CN110372482A - A kind of micromelalopha troglodyte sex pheromone active constituent and its preparation and authentication method - Google Patents

A kind of micromelalopha troglodyte sex pheromone active constituent and its preparation and authentication method Download PDF

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CN110372482A
CN110372482A CN201910688701.1A CN201910688701A CN110372482A CN 110372482 A CN110372482 A CN 110372482A CN 201910688701 A CN201910688701 A CN 201910688701A CN 110372482 A CN110372482 A CN 110372482A
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diethoxy
alkynes
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trans
sex pheromone
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CN110372482B (en
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刘福
张真
孔祥波
张苏芳
崔晓琦
范大整
朱洪
李娟�
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Zhumadian Forest Disease And Insect Control And Quarantine Station
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Research Institute of Forest Ecology Environment and Protection of Chinese Academy of Forestry
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Abstract

The present invention relates to insect sex pheromone Components identification and synthesis technical field, a kind of micromelalopha troglodyte sex pheromone active constituent and its preparation and authentication method are provided.The present invention specify for the first time the structure of micromelalopha troglodyte sex pheromone active constituent be it is suitable, trans- 13,15-, 18 carbon, two olefine aldehydr, the active constituent can cause the significant electrophysiologic response of micromelalopha troglodyte hero moth, observe and predict and trap based theoretical for woodland micromelalopha troglodyte.The present invention is reacted by Wittig-Schlosse and hydroboration-reduction method synthesizes micromelalopha troglodyte sex pheromone active constituent, which has many advantages, such as that high yield, purity is high, stereoselectivity are strong, and as a result reproducibility is high.The present invention uses gas-chromatography-tentaculum electric potential technology, determines micromelalopha troglodyte sex pheromone active constituent by the standard substance of synthesis and the method for micromelalopha troglodyte sex pheromone gland extract comparative analysis, and the identification method period is short, result credibility is high.

Description

A kind of micromelalopha troglodyte sex pheromone active constituent and its preparation and authentication method
Technical field
The present invention relates to insect sex pheromone Components identification and synthesis technical field, in particular to a kind of micromelalopha troglodyte letter Cease plain active constituent and its preparation and authentication method.
Background technique
Micromelalopha troglodyte Micromelalopha troglodyta (Graeser) be China main defoliator in Populur it One, it causes disaster in China northeast, northwest, Central Plains and the regional wildness such as Central-South, not only influences the normal growth of poplar, cause huge Economic loss, and ecological environment is destroyed, seriously constrain the development of forestry.
Currently, mainly include chemical pesticide and natural enemy insect to the control method of the worm, although chemical pesticide is quick, It is the problems such as this method control cost is high, and is also easy to produce pesticide residue, environmental pollution, and pest develops drug resistance；Natural enemy insect Raising and to launch technical requirements high.Therefore, existing Prevention Technique effect is unsatisfactory, it would be highly desirable to which research and development continue efficiently to prevent and treat Technology.
Insect sex pheromone in control of insect have it is efficient, lasting, nontoxic, specificity is strong, do not injure natural enemy, do not pollute The advantage of environment etc.；In addition, insect sex pheromone and other control of insect measure (especially biological controls) are used cooperatively, table Reveal good compatibility, by the great attention of domestic and foreign scholars, and just becomes the important measures in integrated pest management One of.
However so far, the structural information of micromelalopha troglodyte sex pheromone active constituent does not have correlative study report also, because This identification, synthesis micromelalopha troglodyte sex pheromone active constituent have important meaning for carrying out integrated pest management using sex pheromone Justice.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of micromelalopha troglodyte sex pheromone active constituent and its preparation and authentications Method, present invention determine that the structure of micromelalopha troglodyte sex pheromone active constituent, and the active constituent is synthesized and identified, Suitable to further determine that, trans- 18 carbon of 13,15-, two olefine aldehydr is micromelalopha troglodyte sex pheromone active constituent.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of micromelalopha troglodyte sex pheromone active constituent, chemical name be it is suitable, trans- 13,15-, 18 carbon, two olefine aldehydr has Structure shown in Formulas I:
The present invention provides the preparation methods of micromelalopha troglodyte sex pheromone active constituent described in above scheme, including following step It is rapid:
(1) under oxidant effect, the bromo- DODECANOL, 1- of 12- is subjected to oxidation reaction, obtains the bromo- 1- lauric aldehyde of 12-；
(2) under the action of catalyst, the bromo- 1- lauric aldehyde of 12- and triethyl orthoformate are subjected to aldehyde radical protection reaction, obtained 1,1- diethoxy -12- bromododecane；
(3) by sodium iodide and 1,1- diethoxy -12- bromododecane carries out iodide reaction, obtains 1,1- diethoxy - 12- dodecyl iodides；
(4) under that action of n-butyl lithium, by propilolic alcohol and 1,1- diethoxy -12- dodecyl iodides carry out alkynes alkyl Change reaction, obtains 15,15- diethoxy-pentadecane -13- alkynes -1- alcohol；
(5) under electrolytic manganese dioxide effect, 15,15- diethoxy-pentadecane -13- alkynes -1- alcohol is subjected to alkynol oxygen Change reaction, obtains 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde；
(6) under the action of phenyl lithium, lithium bromide, the tert-butyl alcohol and potassium tert-butoxide, by 15,15- diethoxy-pentadecane- 13- alkynes -1- aldehyde and propyl triphenylphosphinebromide carry out Wittig-Schlosser reaction, obtain trans- 1,1- diethoxy -15- Octadecene -13- alkynes；
(7) dicyclohexyl borane and glacial acetic acid effect under, by trans- 1,1- diethoxy -15- octadecene -13- alkynes into The reaction of row Borohydride reduction, obtains suitable, trans- 1,1- diethoxy -13,15-, 18 carbon diene；
(8), will be suitable under oxalic acid effect, it is de- that trans- 1,1- diethoxy -13,15-, 18 carbon diene carries out acetal protecting group Except reaction, suitable, trans- 13,15-, 18 carbon, two olefine aldehydr is obtained.
Preferably, oxidant includes pyridinium chloro-chromate, two pyridinium chloro-chromates, tetramethyl piperidine in the step (1) One or more of nitrogen oxides and the high iodine alkane of Dai Si-Martin；
The molar ratio of the bromo- DODECANOL, 1- of the 12- and oxidant is 1:2~4；
The temperature of the oxidation reaction be room temperature, the time be 2~for 24 hours.
Preferably, catalyst includes p-methyl benzenesulfonic acid and/or pyridine tosylat in the step (2)；
The molar ratio of the bromo- 1- lauric aldehyde of the catalyst, 12- and triethyl orthoformate is 1:100:60~70；
The temperature of aldehyde radical protection reaction is -5~0 DEG C, the time is 10~for 24 hours.
Preferably, the molar ratio of sodium iodide and 1 in the step (3), 1- diethoxy -12- bromododecane is 2~3: 1；
The iodide reaction carries out under reflux conditions, the time be 6~for 24 hours.
Preferably, in the step (4) 1,1- diethoxy -12- dodecyl iodides, propilolic alcohol and n-BuLi mole Than for 1:2~3:4~5；
The temperature of the alkynes alkylated reaction is -15~-30 DEG C, and the time is 2~5h.
Preferably, electrolytic manganese dioxide and 15 in the step (5), 15- diethoxy-pentadecane -13- alkynes -1- alcohol Molar ratio is 30~40:1；
The temperature of the alkynol oxidation reaction be -5~0 DEG C, the time be 4~for 24 hours.
Preferably, 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde, propyl triphenyl phosphonium bromide in the step (6) Phosphine, phenyl lithium, lithium bromide, the tert-butyl alcohol and potassium tert-butoxide molar ratio be 1:1.2~1.5:2:2:1.5~2:1.5~2.0.
Preferably, trans- 1,1- diethoxy -15- octadecene -13- alkynes in the step (7), dicyclohexyl borane and The molar ratio of glacial acetic acid is 1:2~4:6~10；
Trans- 1,1- diethoxy -15- octadecene -13- alkynes rubs in step (8) mesoxalic acid and the step (7) You are than being 3~3.5:1.
The present invention also provides a kind of identification methods of micromelalopha troglodyte sex pheromone active constituent, comprising the following steps:
Using gas-chromatography-tentaculum electric potential instrument to micromelalopha troglodyte sex pheromone gland extract and suitable, trans- 13,15- 18 Two olefine aldehydr of carbon is analyzed respectively, obtains corresponding map；
Spectrogram is analyzed, if showing suitable, trans- 13,15-, 18 carbon, two olefine aldehydr and micromelalopha troglodyte sex pheromone in spectrogram The retention time of gland extract is close, and can cause micromelalopha troglodyte hero moth EAG response, then can determine it is suitable, it is trans- 18 carbon of 13,15-, two olefine aldehydr is micromelalopha troglodyte sex pheromone active constituent.
The present invention provides a kind of micromelalopha troglodyte sex pheromone active constituent, chemical name is suitable, trans- 13,15-, 18 carbon Two olefine aldehydrs have structure shown in Formulas I.The present invention specifies the structure of micromelalopha troglodyte sex pheromone active constituent for the first time, the activity Ingredient can cause the significant electrophysiologic response of micromelalopha troglodyte hero moth, observe and predict and trap based theoretical for woodland micromelalopha troglodyte.
The present invention also provides the preparation methods of micromelalopha troglodyte sex pheromone active constituent.The present invention passes through Wittig- Schlosse reaction and hydroboration-reduction method synthesize micromelalopha troglodyte sex pheromone active constituent, which, which has, produces The advantages that rate is high, with high purity, stereoselectivity is strong, and as a result reproducibility is high.
The present invention also provides the identification methods of micromelalopha troglodyte sex pheromone active constituent.The present invention uses gas-chromatography- Tentaculum electric potential technology is determined by the standard substance of synthesis and the method for micromelalopha troglodyte sex pheromone gland extract comparative analysis Micromelalopha troglodyte sex pheromone active constituent, the identification method period is short, result credibility is high.
Detailed description of the invention
Fig. 1 is gas-chromatography-of the micromelalopha troglodyte hero moth feeler of the present invention to female moth sex pheromone body of gland n-hexane extract Tentaculum electric potential instrument analyzes GC-EAD map；
Fig. 2 is that micromelalopha troglodyte hero moth feeler of the present invention analyzes GC- to gas-chromatography-tentaculum electric potential instrument of synthesis compound EAD map, wherein A is suitable, trans- 13,15-, 18 carbon, two olefine aldehydr.
Specific embodiment
The present invention provides a kind of micromelalopha troglodyte sex pheromone active constituents, have structure shown in Formulas I:
The chemical name of micromelalopha troglodyte sex pheromone active constituent provided by the invention is suitable, trans- 18 carbon two of 13,15- Olefine aldehydr, the present invention specify the structure of micromelalopha troglodyte sex pheromone active constituent for the first time, which can cause micromelalopha troglodyte The significant electrophysiologic response of male moth.
The present invention also provides the preparation method of micromelalopha troglodyte sex pheromone active constituent described in above scheme, feature exists In, comprising the following steps:
(1) under oxidant effect, the bromo- DODECANOL, 1- of 12- is subjected to oxidation reaction, obtains the bromo- 1- lauric aldehyde of 12-；
(2) under the action of catalyst, the bromo- 1- lauric aldehyde of 12- and triethyl orthoformate are subjected to aldehyde radical protection reaction, obtained 1,1- diethoxy -12- bromododecane；
(3) by sodium iodide and 1,1- diethoxy -12- bromododecane carries out iodide reaction, obtains 1,1- diethoxy - 12- dodecyl iodides；
(4) under that action of n-butyl lithium, by propilolic alcohol and 1,1- diethoxy -12- dodecyl iodides carry out alkynes alkyl Change reaction, obtains 15,15- diethoxy-pentadecane -13- alkynes -1- alcohol；
(5) under electrolytic manganese dioxide effect, 15,15- diethoxy-pentadecane -13- alkynes -1- alcohol is subjected to alkynol oxygen Change reaction, obtains 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde；
(6) under the action of phenyl lithium, lithium bromide, the tert-butyl alcohol and potassium tert-butoxide, by 15,15- diethoxy-pentadecane- 13- alkynes -1- aldehyde and propyl triphenylphosphinebromide carry out Wittig-Schlosser reaction, obtain trans- 1,1- diethoxy -15- Octadecene -13- alkynes；
(7) dicyclohexyl borane and glacial acetic acid effect under, by trans- 1,1- diethoxy -15- octadecene -13- alkynes into The reaction of row Borohydride reduction, obtains suitable, trans- 1,1- diethoxy -13,15-, 18 carbon diene；
(8), will be suitable under oxalic acid effect, it is de- that trans- 1,1- diethoxy -13,15-, 18 carbon diene carries out acetal protecting group Except reaction, suitable, trans- 13,15-, 18 carbon, two olefine aldehydr is obtained.
In the present invention, the synthetic route of the micromelalopha troglodyte sex pheromone active constituent is as shown in formula a:
The present invention carries out the bromo- DODECANOL, 1- of 12- under oxidant effect (structural formula is as shown in compound 1 in formula a) Oxidation reaction obtains the bromo- 1- lauric aldehyde of 12- (structural formula is as shown in compound 2 in formula a).In the present invention, the oxidant is excellent Choosing includes one of pyridinium chloro-chromate, two pyridinium chloro-chromates, tetramethyl piperidine nitrogen oxides and the high iodine alkane of Dai Si-Martin Or it is several；The molar ratio of the bromo- DODECANOL, 1- of the 12- and oxidant is preferably 1:2~4, more preferably 1:3；The oxidation The solvent of reaction is preferably methylene chloride.
In the present invention, the temperature of the oxidation reaction is preferably room temperature, and the time is preferably 2~for 24 hours, more preferably 3~ 20h, further preferably 4h.Oxidant is preferably first dissolved in solvent by the present invention, obtains oxidizing agent solution, then that 12- is bromo- DODECANOL, 1- is slowly added to carry out oxidation reaction in oxidizing agent solution, and time of the oxidation reaction is from the bromo- 1- dodecane of 12- Alcohol addition starts to calculate when finishing.
After the completion of oxidation reaction, without carrying out any purifying and post-processing, directly using the product after oxidation reaction as anti- Object is answered to participate in reacting in next step.
After obtaining the bromo- 1- lauric aldehyde of 12-, the present invention under the action of catalyst, by the bromo- 1- lauric aldehyde of 12- and orthoformic acid three Ethyl ester carries out aldehyde radical protection reaction, obtains 1,1- diethoxy -12- bromododecane (structural formula such as 3 institute of compound in formula a Show).In the present invention, the catalyst preferably includes p-methyl benzenesulfonic acid and/or pyridine tosylat, more preferably to toluene Sulfonic acid, the p-methyl benzenesulfonic acid are preferably p-methyl benzenesulfonic acid monohydrate；The bromo- 1- lauric aldehyde of the catalyst, 12- and orthoformic acid The molar ratio of triethyl is preferably 1:100:60~70, more preferably 1:100:63~68, further preferably 1:100:65.? In the present invention, the solvent of aldehyde radical protection reaction is preferably dehydrated alcohol, anhydrous methylene chloride, anhydrous tetrahydro furan and anhydrous One or more of dioxane, the present invention do not have particular/special requirement to the dosage of the solvent, can guarantee that aldehyde radical protection is anti- It should go on smoothly.
In the present invention, the temperature of aldehyde radical protection reaction is preferably -5~0 DEG C, and more preferably 0 DEG C, the time is preferably 10~for 24 hours, more preferably 11~22h, further preferably 12~20h.In a specific embodiment of the present invention, preferably directly will It is added in reaction solution after the completion of oxidation reaction in the solvent of aldehyde radical protection reaction, obtains the bromo- 1- lauric aldehyde solution of 12-, then Triethyl orthoformate is slowly dropped in the bromo- 1- lauric aldehyde solution of 12- at -5~0 DEG C, after being added dropwise at -5~0 DEG C Carry out aldehyde radical protection reaction；The time of aldehyde radical protection reaction since triethyl orthoformate be added dropwise after calculate.
Aldehyde radical is protected after the reaction was completed, and the present invention preferably post-processes aldehyde radical protection reaction solution, in the present invention In, the post-processing preferably includes following steps:
Ethyl acetate extraction is carried out after protecting reaction solution and saturated sodium carbonate solution to mix in aldehyde radical, obtains extracting organic Phase；
Solvent will be evaporated off after extraction organic phase drying, obtains 1,1- diethoxy -12- bromododecane.
In the present invention, the number of the extraction is preferably 3 times, merges organic phase after the completion of extraction；The dry use Desiccant is preferably anhydrous sodium sulfate；The present invention does not have particular/special requirement to the temperature being evaporated off, and solvent can be evaporated off completely ?.
After obtaining 1,1- diethoxy -12- bromododecane, the present invention is by sodium iodide and 1,1- diethoxy -12- bromo Dodecane carries out iodide reaction, obtains 1,1- diethoxy -12- dodecyl iodides (structural formula is as shown in compound 4 in formula a). In the present invention, the molar ratio of the sodium iodide and 1,1- diethoxy -12- bromododecane is preferably 2~3:1；The iodine The generation solvent of reaction is preferably anhydrous propanone；The iodide reaction preferably carries out under reflux conditions, and the time is preferably 6~for 24 hours, More preferably 10~20h, further preferably 12~18h；The temperature of the back flow reaction is configured according to the boiling point of solvent ?.
In a specific embodiment of the present invention, 1,1- diethoxy -12- bromododecane is first preferably dissolved in anhydrous third In ketone, then sodium iodide is added in the anhydrous propanone solution of 1,1- diethoxy -12- bromododecane and is reacted.
After the completion of iodide reaction, the present invention preferably post-processes the iodide reaction liquid, the preferred packet of post-processing Include following steps:
After organic solvent in iodide reaction liquid is evaporated off, residue and water are mixed, then carry out ethyl acetate extraction, Obtain organic phase；
Solvent will be evaporated off after organic phase drying, obtains crude product；
The crude product is subjected to silica gel column chromatography, obtains 1,1- diethoxy -12- dodecyl iodides.
In the present invention, the number of the extraction is preferably 3 times, merges organic phase after the completion of extraction；The dry use Desiccant is preferably anhydrous sodium sulfate；The silica gel column chromatography is preferably n-hexane-ethyl acetate mixed solvent with eluant, eluent；Institute The volume ratio for stating in the mixed solvent n-hexane and ethyl acetate is preferably 25:1；The present invention is not special to the temperature being evaporated off It is required that solvent can be evaporated off completely.
After obtaining 1,1- diethoxy -12- dodecyl iodides, the present invention under that action of n-butyl lithium, by propilolic alcohol and 1, 1- diethoxy -12- dodecyl iodides carry out alkynes alkylated reaction, obtain 15,15- diethoxy-pentadecane -13- alkynes -1- Alcohol (structural formula is as shown in compound 5 in formula a).In the present invention, 1, the 1- diethoxy -12- dodecyl iodides, propilolic alcohol Molar ratio with n-BuLi is preferably 1:2~3:4~5, more preferably 1:2:4；The solvent of the alkynes alkylated reaction is excellent It is selected as tetrahydrofuran-hexamethylphosphoramide mixed solvent；The present invention does not have particular/special requirement, Neng Goubao to the volume of the solvent Card reaction is gone on smoothly；Preferably -15~-30 DEG C of the temperature of the alkynes alkylated reaction, more preferably -20 DEG C, when Between preferably 2~5h, more preferably 2h.
In a specific embodiment of the present invention, preferably n-BuLi is dissolved in tetrahydrofuran, then -15~-30 The tetrahydrofuran solution of n-BuLi and 1,1- diethoxy -12- dodecyl iodides are successively added drop-wise to tetrahydrofuran-six at DEG C Methyl phosphoric triamide in the mixed solvent is reacted；The alkynes alkylated reaction time of the invention is from 1,1- diethoxy -12- iodine Start to calculate after being added dropwise for dodecane.
After the completion of alkynes alkylated reaction, the present invention preferably post-processes alkynes alkylated reaction liquid, locates after described Reason preferably includes following steps:
Ammonium chloride is added into alkynes alkylated reaction liquid and terminates reaction, is then extracted, is obtained using ethyl acetate Organic phase is extracted, solvent will be evaporated off after extraction organic phase drying, obtain 15,15- diethoxy-pentadecane -13- alkynes -1- Alcohol crude product；The crude product directly applies in reaction in next step without being further processed.
In the present invention, the number of the extraction is preferably 3 times, merges organic phase after extraction；The drying drying Agent is preferably anhydrous sodium sulfate；The present invention does not have particular/special requirement to the additional amount of the ammonium chloride, can be by reaction terminating.
After obtaining 15,15- diethoxy-pentadecane -13- alkynes -1- alcohol, the present invention, will under electrolytic manganese dioxide effect 15,15- diethoxies-pentadecane -13- alkynes -1- alcohol carries out alkynol oxidation reaction, obtains 15,15- diethoxy-pentadecane - 13- alkynes -1- aldehyde (structural formula is as shown in compound 6 in formula a).In the present invention, the electrolytic manganese dioxide and 15,15- diethyl Oxygroup-pentadecane -13- alkynes -1- alcohol molar ratio is preferably 30~40:1, more preferably 35:1；The alkynol oxidation reaction Temperature is preferably -5~0 DEG C, and more preferably 0 DEG C, the time is preferably 4~for 24 hours, more preferably 10~20h, further preferably 12 ~18h；The alkynol oxidation reaction preferably carries out under the conditions of nitrogen protection；The solvent of the alkynol oxidation reaction is preferably positive Hexane, the present invention do not have particular/special requirement to the volume of the solvent, and reaction can be made to go on smoothly.
In a specific embodiment of the present invention, preferably by 15,15- diethoxy obtained in the previous step-pentadecane -13- alkynes - 1- alcohol crude product is slowly added to be reacted in the n-hexane suspension of electrolytic manganese dioxide.
After the completion of alkynol oxidation reaction, the present invention preferably post-processes the alkynol oxidation liquid, locates after described Reason preferably includes following steps:
Alkynol oxidation liquid is subjected to diatomite filtering, filtrate is evaporated off organic phase, obtains crude product；
The crude product is subjected to silica gel column chromatography, obtains 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde.
The present invention filters the remaining manganese dioxide of removal by diatomite；In the present invention, the silica gel column chromatography is with washing De- agent is preferably n-hexane-ethyl acetate mixed solvent；The volume ratio of the in the mixed solvent n-hexane and ethyl acetate is preferred For 30:1；The present invention does not have particular/special requirement to the temperature being evaporated off, and solvent can be evaporated off completely.
After obtaining 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde, the present invention phenyl lithium, lithium bromide, the tert-butyl alcohol and Under the action of potassium tert-butoxide, 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde and propyl triphenylphosphinebromide are carried out Wittig-Schlosser reaction obtains trans- 1,1- diethoxy -15- octadecene -13- alkynes (chemical combination in structural formula such as formula a Shown in object 7).In the present invention, 15, the 15- diethoxy-pentadecane -13- alkynes -1- aldehyde, propyl triphenylphosphinebromide, benzene Base lithium, lithium bromide, the tert-butyl alcohol and potassium tert-butoxide molar ratio be preferably 1:1.2~1.5:2:2:1.5~2:1.5~2.0, it is more excellent It is selected as 1:1.3~1.4:2:2:1.6~1.8:1.6~1.8；The lithium bromide is preferably anhydrous lithium bromide；The Wittig- The solvent of Schlosser reaction is preferably anhydrous tetrahydro furan.
In the present invention, the Wittig-Schlosser reaction specifically:
Lithium bromide, propyl triphenylphosphinebromide are dissolved in anhydrous tetrahydro furan, are cooled to -70~-80 after stirring 10min DEG C, preferably -78 DEG C, phenyl lithium solution is then added dropwise, is slowly increased to that 30min is stirred at room temperature after being added dropwise, it is then cold again But to -70~-80 DEG C, preferably -78 DEG C, it is molten that 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde tetrahydrofuran is added dropwise Liquid is added dropwise phenyl lithium solution after reacting 10min again, is stirred to react 30min, then sequentially adds the tert-butyl alcohol and potassium tert-butoxide, 1.5~2.5h, preferably 2h are reacted at room temperature, obtain trans- 1,1- diethoxy -15- octadecene -13- alkynes.
The present invention first heats up after phenyl lithium solution is added dropwise in first time and cools down again, peomotes Wittig-Schlosser The generation of organic phosphine intermediate in reaction；The phenyl lithium solution is added in two portions, and peomotes intermediate to anti-configuration The transformation of product；The solvent of the phenyl lithium solution is preferably ether；The concentration of the phenyl lithium solution is preferably 1mol/L.
After the reaction was completed, the present invention preferably will be after the progress of Wittig-Schlosser reaction solution by Wittig-Schlosser Reason；The post-processing preferably includes following steps:
N-hexane extraction is used after Wittig-Schlosser reaction solution and water are mixed, obtains extraction organic phase；
Solvent will be evaporated off after extraction organic phase drying, obtains crude product；
The crude product is subjected to silica gel column chromatography, obtains trans- 1,1- diethoxy -15- octadecene -13- alkynes.
In the present invention, the drying is preferably anhydrous sodium sulfate with desiccant；The silica gel column chromatography eluant, eluent is excellent It is selected as n-hexane-ethyl acetate mixed solvent；The volume ratio of the in the mixed solvent n-hexane and ethyl acetate is preferably 30:1； The present invention does not have particular/special requirement to the temperature being evaporated off, and solvent can be evaporated off completely.
After obtaining trans- 1,1- diethoxy -15- octadecene -13- alkynes, the present invention is in dicyclohexyl borane and glacial acetic acid Under effect, trans- 1,1- diethoxy -15- octadecene -13- alkynes is subjected to Borohydride reduction reaction, obtains suitable, trans- 1,1- bis- 18 carbon diene of ethyoxyl -13,15- (structural formula is as shown in compound 8 in formula a).In the present invention, trans- 1, the 1- diethyl The molar ratio of Oxy-1 5- octadecene -13- alkynes, dicyclohexyl borane and glacial acetic acid is preferably 1:2~4:6~10, more preferably For 1:3:8；The solvent of the Borohydride reduction reaction is preferably tetrahydrofuran.
In the present invention, the Borohydride reduction reaction is preferred specifically:
The tetrahydrofuran solution of trans- 1,1- diethoxy -15- octadecene -13- alkynes is added drop-wise in dicyclohexyl borane Hydroboration is carried out, glacial acetic acid is then added into reaction solution and carries out reduction reaction.
In the present invention, the tetrahydrofuran solution of trans- 1, the 1- diethoxy -15- octadecene -13- alkynes preferably - It is added drop-wise in dicyclohexyl borane under the conditions of 20 DEG C, in -20 DEG C of reaction 2h after being added dropwise, is then being warmed to room temperature reaction to two Cyclohexyl borine precipitating disappears, i.e. completion hydroboration.In the present invention, the temperature of the reduction reaction is preferably 40~50 DEG C, more preferably 45 DEG C, the time is preferably 12~for 24 hours, more preferably 15~20h.During hydroboration, trans- 1,1- Diethoxy -15- octadecene -13- alkynes is reacted with diborane generates alkenyl borane, during reduction reaction, alkenyl borane With acetic acid reaction, suitable, trans- 1,1- diethoxy -13,15-, 18 carbon diene is generated.
After the reaction was completed, the present invention preferably post-processes Borohydride reduction reaction solution Borohydride reduction, locates after described Reason preferably includes following steps:
Sodium hydroxide solution is added into the Borohydride reduction reaction solution and hydrogen peroxide is reacted, to remove two hexamethylenes Ylboronic acid ester, is extracted using n-hexane after completion of the reaction, obtains extraction organic phase；
Organic solvent in the extraction organic phase is evaporated off, suitable, trans- 1,1- diethoxy -13,15-, 18 carbon is obtained Diene crude product；The crude product is directly used in and reacts in next step without being further processed.
In the present invention, the concentration of the sodium hydroxide solution is preferably 6mol/L, and the quality percentage of the hydrogen peroxide contains Amount preferably 35%；The present invention is to the reaction time after the additional amount and addition of the sodium hydroxide solution and hydrogen peroxide without spy It is different to require, dicyclohexyl borate can be removed complete.In the present invention, the number of the extraction is preferably 3 times, extraction Organic phase is merged after taking.
Obtain it is suitable, after trans- 1,1- diethoxy -13,15-, 18 carbon diene, the present invention oxalic acid effect under, will be suitable, it is trans- 1,1- diethoxy -13,15-, 18 carbon diene carries out acetal protecting group elimination reaction, obtains suitable, trans- 13,15-, 18 carbon two Olefine aldehydr.In the present invention, trans- 1,1- diethoxy -15- octadecene-in step (8) mesoxalic acid and the step (7) The molar ratio of 13- alkynes is preferably 3~3.5:1, more preferably 3:1；The oxalic acid is preferably oxalic acid dihydrate；The acetal is protected The solvent for protecting base elimination reaction is preferably tetrahydrofuran-water mixed solvent；The present invention does not have special want to the dosage of the solvent It asks, can guarantee that reaction is gone on smoothly；The temperature of the acetal protecting group elimination reaction is preferably 50~70 DEG C, more preferably It is 60 DEG C, the time is preferably 30~50min, more preferably 40min.
In a specific embodiment of the present invention, preferably will be obtained in the previous step suitable, trans- 1,1- diethoxy -13,15- ten Eight carbon diene crude products are dissolved in tetrahydrofuran, and then the tetrahydrofuran solution of crude product is added drop-wise in oxalic acid aqueous solution and is carried out Reaction.
After the completion of acetal protecting group elimination reaction, after the present invention preferably carries out gained acetal protecting group elimination reaction liquid Reason；The post-processing preferably includes following steps:
Acetal protecting group elimination reaction liquid is subjected to n-hexane extraction, obtains extraction organic phase；
It will be successively dried and silica gel column chromatography after extraction organic phase washing, and obtain suitable, trans- 13,15-, 18 carbon Two olefine aldehydrs.
In the present invention, the number of the n-hexane extraction is preferably 3 times, merges organic phase after extraction；The washing Preferably successively washed using hydration saturated sodium-chloride；The drying is preferably anhydrous sodium sulfate with desiccant；The silicon Plastic column chromatography is preferably n-hexane-ethyl acetate mixed solvent with eluant, eluent；The in the mixed solvent n-hexane and ethyl acetate Volume ratio be preferably 50:1.
In the art, conventional Wittig reaction product is usually this synthetic method based on cis-configuration double bond product (Wittig-Schlosse reaction) is reacted using the Wittig of improvement, product is therefore of the invention based on the double bond of anti-configuration Synthetic method realizes micromelalopha troglodyte sex pheromone stereoselective syntheses.
The present invention also provides a kind of identification methods of micromelalopha troglodyte sex pheromone active constituent, comprising the following steps:
Using gas-chromatography-tentaculum electric potential instrument to micromelalopha troglodyte sex pheromone gland extract and suitable, trans- 13,15- 18 Two olefine aldehydr of carbon is analyzed respectively, obtains corresponding map；
Spectrogram is analyzed, if showing suitable, trans- 13,15-, 18 carbon, two olefine aldehydr and micromelalopha troglodyte sex pheromone in spectrogram The retention time of gland extract is close, and can cause micromelalopha troglodyte hero moth EAG response, then can determine it is suitable, it is trans- 18 carbon of 13,15-, two olefine aldehydr is micromelalopha troglodyte sex pheromone active constituent.
In the present invention, the extracting method of the micromelalopha troglodyte sex pheromone gland extract preferably includes following steps:
More are acquired gently to be squeezed when its sexual gland is overhanging with hand in the estrous female moth of micromelalopha troglodyte not mated Female moth abdomen, forces its sexual gland fully extended, cuts sexual gland, be immediately placed in the sample bottle of n-hexane and impregnate, obtain extracting solution, It is concentrated after the sexual gland extracting solution of the more female moths of micromelalopha troglodyte is merged, micromelalopha troglodyte sex pheromone gland extract.
In the present invention, the quantity of the female moth of the micromelalopha troglodyte is preferably 10, and the volume of the n-hexane is preferably 100 μ L, the time of immersion are preferably 30min.
The present invention does not have particular/special requirement to the gas-chromatography-tentaculum electric potential instrument, and use is well known to those skilled in the art Gas-chromatography-tentaculum electric potential instrument；In the present invention, the gas-chromatography-tentaculum electric potential instrument GC conditions are preferred Are as follows:
Chromatographic column: DB-5MS, 30m × 0.25mm × 0.25 μm, J&W Scientice, Folsom, CA；
Detector: hydrogen flameionization monitor (FID)；
Burner: hydrogen, flow 40mL/min；
Combustion-supporting gas: dry air, flow 400mL/min；
Carrier gas: nitrogen, flow 2.5mL/min；
Injector temperature: 220 DEG C；
Detector temperature: 280 DEG C；
Chromatographic column program:, keeping 2min by 60 DEG C of initial temperature, is warming up to 280 DEG C with the rate program of 8 DEG C/min, keeps 20min；
Input mode: Splitless injecting samples, sample volume 1 μ L, sample concentration 10ng/ μ L；
Outlet end current divider: 0SS-2.SGE, Australia, split ratio 1:2.
Tentaculum electric potential instrument operating condition is preferred are as follows:
EAG probe: PRG-2, forked feeler fixator；
IDAC converter: Auto Spike, IDAC2/3, Syntech；
Amplifier: UN-06, Syntech；
Feeler source: 2-3 days micromelalopha troglodyte hero moth feelers after emergence；
Feeler length: 10mm；
Processing mode: being cut with dissecting scissors from root, and about 0.5mm is wiped out on feeler top, with conducting resinl by feeler and EAG Two silver electrodes connection of probe (PRG-2) forked feeler fixator.
The present invention uses gas-chromatography-tentaculum electric potential technology, by the standard substance of synthesis and micromelalopha troglodyte sex pheromone gland Body extract compares and analyzes, so that it is determined that micromelalopha troglodyte sex pheromone active constituent, the identification method is short with the period, ties The advantages that fruit is with a high credibility.
Scheme provided by the invention is described in detail below with reference to embodiment, but they cannot be interpreted as pair The restriction of the scope of the present invention.
Embodiment 1
The synthesis of 1,1- diethoxy -12- dodecyl iodides:
The bromo- DODECANOL, 1- of 12- (26.5g, 0.1mol) is added dropwise to the methylene chloride of pyridinium chloro-chromate (0.4mol) In (600mL) solution, normal-temperature reaction 4h generates the bromo- 1- lauric aldehyde of 12-；
Product reacts in dehydrated alcohol with triethyl orthoformate (22.2g, 0.15mol) without further purification, and catalyst is pair Overnight, after completion of the reaction, it is molten that saturated sodium bicarbonate is added in toluenesulfonic acid monohydrate (290mg), 0 DEG C of reaction in reaction solution Liquid, ethyl acetate extract three times, and combining extraction liquid, anhydrous sodium sulfate is dry, and solvent is evaporated off, and obtain aldehyde radical by ethyoxyl and protect production Object 1,1- diethoxy -12- bromododecane；
In anhydrous propanone, 1,1- diethoxy -12- bromododecane is reacted with sodium iodide, molar ratio 2:1, bromo Group is replaced by iodine；After completion of the reaction, organic solvent is evaporated off, distilled water is added, ethyl acetate extracts three times, merges organic phase, nothing Aqueous sodium persulfate is dry；Solvent is evaporated off, crude product obtains 1,1- diethyl through silica gel column chromatography n-hexane/ethyl acetate (25:1, v/v) Oxy-1 2- dodecyl iodides 34.6g, yield 90%.
The synthesis of 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde:
At -20 DEG C, the tetrahydrofuran solution (2.5M, 80mL, 0.2mol) of n-BuLi is slowly added dropwise into propilolic alcohol In tetrahydrofuran/hexamethylphosphoramide (1:1, v/v, the 800mL) solution of (0.1mol), then by 1,1- diethoxy -12- Dodecyl iodides (19.2g, 0.05mol) are slowly added dropwise in above-mentioned reaction solution, react 2h, after completion of the reaction, saturation chlorination are added Ammonium salt solution terminates reaction, and ethyl acetate extracts three times, and organic phase is dried over anhydrous sodium sulfate；Solvent is evaporated off, obtains 15,15- bis- Ethyoxyl-pentadecane -13- alkynes -1- alcohol crude product；
Then crude product is instilled in the suspension of electrolytic manganese dioxide (0.3mol) n-hexane, N2Gas shielded, 0 DEG C of reaction 4h is filtered by diatomite after completion of the reaction, removes remaining manganese dioxide；Organic phase is evaporated off in filtrate, crude product is obtained, through silica gel Column chromatography, n-hexane/ethyl acetate (30:1, v/v) obtain 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde 10.1g, yield 65%.
The synthesis of trans- 1,1- diethoxy -15- octadecene -13- alkynes:
The THF solution of anhydrous LiBr is added in propyl triphenylphosphinebromide (0.06mol), 10min is stirred at room temperature；Then - 78 DEG C are cooled to, PhLi (1M in Et is added dropwise2O, 1.0equiv), it is slowly increased to that 30min is stirred at room temperature；Again, be cooled to- 78 DEG C, the THF solution of alkynes aldehyde (9.3g, 0.03mol) is slowly added dropwise, reacts 10min；PhLi (1M in Et is added dropwise again2O, 1.0equiv), after stirring 30min, the tert-butyl alcohol (0.45mL), potassium tert-butoxide (0.44g) are sequentially added, reacts at room temperature 2h；Reaction After, distilled water is added, with n-hexane extraction, organic phase is dried over anhydrous sodium sulfate, and solvent is evaporated off, just through silica gel column chromatography Hexane/ethyl acetate (30:1, v/v) obtains trans- 1,1- diethoxy -15- octadecene -13- alkynes 7.0g, yield 70%.
It is suitable, the synthesis of trans- 18 carbon of 13,15-, two olefine aldehydr:
The THF solution of trans- 1,1- diethoxy -15- octadecene -13- alkynes (6.72g, 0.02mol) is added to two rings In hexyl borine (7.12g, 0.04mol), then -20 DEG C of reaction 2h react at room temperature 2h, until dicyclohexyl borane precipitating disappears； Then glacial acetic acid (5mL) is added, 45 DEG C of reactions are overnight；Sequentially add NaOH (6M, 6mL), H2O2(35%, 7mL) removes two hexamethylenes Ylboronic acid ester；After completion of the reaction, n-hexane extraction three times, is evaporated off organic phase and obtains suitable, trans- 1,1- diethoxy -13,15- ten Eight carbon diene crude products；
Then crude product is dissolved in THF, be added in the aqueous solution of oxalic acid dihydrate (3.0g), 60 DEG C are stirred to react 40min；After the reaction was completed, n-hexane extraction reaction solution three times, through washing, wash organic phase by saturated sodium-chloride, and anhydrous sodium sulfate is dry Dry, through silicagel column purified n-hexane/ethyl acetate (50:1, v/v), it is suitable to obtain compound, trans- 13,15-, 18 carbon, two olefine aldehydr 3.17g, yield 60%.
The appraising datum of product structure:
1H-NMR(500MHz,CDCl3) δ 1.00 (3H, t, J=7.5Hz), 1.24-1.30 (16H, m), 1.59-1.65 (2H, m), 2.09-2.22 (4H, m), 2.42 (2H, td, J=7.5,2.0Hz), 5.41-5.47 (2H, m), 6.19-6.32 (2H, M), 9.76 (1H, t, J=2.0Hz)；13C-NMR(125MHz,CDCl3)δ202.9,133.6,132.1,123.4,123.0, 43.9,29.6,29.5,29.5,29.4,29.3,29.3,29.2,29.1,27.5,22.1,2 0.8,14.2.GC-MS of is suitable, Trans- 18 carbon of 13,15-, two olefine aldehydr (70eV, EI): 264.
Embodiment 2
The identification method of micromelalopha troglodyte sex pheromone active constituent
Instrument: U.S.'s Agilent Agilent 7890A gas chromatograph-Holland Syntech tentaculum electric potential combined instrument (GC- EAD)；
Chromatographic column: DB-5MS, 30m × 0.25mm × 0.25 μm, J&W Scientice, Folsom, CA；
Gas-chromatography operating condition:
Detector: hydrogen flameionization monitor (FID)；
Burner: hydrogen, flow 40mL/min；
Combustion-supporting gas: dry air.Flow 400mL/min；
Carrier gas: nitrogen, flow 2.5mL/min；
Injector temperature: 220 DEG C；
Detector temperature: 280 DEG C；
Chromatographic column program:, keeping 2min by 60 DEG C of initial temperature, is warming up to 280 DEG C with the rate program of 8 DEG C/min, keeps 20min；
Input mode: Splitless injecting samples, sample volume 1 μ L, sample concentration 10ng/uL；
Outlet end current divider: 0SS-2.SGE, Australia, split ratio 1:2；Tentaculum electric potential instrument operating condition:
EAG probe: PRG-2, forked feeler fixator；
IDAC converter: Auto Spike, IDAC2/3, Syntech；
Amplifier: UN-06, Syntech；
Feeler source: 2~3 days micromelalopha troglodyte hero moth feelers after emergence；
Length: 10mm；
Processing mode: being cut with dissecting scissors from root, and about 0.5mm is wiped out on feeler top, with conducting resinl by feeler and EAG Two silver electrodes connection of probe (PRG-2) forked feeler fixator.
The authentication step of micromelalopha troglodyte sex pheromone active constituent:
The extraction of micromelalopha troglodyte sex pheromone: acquisition does not mate female moth 10 in estrous micromelalopha troglodyte, to its property When body of gland is overhanging, female moth abdomen is gently squeezed with hand, is forced its sexual gland body fully extended, is cut with eye scissors, is immediately placed in pre- First in the sample bottle equipped with 100 μ L n-hexanes, body of gland is taken out after impregnating 30min, is concentrated after combined extract, concentration gained is mentioned It takes object sealing to be placed on -20 DEG C to save backup；
The compound that micromelalopha troglodyte sex pheromone gland extract and embodiment 1 are synthesized is suitable, trans- 18 carbon two of 13,15- Olefine aldehydr carries out gas-chromatography-tentaculum electric potential instrument analysis respectively, obtains corresponding gas-chromatography-tentaculum electric potential instrument analysis map, such as Shown in Fig. 1~2, wherein Fig. 1 is gas-chromatography-of the micromelalopha troglodyte hero moth feeler to female moth sex pheromone body of gland n-hexane extract Tentaculum electric potential instrument analyzes GC-EAD map；Fig. 2 is gas-chromatography-tentaculum electric potential of the micromelalopha troglodyte hero moth feeler to synthesis compound Instrument analyzes GC-EAD map, and wherein A is suitable, trans- 13,15-, 18 carbon, two olefine aldehydr.
According to Fig. 1~2 as can be seen that having in gland extract makes the significant electrophysiologic response of micromelalopha troglodyte hero moth feeler Sex pheromone ingredient, in the presence of the property information that can cause micromelalopha troglodyte hero moth EAG response at retention time 21.89min Plain ingredient；By the data from gas chromatography analysis in Fig. 2 it is found that the finally obtained compound of the embodiment of the present invention 1 is with cis-trans configurations Based on product, simultaneously containing a small amount of along anomeric product (peak on the left of A), compound is suitable, trans- 13,15-, 18 carbon, two olefine aldehydr Retention time be 22.10min, and apparent EAG response can be caused, and suitable, 18 carbon diene of cis- 13,15- Aldehyde fails that male moth feeler is made to generate electrophysiologic response；It is possible thereby to which determination is suitable, trans- 18 carbon of 13,15-, two olefine aldehydr is micromelalopha troglodyte Female moth sex pheromone active constituent.
As can be seen from the above embodiments, present invention firstly provides the structures of micromelalopha troglodyte sex pheromone active constituent is Suitable, trans- 13,15-, 18 carbon, two olefine aldehydr, the compound can cause micromelalopha troglodyte hero moth electrophysiologic response, and the present invention provides Synthetic method have many advantages, such as that yield high, purity is high, stereoselectivity are strong, identification method provided by the invention has the period Short, the advantages that result credibility is high.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of micromelalopha troglodyte sex pheromone active constituent, which is characterized in that chemical name is suitable, trans- 13,15-, 18 carbon two Olefine aldehydr has structure shown in Formulas I:
2. the preparation method of micromelalopha troglodyte sex pheromone active constituent described in claim 1, which is characterized in that including following step It is rapid:
(1) under oxidant effect, the bromo- DODECANOL, 1- of 12- is subjected to oxidation reaction, obtains the bromo- 1- lauric aldehyde of 12-；
(2) under the action of catalyst, the bromo- 1- lauric aldehyde of 12- and triethyl orthoformate are subjected to aldehyde radical protection reaction, obtain 1,1- Diethoxy -12- bromododecane；
(3) by sodium iodide and 1,1- diethoxy -12- bromododecane carries out iodide reaction, obtains 1,1- diethoxy -12- Dodecyl iodides；
(4) under that action of n-butyl lithium, by propilolic alcohol and 1, it is anti-that 1- diethoxy -12- dodecyl iodides carry out alkynes alkylation It answers, obtains 15,15- diethoxy-pentadecane -13- alkynes -1- alcohol；
(5) under electrolytic manganese dioxide effect, it is anti-that 15,15- diethoxy-pentadecane -13- alkynes -1- alcohol is subjected to alkynol oxidation It answers, obtains 15,15- diethoxy-pentadecane -13- alkynes -1- aldehyde；
(6) under the action of phenyl lithium, lithium bromide, the tert-butyl alcohol and potassium tert-butoxide, by 15,15- diethoxy-pentadecane -13- Alkynes -1- aldehyde and propyl triphenylphosphinebromide carry out Wittig-Schlosser reaction, obtain trans- 1,1- diethoxy -15- 18 Carbene -13- alkynes；
(7) under dicyclohexyl borane and glacial acetic acid effect, trans- 1,1- diethoxy -15- octadecene -13- alkynes is subjected to boron Hydro-reduction reaction, obtains suitable, trans- 1,1- diethoxy -13,15-, 18 carbon diene；
(8), will be suitable under oxalic acid effect, it is anti-that trans- 1,1- diethoxy -13,15-, 18 carbon diene carries out acetal protecting group removing It answers, obtains suitable, trans- 13,15-, 18 carbon, two olefine aldehydr.
3. preparation method according to claim 2, which is characterized in that oxidant includes chloro-chromic acid pyrrole in the step (1) One or more of pyridine salt, two pyridinium chloro-chromates, tetramethyl piperidine nitrogen oxides and the high iodine alkane of Dai Si-Martin；
The molar ratio of the bromo- DODECANOL, 1- of the 12- and oxidant is 1:2~4；
The temperature of the oxidation reaction be room temperature, the time be 2~for 24 hours.
4. preparation method according to claim 2, which is characterized in that catalyst includes to toluene sulphur in the step (2) Acid and/or pyridine tosylat；
The molar ratio of the bromo- 1- lauric aldehyde of the catalyst, 12- and triethyl orthoformate is 1:100:60~70；
The temperature of aldehyde radical protection reaction is -5~0 DEG C, the time is 10~for 24 hours.
5. preparation method according to claim 2, which is characterized in that sodium iodide and 1 in the step (3), 1- diethoxy The molar ratio of base -12- bromododecane is 2~3:1；
The iodide reaction carries out under reflux conditions, the time be 6~for 24 hours.
6. preparation method according to claim 2, which is characterized in that 1,1- diethoxy -12- iodine in the step (4) Molar ratio for dodecane, propilolic alcohol and n-BuLi is 1:2~3:4~5；
The temperature of the alkynes alkylated reaction is -15~-30 DEG C, and the time is 2~5h.
7. preparation method according to claim 2, which is characterized in that electrolytic manganese dioxide and 15 in the step (5), 15- diethoxy-pentadecane -13- alkynes -1- alcohol molar ratio is 30~40:1；
The temperature of the alkynol oxidation reaction be -5~0 DEG C, the time be 4~for 24 hours.
8. preparation method according to claim 2, which is characterized in that 15,15- diethoxy-ten five in the step (6) Carbon -13- alkynes -1- aldehyde, propyl triphenylphosphinebromide, phenyl lithium, lithium bromide, the tert-butyl alcohol and potassium tert-butoxide molar ratio be 1:1.2 ~1.5:2:2:1.5~2:1.5~2.0.
9. preparation method according to claim 2, which is characterized in that trans- 1,1- diethoxy -15- in the step (7) The molar ratio of octadecene -13- alkynes, dicyclohexyl borane and glacial acetic acid is 1:2~4:6~10；
The molar ratio of trans- 1,1- diethoxy -15- octadecene -13- alkynes in step (8) mesoxalic acid and the step (7) For 3~3.5:1.
10. a kind of identification method of micromelalopha troglodyte sex pheromone active constituent, which comprises the following steps:
Using gas-chromatography-tentaculum electric potential instrument to micromelalopha troglodyte sex pheromone gland extract and suitable, trans- 18 carbon two of 13,15- Olefine aldehydr is analyzed respectively, obtains corresponding map；
Spectrogram is analyzed, if showing suitable, trans- 13,15-, 18 carbon, two olefine aldehydr and micromelalopha troglodyte sex pheromone body of gland in spectrogram The retention time of extract is close, and can cause micromelalopha troglodyte hero moth EAG response, then can determine it is suitable, trans- 13, 18 carbon of 15-, two olefine aldehydr is micromelalopha troglodyte sex pheromone active constituent.
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CN110724042A (en) * 2019-12-09 2020-01-24 中国林业科学研究院森林生态环境与保护研究所 Method for synthesizing sex pheromone active ingredient of populus canula
CN110959613A (en) * 2019-12-19 2020-04-07 中国林业科学研究院森林生态环境与保护研究所 Poplar canula moth sex pheromone attractant composition, lure core and preparation method and application thereof
CN111302918A (en) * 2020-04-03 2020-06-19 中国林业科学研究院森林生态环境与保护研究所 Stereoselective synthesis method of (Z, E) -13, 15-octadecadienal
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CN111943821A (en) * 2020-09-15 2020-11-17 苏州华道生物药业股份有限公司 Synthesis method of (13 cis, 15 trans) -octadecadienal
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JP2022006362A (en) * 2020-06-24 2022-01-13 信越化学工業株式会社 Production method of (9z,11e)-9,11-hexadecadienal

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CN110724042A (en) * 2019-12-09 2020-01-24 中国林业科学研究院森林生态环境与保护研究所 Method for synthesizing sex pheromone active ingredient of populus canula
CN110959613A (en) * 2019-12-19 2020-04-07 中国林业科学研究院森林生态环境与保护研究所 Poplar canula moth sex pheromone attractant composition, lure core and preparation method and application thereof
CN111302918A (en) * 2020-04-03 2020-06-19 中国林业科学研究院森林生态环境与保护研究所 Stereoselective synthesis method of (Z, E) -13, 15-octadecadienal
CN111766316A (en) * 2020-06-15 2020-10-13 宁夏大学 Extraction and component analysis method of elm jumping figure sex pheromone
JP2022006362A (en) * 2020-06-24 2022-01-13 信越化学工業株式会社 Production method of (9z,11e)-9,11-hexadecadienal
JP7291105B2 (en) 2020-06-24 2023-06-14 信越化学工業株式会社 Method for producing (9Z,11E)-9,11-hexadecadienal
CN111943821A (en) * 2020-09-15 2020-11-17 苏州华道生物药业股份有限公司 Synthesis method of (13 cis, 15 trans) -octadecadienal
CN111943821B (en) * 2020-09-15 2022-04-05 苏州华道生物药业股份有限公司 Synthesis method of (13 cis, 15 trans) -octadecadienal
CN113307728A (en) * 2021-06-17 2021-08-27 南京蕃茂生物科技有限公司 Preparation method of populus canula pheromone

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