CN110372482B - Poplar canula moth sex pheromone active ingredient and preparation and identification method thereof - Google Patents
Poplar canula moth sex pheromone active ingredient and preparation and identification method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of insect sex pheromone component identification and synthesis, and provides a sex pheromone active component of a populus canescens and a preparation method and an identification method thereof. The invention firstly defines that the structure of the sex pheromone active component of the populus canescens is cis-trans-13, 15-octadecadienal aldehyde, the active component can cause the remarkable electrophysiological reaction of the male populus canescens, and lays a theoretical foundation for the measurement and the report and the trapping of the woodland populus canescens. The method synthesizes the sex pheromone active ingredients of the populus canula by a Wittig-Schlosse reaction and a hydroboration-reduction method, and has the advantages of high yield, high purity, strong stereoselectivity, high result reproducibility and the like. The invention adopts a gas chromatography-antenna potential technology, and determines the active ingredients of the sex pheromone of the populus canula moth by a method of comparing and analyzing a synthesized standard substance and the sex pheromone gland extract of the populus canula moth, and the identification method has short period and high result reliability.
Description
Technical Field
The invention relates to the technical field of insect sex pheromone component identification and synthesis, in particular to a sex pheromone active component of a populus canescens and a preparation method and an identification method thereof.
Background
The Micromelalopha troglodyta (Graeser) is one of main poplar leaf-eating pests in China, is rampant and disastrous in northeast, northwest, central plains and central south and other areas of China, not only influences the normal growth of poplar and causes huge economic loss, but also destroys ecological environment and seriously restricts the development of forestry.
At present, the prevention and control method for the insects mainly comprises chemical pesticides and natural enemy insects, and although the chemical pesticides have quick effect, the prevention and control method has high prevention and control cost, and is easy to generate pesticide residues, environmental pollution, drug resistance of pests and other problems; the feeding and throwing technical requirements of the natural enemy insects are high. Therefore, the existing control technology is not satisfactory in effect, and a continuous and efficient control technology needs to be researched and developed urgently.
The insect sex pheromone has the advantages of high efficiency, durability, no toxicity, strong specificity, no harm to natural enemies, no environmental pollution and the like in pest control; in addition, the insect sex pheromone is matched with other pest control measures (especially biological control) to show good compatibility, has been highly valued by scholars at home and abroad, and is becoming one of important measures in comprehensive pest control.
However, until now, no relevant research reports exist on the structural information of the sex pheromone active ingredient of the populus canescens, so that the identification and synthesis of the sex pheromone active ingredient of the populus canescens have important significance for utilizing the sex pheromone to comprehensively control pests.
Disclosure of Invention
In view of the above, the invention aims to provide an active ingredient of sex pheromone of populus canula, and a preparation and identification method thereof, the invention determines the structure of the active ingredient of the sex pheromone of populus canula, and synthesizes and identifies the active ingredient, thereby further determining cis-trans-13, 15-octadecadienal as the active ingredient of the sex pheromone of populus canula.
In order to achieve the above object, the present invention provides the following technical solutions:
the sex pheromone active ingredient of the populus canula is cis, trans-13, 15-octadecadienal and has a structure shown in a formula I:
the invention provides a preparation method of sex pheromone active ingredients of Populus mauritiana in the scheme, which comprises the following steps:
(1) under the action of an oxidant, carrying out oxidation reaction on 12-bromo-1-dodecanol to obtain 12-bromo-1-dodecanal;
(2) under the action of a catalyst, performing aldehyde group protection reaction on 12-bromo-1-dodecanal and triethyl orthoformate to obtain 1, 1-diethoxy-12-bromododecane;
(3) performing iodination reaction on sodium iodide and 1, 1-diethoxy-12-bromododecane to obtain 1, 1-diethoxy-12-iodododecane;
(4) under the action of n-butyllithium, carrying out alkyne alkylation reaction on propiolic alcohol and 1, 1-diethoxy-12-iodododecane to obtain 15, 15-diethoxy-pentadecan-13-alkyne-1-alcohol;
(5) under the action of electrolytic manganese dioxide, carrying out alkynol oxidation reaction on 15, 15-diethoxy-pentadec-13-alkyne-1-alcohol to obtain 15, 15-diethoxy-pentadec-13-alkyne-1-aldehyde;
(6) under the action of phenyl lithium, lithium bromide, tert-butyl alcohol and potassium tert-butoxide, carrying out Wittig-Schlosser reaction on 15, 15-diethoxy-pentadecan-13-alkyne-1-aldehyde and propyltriphenyl phosphine bromide to obtain trans-1, 1-diethoxy-15-octadecene-13-alkyne;
(7) under the action of dicyclohexylborane and glacial acetic acid, carrying out hydroboration reduction reaction on trans-1, 1-diethoxy-15-octadecene-13-alkyne to obtain cis-trans-1, 1-diethoxy-13, 15-octadecadiene;
(8) under the action of oxalic acid, the cis, trans-1, 1-diethoxy-13, 15-octadecadienol is subjected to acetal protecting group removing reaction to obtain the cis, trans-13, 15-octadecadienal.
Preferably, the oxidant in the step (1) comprises one or more of pyridinium chlorochromate, pyridinium dichlorochromate, tetramethylpiperidine oxynitride and dess-martin periodinane;
the molar ratio of the 12-bromo-1-dodecanol to the oxidant is 1: 2-4;
the temperature of the oxidation reaction is room temperature, and the time is 2-24 hours.
Preferably, the catalyst in the step (2) comprises p-toluenesulfonic acid and/or pyridine tosylate;
the molar ratio of the catalyst to the 12-bromo-1-dodecanal to the triethyl orthoformate is 1: 100: 60-70 parts of;
the aldehyde group protection reaction is carried out at the temperature of-5-0 ℃ for 10-24 hours.
Preferably, in the step (3), the molar ratio of the sodium iodide to the 1, 1-diethoxy-12-bromododecane is 2-3: 1;
the iodination reaction is carried out under the reflux condition for 6-24 h.
Preferably, the molar ratio of 1, 1-diethoxy-12-iodododecane, propiolic alcohol and n-butyllithium in the step (4) is 1: 2-3: 4-5;
the temperature of the alkyne alkylation reaction is-15 to-30 ℃, and the time is 2 to 5 hours.
Preferably, the molar ratio of the electrolytic manganese dioxide to the 15, 15-diethoxy-pentadecan-13-alkyne-1-alcohol in the step (5) is 30-40: 1;
the temperature of the alkynol oxidation reaction is-5-0 ℃, and the time is 4-24 h.
Preferably, the molar ratio of 15, 15-diethoxy-pentadecan-13-yne-1-aldehyde, propyltriphenylphosphonium bromide, phenyllithium, lithium bromide, tert-butanol and potassium tert-butoxide in step (6) is 1: 1.2-1.5: 2: 2: 1.5-2: 1.5 to 2.0.
Preferably, the molar ratio of trans-1, 1-diethoxy-15-octadecen-13-yne, dicyclohexylborane and glacial acetic acid in the step (7) is 1: 2-4: 6-10;
the molar ratio of oxalic acid in the step (8) to trans-1, 1-diethoxy-15-octadecene-13-yne in the step (7) is 3-3.5: 1.
the invention also provides an identification method of sex pheromone active ingredients of the populus canula, which comprises the following steps:
respectively analyzing the sex pheromone gland extract of the populus canula and cis, trans-13, 15-octadecadienal by adopting a gas chromatography-antennal potentiometer to obtain corresponding maps;
and analyzing the spectrogram, and determining that the cis-trans-13, 15-octadecadienal is the active ingredient of the sex pheromone of the populus plutella if the retention time of the cis-trans-13, 15-octadecadienal and the sex pheromone gland extract of the populus plutella are similar and the androgenic reaction of the male tentacles of the populus plutella can be caused in the spectrogram.
The invention provides a sex pheromone active ingredient of a Populus plutella, the chemical name of which is cis, trans-13, 15-octadecadienal and the sex pheromone active ingredient has a structure shown in a formula I. The invention firstly defines the structure of the sex pheromone active ingredient of the populus canescens, the active ingredient can cause the remarkable electrophysiological reaction of the male populus canescens, and the theoretical basis is laid for the measurement and the report and the trapping of the populus canescens in forests.
The invention also provides a preparation method of the sex pheromone active ingredient of the populus canula. The method synthesizes the sex pheromone active ingredients of the populus canula by a Wittig-Schlosse reaction and a hydroboration-reduction method, and has the advantages of high yield, high purity, strong stereoselectivity, high result reproducibility and the like.
The invention also provides an identification method of the sex pheromone active ingredients of the populus canula. The invention adopts a gas chromatography-antenna potential technology, and determines the active ingredients of the sex pheromone of the populus canula moth by a method of comparing and analyzing a synthesized standard substance and the sex pheromone gland extract of the populus canula moth, and the identification method has short period and high result reliability.
Drawings
FIG. 1 is a GC-EAD spectrum of the analysis of a gas chromatography-antennal potentiostat of the n-hexane extract of the male-antennal moth-male sex pheromone gland of the invention;
FIG. 2 is a GC-EAD spectrum of the gas chromatography-antennal potentiostat analysis of the synthetic compound by the antennal moth of the invention, wherein A is cis, trans-13, 15-octadecadienal.
Detailed Description
The invention provides a sex pheromone active ingredient of a populus canula, which has a structure shown in a formula I:
the chemical name of the sex pheromone active ingredient of the populus canula is cis, trans-13, 15-octadecadienal, the invention firstly defines the structure of the sex pheromone active ingredient of the populus canula, and the active ingredient can cause the remarkable electrophysiological reaction of the male populus canula.
The invention also provides a preparation method of the sex pheromone active ingredient of the populus canula, which is characterized by comprising the following steps:
(1) under the action of an oxidant, carrying out oxidation reaction on 12-bromo-1-dodecanol to obtain 12-bromo-1-dodecanal;
(2) under the action of a catalyst, performing aldehyde group protection reaction on 12-bromo-1-dodecanal and triethyl orthoformate to obtain 1, 1-diethoxy-12-bromododecane;
(3) performing iodination reaction on sodium iodide and 1, 1-diethoxy-12-bromododecane to obtain 1, 1-diethoxy-12-iodododecane;
(4) under the action of n-butyllithium, carrying out alkyne alkylation reaction on propiolic alcohol and 1, 1-diethoxy-12-iodododecane to obtain 15, 15-diethoxy-pentadecan-13-alkyne-1-alcohol;
(5) under the action of electrolytic manganese dioxide, carrying out alkynol oxidation reaction on 15, 15-diethoxy-pentadec-13-alkyne-1-alcohol to obtain 15, 15-diethoxy-pentadec-13-alkyne-1-aldehyde;
(6) under the action of phenyl lithium, lithium bromide, tert-butyl alcohol and potassium tert-butoxide, carrying out Wittig-Schlosser reaction on 15, 15-diethoxy-pentadecan-13-alkyne-1-aldehyde and propyltriphenyl phosphonium bromide to obtain trans-1, 1-diethoxy-15-octadecene-13-alkyne;
(7) under the action of dicyclohexylborane and glacial acetic acid, carrying out hydroboration reduction reaction on trans-1, 1-diethoxy-15-octadecene-13-alkyne to obtain cis-trans-1, 1-diethoxy-13, 15-octadecadiene;
(8) under the action of oxalic acid, the cis, trans-1, 1-diethoxy-13, 15-octadecadienol is subjected to acetal protecting group removing reaction to obtain the cis, trans-13, 15-octadecadienal.
In the invention, the synthetic route of the sex pheromone active ingredient of the populus canula is shown as a formula:
under the action of an oxidant, 12-bromo-1-dodecanol (the structural formula is shown as a compound 1 in a formula a) is subjected to an oxidation reaction to obtain 12-bromo-1-dodecanal (the structural formula is shown as a compound 2 in a formula a). In the invention, the oxidant preferably comprises one or more of pyridinium chlorochromate, pyridinium dichlorochromate, tetramethylpiperidine nitroxide and dess-martin periodinane; the molar ratio of the 12-bromo-1-dodecanol and the oxidant is preferably 1: 2-4, more preferably 1: 3; the solvent for the oxidation reaction is preferably dichloromethane.
In the invention, the temperature of the oxidation reaction is preferably room temperature, and the time is preferably 2-24 h, more preferably 3-20 h, and even more preferably 4 h. According to the invention, the oxidant is preferably dissolved in the solvent to obtain the oxidant solution, then the 12-bromo-1-dodecanol is slowly added into the oxidant solution for oxidation reaction, and the time of the oxidation reaction is calculated from the time when the 12-bromo-1-dodecanol is completely added.
After the oxidation reaction is finished, any purification and post-treatment are not needed, and the product after the oxidation reaction is directly used as a reactant to participate in the next reaction.
After 12-bromo-1-dodecanal is obtained, under the action of a catalyst, performing aldehyde group protection reaction on 12-bromo-1-dodecanal and triethyl orthoformate to obtain 1, 1-diethoxy-12-bromododecane (the structural formula is shown as a compound 3 in a formula a). In the present invention, the catalyst preferably comprises p-toluenesulfonic acid and/or pyridine tosylate, more preferably p-toluenesulfonic acid, which is preferably p-toluenesulfonic acid monohydrate; the molar ratio of the catalyst, 12-bromo-1-dodecanal and triethyl orthoformate is preferably 1: 100: 60-70, more preferably 1: 100: 63-68, and more preferably 1: 100: 65. in the invention, the solvent for aldehyde group protection reaction is preferably one or more of absolute ethyl alcohol, absolute dichloromethane, absolute tetrahydrofuran and anhydrous dioxane, and the invention has no special requirement on the dosage of the solvent and can ensure that the aldehyde group protection reaction is smoothly carried out.
In the invention, the temperature of the aldehyde group protection reaction is preferably-5-0 ℃, more preferably 0 ℃, and the time is preferably 10-24 hours, more preferably 11-22 hours, and further preferably 12-20 hours. In the specific embodiment of the invention, preferably, the reaction solution after the oxidation reaction is directly added into the aldehyde group protection reaction solvent to obtain a 12-bromo-1-dodecanal solution, then triethyl orthoformate is slowly dripped into the 12-bromo-1-dodecanal solution at the temperature of-5 to 0 ℃, and the aldehyde group protection reaction is carried out at the temperature of-5 to 0 ℃ after the dripping is finished; the aldehyde group protection reaction time is calculated from the point that triethyl orthoformate is dripped.
After the aldehyde protection reaction is completed, the invention preferably performs post-treatment on the aldehyde protection reaction solution, and in the invention, the post-treatment preferably comprises the following steps:
mixing aldehyde group protection reaction liquid and saturated sodium carbonate solution, and then extracting with ethyl acetate to obtain an extracted organic phase;
and drying the extracted organic phase, and then evaporating the solvent to obtain the 1, 1-diethoxy-12-bromododecane.
In the present invention, the number of times of extraction is preferably 3, and the organic phases are combined after the extraction is completed; the drying desiccant is preferably anhydrous sodium sulfate; the invention has no special requirement on the steaming temperature, and can completely steam the solvent.
After 1, 1-diethoxy-12-bromododecane is obtained, sodium iodide and 1, 1-diethoxy-12-bromododecane are subjected to iodination reaction to obtain 1, 1-diethoxy-12-iodododecane (the structural formula is shown as a compound 4 in a formula a). In the invention, the molar ratio of the sodium iodide to the 1, 1-diethoxy-12-bromododecane is preferably 2-3: 1; the solvent for the iodination reaction is preferably anhydrous acetone; the iodination reaction is preferably carried out under a reflux condition, the time is preferably 6-24 h, more preferably 10-20 h, and further preferably 12-18 h; the temperature of the reflux reaction is set according to the boiling point of the solvent.
In the embodiment of the present invention, it is preferable that 1, 1-diethoxy-12-bromododecane is dissolved in anhydrous acetone, and then sodium iodide is added to the anhydrous acetone solution of 1, 1-diethoxy-12-bromododecane to carry out the reaction.
After the iodination reaction is completed, the present invention preferably performs a post-treatment on the iodination reaction solution, and the post-treatment preferably includes the following steps:
after the organic solvent in the iodo reaction solution is distilled off, mixing the residue with water, and then extracting with ethyl acetate to obtain an organic phase;
drying the organic phase, and evaporating to remove the solvent to obtain a crude product;
and performing silica gel column chromatography on the crude product to obtain 1, 1-diethoxy-12-iodododecane.
In the present invention, the number of times of extraction is preferably 3, and the organic phases are combined after the extraction is completed; the drying desiccant is preferably anhydrous sodium sulfate; the eluent for silica gel column chromatography is preferably a mixed solvent of n-hexane and ethyl acetate; the volume ratio of n-hexane to ethyl acetate in the mixed solvent is preferably 25: 1; the invention has no special requirement on the steaming temperature, and can completely steam the solvent.
After 1, 1-diethoxy-12-iodododecane is obtained, under the action of n-butyllithium, propargyl alcohol and 1, 1-diethoxy-12-iodododecane are subjected to alkyne alkylation reaction to obtain 15, 15-diethoxy-pentadeca-13-alkyne-1-alcohol (the structural formula is shown as a compound 5 in a formula a). In the present invention, the molar ratio of 1, 1-diethoxy-12-iodododecane, propiolic alcohol and n-butyllithium is preferably 1: 2-3: 4-5, more preferably 1: 2: 4; the solvent for the alkyne alkylation reaction is preferably a tetrahydrofuran-hexamethylphosphoric triamide mixed solvent; the invention has no special requirement on the volume of the solvent, and can ensure that the reaction is carried out smoothly; the temperature of the alkyne alkylation reaction is preferably-15 to-30 ℃, more preferably-20 ℃, and the time is preferably 2 to 5 hours, more preferably 2 hours.
In the embodiment of the present invention, n-butyllithium is preferably dissolved in tetrahydrofuran, and then a tetrahydrofuran solution of n-butyllithium and 1, 1-diethoxy-12-iodododecane are added dropwise to a tetrahydrofuran-hexamethylphosphoric triamide mixed solvent in sequence at-15 to-30 ℃ to react; the alkyne alkylation reaction time of the invention is calculated from the completion of the dropwise addition of 1, 1-diethoxy-12-iodododecane.
After the alkyne alkylation reaction is completed, the present invention preferably performs post-treatment on the alkyne alkylation reaction solution, and the post-treatment preferably comprises the following steps:
adding ammonium chloride into alkyne alkylation reaction liquid to terminate the reaction, then extracting by using ethyl acetate to obtain an extracted organic phase, drying the extracted organic phase, and evaporating to remove the solvent to obtain a crude product of 15, 15-diethoxy-pentadec-13-alkyne-1-alcohol; the crude product is directly used in the next reaction without further treatment.
In the present invention, the number of the extractions is preferably 3, and the organic phases are combined after the extractions; the drying desiccant is preferably anhydrous sodium sulfate; the invention has no special requirement on the addition amount of the ammonium chloride and can terminate the reaction.
After 15, 15-diethoxy-pentadec-13-alkyne-1-alcohol is obtained, under the action of electrolytic manganese dioxide, 15-diethoxy-pentadec-13-alkyne-1-alcohol is subjected to alkynol oxidation reaction to obtain 15, 15-diethoxy-pentadec-13-alkyne-1-aldehyde (the structural formula is shown as a compound 6 in a formula a). In the invention, the molar ratio of the electrolytic manganese dioxide to the 15, 15-diethoxy-pentadecan-13-alkyne-1-alcohol is preferably 30-40: 1, more preferably 35: 1; the temperature of the alkynol oxidation reaction is preferably-5-0 ℃, more preferably 0 ℃, and the time is preferably 4-24 hours, more preferably 10-20 hours, and further preferably 12-18 hours; the alkynol oxidation reaction is preferably carried out under the protection of nitrogen; the solvent for the alkynol oxidation reaction is preferably n-hexane, and the volume of the solvent is not particularly required, so that the reaction can be smoothly carried out.
In the embodiment of the present invention, it is preferable that the crude product of 15, 15-diethoxy-pentadecan-13-yn-1-ol obtained in the previous step is slowly added to an n-hexane suspension of electrolytic manganese dioxide to carry out the reaction.
After the alkynol oxidation reaction is finished, the alkynol oxidation reaction liquid is preferably subjected to post-treatment in the invention, and the post-treatment preferably comprises the following steps:
filtering the alkynol oxidation reaction liquid by using diatomite, and evaporating an organic phase from the filtrate to obtain a crude product;
and (3) performing silica gel column chromatography on the crude product to obtain 15, 15-diethoxy-pentadec-13-alkyne-1-aldehyde.
The invention removes the residual manganese dioxide by diatomite filtration; in the present invention, the eluent for silica gel column chromatography is preferably a mixed solvent of n-hexane and ethyl acetate; the volume ratio of n-hexane to ethyl acetate in the mixed solvent is preferably 30: 1; the invention has no special requirement on the steaming temperature, and can completely steam the solvent.
After 15, 15-diethoxy-pentadec-13-alkyne-1-aldehyde is obtained, under the action of phenyl lithium, lithium bromide, tert-butyl alcohol and potassium tert-butoxide, the Wittig-Schlosser reaction is carried out on 15, 15-diethoxy-pentadec-13-alkyne-1-aldehyde and propyltriphenyl phosphonium bromide to obtain trans-1, 1-diethoxy-15-octadecene-13-alkyne (the structural formula is shown as a compound 7 in a formula a). In the present invention, the molar ratio of 15, 15-diethoxy-pentadecan-13-yne-1-al, propyltriphenylphosphonium bromide, phenyllithium, lithium bromide, tert-butanol and potassium tert-butoxide is preferably 1: 1.2-1.5: 2: 2: 1.5-2: 1.5 to 2.0, more preferably 1: 1.3-1.4: 2: 2: 1.6-1.8: 1.6 to 1.8; the lithium bromide is preferably anhydrous lithium bromide; the solvent for the Wittig-Schlosser reaction is preferably anhydrous tetrahydrofuran.
In the invention, the Wittig-Schlosser reaction specifically comprises the following steps:
dissolving lithium bromide and propyltriphenyl phosphonium bromide in anhydrous tetrahydrofuran, stirring for 10min, cooling to-70-80 ℃, preferably-78 ℃, then dropwise adding a phenyl lithium solution, slowly raising the temperature to room temperature after dropwise adding, stirring for 30min, then cooling to-70-80 ℃, preferably-78 ℃, dropwise adding a tetrahydrofuran solution of 15, 15-diethoxy-pentadecan-13-alkyne-1-aldehyde, reacting for 10min, dropwise adding a phenyl lithium solution again, stirring for reacting for 30min, then sequentially adding tert-butyl alcohol and potassium tert-butoxide, and reacting for 1.5-2.5 h, preferably 2h, at room temperature to obtain trans-1, 1-diethoxy-15-octadecene-13-alkyne.
According to the invention, the temperature is raised and then the solution is cooled after the phenyllithium solution is dripped for the first time, which is beneficial to promoting the generation of an organic phosphine intermediate in the Wittig-Schlosser reaction; the phenyllithium solution is added in two times, which helps to promote the conversion of the intermediate to the trans-configuration product; the solvent of the phenyllithium solution is preferably diethyl ether; the concentration of the phenyllithium solution is preferably 1 mol/L.
After the Wittig-Schlosser reaction is finished, the Wittig-Schlosser reaction solution is preferably subjected to post-treatment; the post-treatment preferably comprises the steps of:
mixing the Wittig-Schlosser reaction solution with water, and extracting with n-hexane to obtain an extracted organic phase;
drying the extracted organic phase, and evaporating to remove the solvent to obtain a crude product;
and performing silica gel column chromatography on the crude product to obtain trans-1, 1-diethoxy-15-octadecene-13-alkyne.
In the present invention, the drying agent is preferably anhydrous sodium sulfate; the eluent for silica gel column chromatography is preferably a mixed solvent of n-hexane and ethyl acetate; the volume ratio of n-hexane to ethyl acetate in the mixed solvent is preferably 30: 1; the invention has no special requirement on the steaming temperature, and can completely steam the solvent.
After trans-1, 1-diethoxy-15-octadecene-13-alkyne is obtained, under the action of dicyclohexylborane and glacial acetic acid, trans-1, 1-diethoxy-15-octadecene-13-alkyne is subjected to hydroboration reduction reaction to obtain cis, trans-1, 1-diethoxy-13, 15-octadecadiene (the structural formula is shown as a compound 8 in a formula a). In the present invention, the molar ratio of trans-1, 1-diethoxy-15-octadecen-13-yne, dicyclohexylborane and glacial acetic acid is preferably 1: 2-4: 6-10, more preferably 1: 3: 8; the solvent for the hydroboration reduction reaction is preferably tetrahydrofuran.
In the present invention, the hydroboration reduction reaction is preferably specifically:
and (2) dropwise adding a tetrahydrofuran solution of trans-1, 1-diethoxy-15-octadecene-13-alkyne into dicyclohexylborane to perform hydroboration reaction, and then adding glacial acetic acid into the reaction liquid to perform reduction reaction.
In the invention, the tetrahydrofuran solution of trans-1, 1-diethoxy-15-octadecene-13-alkyne is preferably dropwise added into dicyclohexylborane at the temperature of-20 ℃, and after dropwise addition, the dicyclohexylborane reacts at the temperature of-20 ℃ for 2 hours and then reacts at the temperature of room temperature until dicyclohexylborane precipitate disappears, namely, the hydroboration reaction is completed. In the invention, the temperature of the reduction reaction is preferably 40-50 ℃, more preferably 45 ℃, and the time is preferably 12-24 hours, more preferably 15-20 hours. In the hydroboration reaction process, trans-1, 1-diethoxy-15-octadecene-13-alkyne reacts with diborane to generate alkenyl borane, and in the reduction reaction process, the alkenyl borane reacts with acetic acid to generate cis, trans-1, 1-diethoxy-13, 15-octadecadiene.
After the hydroboration reduction reaction is completed, the invention preferably carries out post-treatment on the hydroboration reduction reaction liquid, and the post-treatment preferably comprises the following steps:
adding a sodium hydroxide solution and hydrogen peroxide into the hydroboration reduction reaction liquid for reaction to remove dicyclohexyl borate, and extracting by using normal hexane after the reaction is finished to obtain an extracted organic phase;
evaporating the organic solvent in the extracted organic phase to obtain a cis-trans-1, 1-diethoxy-13, 15-octadecadiene crude product; the crude product is directly used for the next reaction without further treatment.
In the invention, the concentration of the sodium hydroxide solution is preferably 6mol/L, and the mass percentage of the hydrogen peroxide is preferably 35%; the invention has no special requirements on the addition amount of the sodium hydroxide solution and the hydrogen peroxide and the reaction time after the addition, and can completely remove the dicyclohexyl borate. In the present invention, the number of extractions is preferably 3, and the organic phases are combined after the extractions.
After cis-trans-1, 1-diethoxy-13, 15-octadecadienol is obtained, the invention carries out acetal protective group removal reaction on the cis-trans-1, 1-diethoxy-13, 15-octadecadienol under the action of oxalic acid to obtain the cis-trans-13, 15-octadecadienal. In the invention, the molar ratio of the oxalic acid in the step (8) to the trans-1, 1-diethoxy-15-octadecen-13-yne in the step (7) is preferably 3-3.5: 1, more preferably 3: 1; the oxalic acid is preferably oxalic acid dihydrate; the solvent for the acetal protecting group removing reaction is preferably a tetrahydrofuran-water mixed solvent; the invention has no special requirements on the dosage of the solvent, and can ensure that the reaction is carried out smoothly; the temperature of the acetal protecting group removing reaction is preferably 50-70 ℃, more preferably 60 ℃, and the time is preferably 30-50 min, more preferably 40 min.
In the embodiment of the present invention, it is preferable that the crude cis, trans-1, 1-diethoxy-13, 15-octadecadien obtained in the previous step is dissolved in tetrahydrofuran, and then the tetrahydrofuran solution of the crude product is added dropwise to the aqueous oxalic acid solution to carry out the reaction.
After the acetal protecting group removal reaction is completed, the present invention preferably performs post-treatment on the obtained acetal protecting group removal reaction solution; the post-treatment preferably comprises the steps of:
carrying out n-hexane extraction on the acetal protecting group removing reaction liquid to obtain an extracted organic phase;
and washing the extracted organic phase, and then sequentially carrying out drying and silica gel column chromatography to obtain cis-trans-13, 15-octadecadienal.
In the invention, the number of times of n-hexane extraction is preferably 3, and the organic phases are combined after extraction; the washing is preferably carried out by sequentially using hydrated saturated sodium chloride; the drying desiccant is preferably anhydrous sodium sulfate; the eluent for silica gel column chromatography is preferably a mixed solvent of n-hexane and ethyl acetate; the volume ratio of n-hexane to ethyl acetate in the mixed solvent is preferably 50: 1.
in the field, a conventional Wittig reaction product usually is a cis-configuration double bond product, an improved Wittig reaction (Wittig-Schlosse reaction) is adopted in the synthesis method, and the product mainly contains a trans-configuration double bond, so that the synthesis method realizes the stereoselective synthesis of the sex pheromone of the populus canula.
The invention also provides an identification method of sex pheromone active ingredients of the populus canula, which comprises the following steps:
respectively analyzing the sex pheromone gland extract of the populus canula and cis, trans-13, 15-octadecadienal by adopting a gas chromatography-antennal potentiometer to obtain corresponding maps;
and analyzing the spectrogram, and determining that the cis-trans-13, 15-octadecadienal is the active ingredient of the sex pheromone of the populus plutella if the retention time of the cis-trans-13, 15-octadecadienal and the sex pheromone gland extract of the populus plutella are similar and the androgenic reaction of the male tentacles of the populus plutella can be caused in the spectrogram.
In the present invention, the extraction method of the sex pheromone gland extract of the populus canula preferably comprises the following steps:
collecting a plurality of unmated female poplars in the coupling stage, slightly pressing the abdomen of the female moths by hands when the gonads of the female moths extend outwards to force the gonads of the female moths to extend completely, cutting off the gonads, quickly placing the female moths in a sample bottle of n-hexane for soaking to obtain an extracting solution, combining the gonad extracting solutions of the female moths of the poplars, concentrating the combined extracting solutions, and extracting sex pheromone glands of the poplars.
In the invention, the number of the female moths of the populus canescens is preferably 10, the volume of the n-hexane is preferably 100 mu L, and the soaking time is preferably 30 min.
The invention has no special requirements on the gas chromatography-electroantennal potentionmeter, and the gas chromatography-electroantennal potentionmeter which is well known by the technicians in the field can be used; in the present invention, the gas chromatography conditions of the gas chromatography-electroantennal potentiostat are preferably:
a chromatographic column: DB-5MS, 30m × 0.25mm × 0.25 μm, J & W scientific, Folsom, CA;
a detector: hydrogen flame ionization monitors (FID);
a combustor: hydrogen with the flow rate of 40 mL/min;
combustion-supporting gas: drying air with the flow rate of 400 mL/min;
carrier gas: nitrogen with the flow rate of 2.5 mL/min;
sample inlet temperature: 220 ℃;
detector temperature: 280 ℃;
column procedure: the initial temperature is 60 ℃, the temperature is kept for 2min, the temperature is programmed to 280 ℃ at the speed of 8 ℃/min, and the temperature is kept for 20 min;
and (3) sample introduction mode: the sample is injected without shunting, the sample injection amount is 1 mu L, and the sample concentration is 10 ng/mu L;
an outlet end flow divider: 0SS-2.SGE, Australia, split ratio 1: 2.
the working conditions of the antennal potentiometer are preferably as follows:
an EAG probe: PRG-2, forked antenna holders;
an IDAC converter: auto Spike, IDAC2/3, Syntech;
an amplifier: UN-06, Syntech;
the antenna source is as follows: 2-3 days after eclosion, the male moth feeler of the populus canula;
the antenna length is as follows: 10 mm;
the treatment method comprises the following steps: the tip of the antenna is cut off by 0.5mm from the root by a dissecting scissors, and the antenna is connected with two silver electrodes of a fork-shaped antenna fixer of an EAG probe (PRG-2) by conductive adhesive.
The method adopts a gas chromatography-antenna potential technology to compare and analyze the synthesized standard substance and the sex pheromone gland extract of the populus canescens so as to determine the active ingredients of the sex pheromone of the populus canescens, and the identification method has the advantages of short period, high result reliability and the like.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Synthesis of 1, 1-diethoxy-12-iodododecane:
dropwise adding 12-bromo-1-dodecanol (26.5g, 0.1mol) into a dichloromethane (600mL) solution of pyridinium chlorochromate (0.4mol), and reacting at normal temperature for 4h to generate 12-bromo-1-dodecanal;
reacting the product with triethyl orthoformate (22.2g and 0.15mol) in absolute ethyl alcohol without purification, wherein the catalyst is p-toluenesulfonic acid monohydrate (290mg), reacting at 0 ℃ overnight, after the reaction is finished, adding saturated sodium bicarbonate solution into reaction liquid, extracting with ethyl acetate for three times, combining extract liquor, drying with anhydrous sodium sulfate, and evaporating to remove the solvent to obtain a product 1, 1-diethoxy-12-bromododecane with aldehyde groups protected by ethoxy;
reacting 1, 1-diethoxy-12-bromododecane with sodium iodide in anhydrous acetone in a molar ratio of 2: 1, the bromine group is replaced by iodine; after the reaction is finished, evaporating to remove the organic solvent, adding distilled water, extracting for three times by ethyl acetate, combining organic phases, and drying by anhydrous sodium sulfate; the solvent was distilled off, and the crude product was subjected to silica gel column chromatography using n-hexane/ethyl acetate (25: 1, v/v) to give 34.6g of 1, 1-diethoxy-12-iodododecane, in 90% yield.
Synthesis of 15, 15-diethoxy-pentadecan-13-yne-1-aldehyde:
slowly adding a tetrahydrofuran solution (2.5M, 80mL, 0.2mol) of n-butyllithium into a tetrahydrofuran/hexamethylphosphoric triamide (1: 1, v/v, 800mL) solution of propiolic alcohol (0.1mol) at the temperature of-20 ℃, then slowly adding 1, 1-diethoxy-12-iodododecane (19.2g, 0.05mol) into the reaction liquid, reacting for 2 hours, adding a saturated ammonium chloride solution to terminate the reaction after the reaction is finished, extracting ethyl acetate for three times, and drying an organic phase by anhydrous sodium sulfate; evaporating the solvent to obtain a crude product of 15, 15-diethoxy-pentadecan-13-alkyne-1-alcohol;
the crude product is subsequently added dropwise to a suspension of electrolytic manganese dioxide (0.3mol) in N-hexane, N2Gas protection, reacting for 4 hours at 0 ℃, and filtering through diatomite to remove residual manganese dioxide after the reaction is finished; the organic phase of the filtrate was distilled off to obtain a crude product, which was subjected to silica gel column chromatography and n-hexane/ethyl acetate (30: 1, v/v) to give 10.1g of 15, 15-diethoxy-pentadecan-13-yne-1-aldehyde in a yield of 65%.
Synthesis of trans-1, 1-diethoxy-15-octadecen-13-yne:
adding a THF solution of anhydrous LiBr into propyltriphenyl phosphonium bromide (0.06mol), and stirring at room temperature for 10 min; then cooled to-78 ℃ and PhLi (1M in Et) is added dropwise2O, 1.0equiv), slowly raising the temperature to room temperature and stirring for 30 min; cooling to-78 deg.c, adding alkyne aldehyde (9.3g, 0.03mol) in THF solution slowly, reacting for 10 min; PhLi (1M in Et) was added dropwise again2O, 1.0equiv), stirring for 30min, adding tert-butyl alcohol (0.45mL) and potassium tert-butoxide (0.44g) in sequence, and reacting for 2h at room temperature; after the reaction, distilled water was added, and extraction was carried out with n-hexane, the organic phase was dried over anhydrous sodium sulfate, the solvent was distilled off, and n-hexane/ethyl acetate (30: 1, v/v) was subjected to silica gel column chromatography to obtain trans-1, 1-diethoxy-15-octadecene-13-yne 7.0g in a yield of 70%.
Synthesis of cis, trans-13, 15-octadecadienal:
adding a THF solution of trans-1, 1-diethoxy-15-octadecen-13-yne (6.72g, 0.02mol) into dicyclohexylborane (7.12g, 0.04mol) to react at-20 ℃ for 2h, then at room temperature for 2h until dicyclohexylborane precipitate disappears; then adding glacial acetic acid (5mL) and reacting at 45 ℃ overnight; NaOH (6M, 6mL) and H were added in this order2O2(35%, 7mL) dicyclohexylborate was removed; after the reaction is finished, extracting the normal hexane for three times, and evaporating an organic phase to obtain a cis, trans-1, 1-diethoxy-13, 15-octadecadiene crude product;
then the crude product is dissolved in THF, added into the aqueous solution of oxalic acid dihydrate (3.0g), and stirred to react for 40min at 60 ℃; after the reaction is finished, n-hexane is used for extracting the reaction liquid for three times, an organic phase is washed by water, washed by saturated sodium chloride, dried by anhydrous sodium sulfate, and purified by a silica gel column to obtain 3.17g of cis-, trans-13, 15-octadecadienal with the yield of 60 percent, wherein the n-hexane/ethyl acetate (50: 1, v/v).
Identification data of product structure:
1H-NMR(500MHz,CDCl3)δ1.00(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)δ202.9,133.6,132.1,123.4,123.0,43.9,29.6,29.5,29.5,29.4,29.3,29.3,29GC-MS of cis, trans-13, 15-octadecadienal (70eV, EI):264.
Example 2
Method for identifying sex pheromone active ingredients of populus canula
The instrument comprises the following steps: agilent 7890A gas chromatograph-Holland Syntech antenna potential combination instrument (GC-EAD) of Agilent USA;
a chromatographic column: DB-5MS, 30m × 0.25mm × 0.25 μm, J & W scientific, Folsom, CA;
gas chromatography working conditions:
a detector: hydrogen flame ionization monitors (FID);
a combustor: hydrogen with the flow rate of 40 mL/min;
combustion-supporting gas: the air is dried. The flow rate is 400 mL/min;
carrier gas: nitrogen with the flow rate of 2.5 mL/min;
sample inlet temperature: 220 ℃;
detector temperature: 280 ℃;
column procedure: the initial temperature is 60 ℃, the temperature is kept for 2min, the temperature is programmed to 280 ℃ at the speed of 8 ℃/min, and the temperature is kept for 20 min;
and (3) sample introduction mode: no shunt sample introduction, the sample introduction amount is 1 mu L, and the sample concentration is 10 ng/uL;
an outlet end flow divider: 0SS-2.SGE, Australia, split ratio 1: 2; the working conditions of the antennal potentiometer are as follows:
an EAG probe: PRG-2, forked antenna holders;
an IDAC converter: auto Spike, IDAC2/3, Syntech;
an amplifier: UN-06, Syntech;
the antenna source is as follows: 2-3 days after emergence of the male tentacles of the populus canescens;
length: 10 mm;
the treatment method comprises the following steps: the tip of the antenna is cut off by 0.5mm from the root by a dissecting scissors, and the antenna is connected with two silver electrodes of a fork-shaped antenna fixer of an EAG probe (PRG-2) by conductive adhesive.
The identification step of the sex pheromone active ingredients of the populus canula:
extracting sex pheromone of the populus canula: collecting 10 female moths which are not mated of the populus canescens in the coupling period, slightly pressing the abdomen of the female moths by hands when the gonads of the female moths extend outside, forcing the gonads of the female moths to extend completely, shearing the female moths by using the ophthalmology, quickly placing the female moths in a sample bottle which is pre-filled with 100 mu L of n-hexane, taking out the glands after soaking for 30min, combining extracting solutions, concentrating, sealing the concentrated extract, and placing the extract at the temperature of minus 20 ℃ for later use;
respectively carrying out gas chromatography-antennal potentiostat analysis on the sex pheromone gland extract of the populus stella and the cis, trans-13, 15-octadecadienal synthesized in the example 1 to obtain a corresponding gas chromatography-antennal potentiostat analysis map, as shown in figures 1-2, wherein figure 1 is a gas chromatography-antennal potentiostat analysis GC-EAD map of the sex pheromone gland normal hexane extract of the populus stella from the antennal male moth to the female moth; FIG. 2 is a GC-EAD spectrum of the gas chromatography-antennal potentiostat analysis of the synthetic compound by the antennal moth antennal, wherein A is cis, trans-13, 15-octadecadienal.
As can be seen from the figures 1-2, the gland extract contains a sex pheromone component which enables the tentacle of the male plutella xylostella to have obvious electrophysiological reaction, and the sex pheromone component which can cause the electrophysiological reaction of the tentacle of the male plutella xylostella exists at the retention time of 21.89 min; as can be seen from the gas chromatographic data analysis in FIG. 2, the compound finally obtained in the embodiment 1 of the present invention mainly comprises cis-trans configuration products, and simultaneously contains a small amount of cis-cis configuration products (the peak on the left side of A), the retention time of the compound cis, trans-13, 15-octadecadienal is 22.10min, and can cause obvious tentacle electrophysiological reaction, while the cis, cis-13, 15-octadecadienal cannot cause the tentacle of male moths to generate electrophysiological reaction; therefore, the cis, trans-13, 15-octadecadienal can be determined to be the sex pheromone active ingredient of the female Adenophora xylostella.
It can be seen from the above examples that the invention provides for the first time that the structure of sex pheromone active ingredient of the Populus mauritiana is cis, trans-13, 15-octadecadienal, the compound can cause the electrophysiological reaction of the Male Bombycis mauritiana, and the synthesis method provided by the invention has the advantages of high yield, high purity, strong stereoselectivity, etc., and the identification method provided by the invention has the advantages of short period, high reliability of results, etc.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The sex pheromone active ingredient of the populus canula is characterized in that the chemical name is cis, trans-13, 15-octadecadienal, and the sex pheromone active ingredient has a structure shown in a formula I:
2. the method of preparing a sex pheromone active ingredient of populus canula as claimed in claim 1, comprising the steps of:
(1) under the action of an oxidant, carrying out oxidation reaction on 12-bromo-1-dodecanol to obtain 12-bromo-1-dodecanal;
(2) under the action of a catalyst, performing aldehyde group protection reaction on 12-bromo-1-dodecanal and triethyl orthoformate to obtain 1, 1-diethoxy-12-bromododecane;
(3) performing iodination reaction on sodium iodide and 1, 1-diethoxy-12-bromododecane to obtain 1, 1-diethoxy-12-iodododecane;
(4) under the action of n-butyllithium, carrying out alkyne alkylation reaction on propiolic alcohol and 1, 1-diethoxy-12-iodododecane to obtain 15, 15-diethoxy-pentadecan-13-alkyne-1-alcohol;
(5) under the action of electrolytic manganese dioxide, carrying out alkynol oxidation reaction on 15, 15-diethoxy-pentadec-13-alkyne-1-alcohol to obtain 15, 15-diethoxy-pentadec-13-alkyne-1-aldehyde;
(6) under the action of phenyl lithium, lithium bromide, tert-butyl alcohol and potassium tert-butoxide, carrying out Wittig-Schlosser reaction on 15, 15-diethoxy-pentadecan-13-alkyne-1-aldehyde and propyltriphenyl phosphonium bromide to obtain trans-1, 1-diethoxy-15-octadecene-13-alkyne;
(7) under the action of dicyclohexylborane and glacial acetic acid, carrying out hydroboration reduction reaction on trans-1, 1-diethoxy-15-octadecene-13-alkyne to obtain cis-trans-1, 1-diethoxy-13, 15-octadecadiene;
(8) under the action of oxalic acid, the cis, trans-1, 1-diethoxy-13, 15-octadecadienol is subjected to acetal protecting group removing reaction to obtain the cis, trans-13, 15-octadecadienal.
3. The method according to claim 2, wherein the oxidizing agent in step (1) comprises one or more of pyridinium chlorochromate, pyridinium dichlorochromate, tetramethylpiperidine nitroxide, and dess-martin periodinane;
the molar ratio of the 12-bromo-1-dodecanol to the oxidant is 1: 2-4;
the temperature of the oxidation reaction is room temperature, and the time is 2-24 hours.
4. The method according to claim 2, wherein the catalyst in the step (2) comprises p-toluenesulfonic acid and/or pyridine tosylate;
the molar ratio of the catalyst to the 12-bromo-1-dodecanal to the triethyl orthoformate is 1: 100: 60-70 parts of;
the aldehyde group protection reaction is carried out at the temperature of-5-0 ℃ for 10-24 hours.
5. The preparation method according to claim 2, wherein the molar ratio of sodium iodide to 1, 1-diethoxy-12-bromododecane in the step (3) is 2 to 3: 1;
the iodination reaction is carried out under the reflux condition for 6-24 h.
6. The method according to claim 2, wherein the molar ratio of 1, 1-diethoxy-12-iodododecane, propiolic alcohol and n-butyllithium in the step (4) is 1: 2-3: 4-5;
the temperature of the alkyne alkylation reaction is-15 to-30 ℃, and the time is 2 to 5 hours.
7. The preparation method according to claim 2, wherein the molar ratio of the electrolytic manganese dioxide to the 15, 15-diethoxy-pentadecan-13-yne-1-ol in the step (5) is 30 to 40: 1;
the temperature of the alkynol oxidation reaction is-5-0 ℃, and the time is 4-24 h.
8. The method according to claim 2, wherein the molar ratio of 15, 15-diethoxy-pentadecan-13-yne-1-al, propyltriphenylphosphonium bromide, phenyllithium, lithium bromide, t-butanol, and potassium t-butoxide in step (6) is 1: 1.2-1.5: 2: 2: 1.5-2: 1.5 to 2.0.
9. The method according to claim 2, wherein the molar ratio of trans-1, 1-diethoxy-15-octadecen-13-yne, dicyclohexylborane and glacial acetic acid in the step (7) is 1: 2-4: 6-10;
the molar ratio of oxalic acid in the step (8) to trans-1, 1-diethoxy-15-octadecene-13-yne in the step (7) is 3-3.5: 1.
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| 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 |
| 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 |
| 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 |
| CN113307728B (en) * | 2021-06-17 | 2022-02-11 | 南京蕃茂生物科技有限公司 | Preparation method of populus canula pheromone |
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