | 2015-10-14 | 黑龙江省科学院微生物研究所 | Synthesis method of Chilosuppressalis (Walker) pheromone cis-11-hexedecanal |
| CN105418418A (en) * | 2015-11-06 | 2016-03-23 | 山西农业大学 | Method for synthesizing cis-7-tetradecenol acetate which is main component of sex pheromone of holcocerus vicarius walker |
| CN105766907A (en) * | 2016-03-29 | 2016-07-20 | 西北农林科技大学 | Atrijuglans hetaohei Yang sex pheromone component |
| CN112299991A (en) * | 2020-09-08 | 2021-02-02 | 宁波纽康生物技术有限公司 | Preparation method of (E, E, Z) -10,12, 14-hexadecatriene acetate, composition and lure |
| CN114814021A (en) * | 2022-04-21 | 2022-07-29 | 浙江省化工产品质量检验站有限公司 | Detection method and application of sex pheromone pesticide of ostrinia furnacalis |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974027A (en) * | 2015-07-30 | 2015-10-14 | 黑龙江省科学院微生物研究所 | Synthesis method of Chilosuppressalis (Walker) pheromone cis-11-hexedecanal |
| CN105418418A (en) * | 2015-11-06 | 2016-03-23 | 山西农业大学 | Method for synthesizing cis-7-tetradecenol acetate which is main component of sex pheromone of holcocerus vicarius walker |
| CN105418418B (en) * | 2015-11-06 | 2017-04-26 | 山西农业大学 | Method for synthesizing cis-7-tetradecenol acetate which is main component of sex pheromone of holcocerus vicarius walker |
| CN105766907A (en) * | 2016-03-29 | 2016-07-20 | 西北农林科技大学 | Atrijuglans hetaohei Yang sex pheromone component |
| CN112299991A (en) * | 2020-09-08 | 2021-02-02 | 宁波纽康生物技术有限公司 | Preparation method of (E, E, Z) -10,12, 14-hexadecatriene acetate, composition and lure |
| CN114814021A (en) * | 2022-04-21 | 2022-07-29 | 浙江省化工产品质量检验站有限公司 | Detection method and application of sex pheromone pesticide of ostrinia furnacalis |
| CN114814021B (en) * | 2022-04-21 | 2023-02-24 | 浙江省化工产品质量检验站有限公司 | Detection method and application of sex pheromone pesticide of ostrinia furnacalis |
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