CN101875607A - (2S, 8Z)-2-butanoyloxy-8-heptadecene and preparation method thereof - Google Patents
(2S, 8Z)-2-butanoyloxy-8-heptadecene and preparation method thereof Download PDFInfo
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- CN101875607A CN101875607A CN2010102038607A CN201010203860A CN101875607A CN 101875607 A CN101875607 A CN 101875607A CN 2010102038607 A CN2010102038607 A CN 2010102038607A CN 201010203860 A CN201010203860 A CN 201010203860A CN 101875607 A CN101875607 A CN 101875607A
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- chrysanthemum
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HQBGDHCWJRCFTO-FQEVSTJZSA-N [(Z,2S)-heptadec-8-en-2-yl] butanoate Chemical compound C(CCC)(=O)O[C@@H](C)CCCCCC=C/CCCCCCCC HQBGDHCWJRCFTO-FQEVSTJZSA-N 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 108010088545 esterase B Proteins 0.000 claims abstract description 4
- 150000001336 alkenes Chemical class 0.000 claims description 19
- CIJHBFKEUTYXGP-UHFFFAOYSA-M C[Mg+].I(=O)(=O)[O-] Chemical compound C[Mg+].I(=O)(=O)[O-] CIJHBFKEUTYXGP-UHFFFAOYSA-M 0.000 claims description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 241000222120 Candida <Saccharomycetales> Species 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 241000723353 Chrysanthemum Species 0.000 abstract description 47
- 235000007516 Chrysanthemum Nutrition 0.000 abstract description 46
- 241001465828 Cecidomyiidae Species 0.000 abstract description 19
- 238000012360 testing method Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 241001661345 Moesziomyces antarcticus Species 0.000 abstract description 2
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 abstract description 2
- BLJFSPZWKBTYHR-KTKRTIGZSA-N 7Z-Hexadecenal Chemical compound CCCCCCCC\C=C/CCCCCC=O BLJFSPZWKBTYHR-KTKRTIGZSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000877 Sex Attractant Substances 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 241000238631 Hexapoda Species 0.000 description 13
- 241000255925 Diptera Species 0.000 description 8
- 241000607479 Yersinia pestis Species 0.000 description 8
- YKPQYKBIAFGWBT-KAMYIIQDSA-N [(Z)-18-hydroxyoctadec-9-en-7-yl] acetate Chemical compound CCCCCCC(C\C=C/CCCCCCCCO)OC(C)=O YKPQYKBIAFGWBT-KAMYIIQDSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 230000013011 mating Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001663467 Contarinia tritici Species 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000000023 Kugelrohr distillation Methods 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000011064 split stream procedure Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 1
- 240000000011 Artemisia annua Species 0.000 description 1
- 235000001405 Artemisia annua Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 235000000540 Brassica rapa subsp rapa Nutrition 0.000 description 1
- 108010031797 Candida antarctica lipase B Proteins 0.000 description 1
- 241001674939 Caulanthus Species 0.000 description 1
- 235000008495 Chrysanthemum leucanthemum Nutrition 0.000 description 1
- 244000192528 Chrysanthemum parthenium Species 0.000 description 1
- 235000000604 Chrysanthemum parthenium Nutrition 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 241001422926 Mayetiola hordei Species 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 240000007263 Pinus koraiensis Species 0.000 description 1
- 235000011615 Pinus koraiensis Nutrition 0.000 description 1
- 240000001416 Pseudotsuga menziesii Species 0.000 description 1
- 235000008572 Pseudotsuga menziesii Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000684808 Rhopalomyia longicauda Species 0.000 description 1
- 240000007651 Rubus glaucus Species 0.000 description 1
- 235000011034 Rubus glaucus Nutrition 0.000 description 1
- 235000009122 Rubus idaeus Nutrition 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003559 chemosterilizing effect Effects 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000008384 feverfew Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007758 mating behavior Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 239000002953 phosphate buffered saline Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 238000004448 titration Methods 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a compound, i.e. (2S, 8Z)-2-butanoyloxy-8-heptadecene as shown in a formula (1) as well as a preparation method and application thereof. The structural formula of the compound is shown in the formula (1). The preparation method of the compound comprises the steps of: reacting methylmagnesium iodide with (Z)-7-hexadecenal to obtain (Z)-8-heptadecene-2-alcohol and then esterifying the (Z)-8-heptadecene-2-alcohol by using butyric acid; and hydrolyzing obtained butyric acid raceme by using esterase B generated by Candida antarctica to obtain the compound shown in the formula (1). Proved by a test result of a trapping effect on chrysanthemum gall midges in the field, the compound, i.e. the (2S, 8Z)-2-butanoyloxy-8-heptadecene has strong attraction action on the male chrysanthemum gall midges; and moreover, the product has appropriate price and favorable social and ecological benefits and is suitable for popularization and application. The formula (1) is shown in the specification.
Description
Technical field
The present invention relates to (2S, 8Z)-2-butyryl acyloxy-8-17 alkene and preparation method thereof.
Background technology
Chrysanthemum cecidomyiia Rhopalomyia longicauda belongs to Diptera Cecidomyiidae insect, widely distributed in China, it is the important pests on chrysanthemum, sweet wormwood and other feverfews, mainly by larva cause harm plant strain growth point, tender leaf and bud, form insect gall, cause plant strain growth slow, downgrade deformity, bud reduces.Because larva is hidden in insect gall inside, be difficult to directly tag, produce the medium-term and long-term systemic pesticide controls such as thiophos, monocrotophos of using, the result causes the pesticide residue severe overweight, chrysanthemum cecidomyiia resistance improves constantly, and the natural enemy population quantity falls sharply, and problem such as contaminate environment.Efficiently, the novel method of nontoxic, pollution-free control chrysanthemum cecidomyiia has certain scientific meaning and application prospect.Use insect sex pheromone and carry out detecting and reporting pest information, disturb mating and mass trapping control agriculture and forestry injurious insect, owing to its have highly sensitive, selectivity strong, harmless to natural enemy, do not cause characteristics such as environmental pollution to receive an acclaim.In addition, also can utilize the insect sex pheromone trap to detect between country variant or the area, whether invade to determine certain external crushing insect.Known nearly 5000 kinds of the Cecidomyiidae insect whole world, there have Hessian fly, pea cecidomyiia, turnip wild cabbage cecidomyiia, Pseudotsuga menziesii (Mirbel) Franco pine nut cecidomyiia, Korean pine pine nut cecidomyiia, gall aphid, wheat midge, 8 kinds of Cecidomyiidae insect sex pheromones of raspberry cecidomyiia chemical structure to be identified at present to be synthetic, and wherein wheat midge and pea cecidomyiia synthetic sex pheromone have been successfully applied to detecting and reporting pest information.
Summary of the invention
The purpose of this invention is to provide the compound shown in the formula I (2S, 8Z)-2-butyryl acyloxy-8-17 alkene and preparation method thereof.
Compound provided by the present invention (2S, 8Z)-structural formula of 2-butyryl acyloxy-8-17 alkene is as follows:
The preparation method of the compound shown in the formula I, be with the iodate methyl magnesium with (Z)-7-hexadecylene aldehyde reaction obtains (Z)-8-17 alkene-2-alcohol, and then will (Z)-8-17 alkene-2-purely uses the butyric acid esterification; The butyric ester racemic modification that obtains is hydrolyzed by antarctic candida esterase B (Candida antarctica lipase B), produce the 2R configuration alcohol that unreacted 2S configuration ester (compound shown in the formula I) and hydrolysis obtain, and 2R configuration alcohol can change into corresponding 2R-butyric ester again.
Compound shown in the formula I provided by the present invention is a chrysanthemum cecidomyiia sex pheromone, can be used for preparing chrysanthemum gall midge sex attractant.
Another object of the present invention provides a kind of chrysanthemum gall midge sex attractant.
Chrysanthemum gall midge sex attractant provided by the present invention comprises the compound shown in the formula I.
Described sex attractant also can comprise following at least a deactivation composition: chemosterilant, virus and bacterium.
A further object of the present invention provide described chrysanthemum gall midge sex attractant preparation following arbitrary in application in the product:
1) is used for monitoring the application of the product that chrysanthemum cecidomyiia situation occurred and/or the insect pest of prediction chrysanthemum cecidomyiia take place in preparation;
2) be used for the application disturbing mating of chrysanthemum cecidomyiia and/or trapping, kill the product of chrysanthemum cecidomyiia in preparation;
3) be used for detecting the application of the product of chrysanthemum cecidomyiia insect pest in preparation.
Chrysanthemum gall midge sex attractant provided by the present invention also can be used for catching and killing the chrysanthemum cecidomyiia.
A further object of the invention provides a kind of chrysanthemum gall midge sex attractant and lures core and preparation method thereof.
Chrysanthemum gall midge sex attractant provided by the present invention lures core, comprises described chrysanthemum gall midge sex attractant.
Described chrysanthemum gall midge sex attractant lures the preparation method of core, comprise: be carrier with the rubber plug, the solution of claim 2 or 3 described chrysanthemum gall midge sex attractant is added described rubber plug recess, treat solvent evaporates after, obtain described chrysanthemum gall midge sex attractant and lure core.
Wherein, the solvent in the solution of described chrysanthemum gall midge sex attractant is normal hexane, sherwood oil or normal heptane; It is 5-20ug that described chrysanthemum gall midge sex attractant lures the quality of chrysanthemum gall midge sex attractant described in the core, specifically can be 10ug, 15ug etc.
Chrysanthemum cecidomyiia sex pheromone provided by the invention lures the purposes of core to comprise:
(1) chrysanthemum cecidomyiia population monitoring forecast
1 year number of chrysanthemum cecidomyiia generation, can in time and accurately monitor and predict chrysanthemum cecidomyiia emergence period, generating capacity and distributed areas with chrysanthemum cecidomyiia gyplure provided by the invention, and can estimate pest damage area and control period.Observe and predict insect pest situation with chrysanthemum cecidomyiia gyplure of the present invention, have highly sensitively, accuracy is good, and is easy to use, and expense is cheap, is suitable for generally promoting the use of.
(2) mass trapping
Chrysanthemum cecidomyiia gyplure trap trapping male worm is set in the field, causes female-male proportion seriously to be lacked of proper care, reduce the mating behavior of male and female, reduce progeny population density, reduce harm.
(3) disturb mating
Discharge chrysanthemum cecidomyiia gyplure of the present invention in the field, in the environment that is full of female mosquito sex pheromone smell, male mosquito forfeiture causes the mating probability between the male and female of field greatly to reduce to the orientation property of female mosquito, thereby population density of future generation is descended.
The sex attractant that utilizes sex pheromone provided by the present invention to make lures core, can carry out population monitoring and integrated control to the chrysanthemum cecidomyiia.This attractive substance has that cost is low, efficient is high, is suitable for forecasting the pests occurrence rule of hiding the inner insect of insect gall.
The invention has the advantages that:
(1) the containing of preparation (2S, 8Z)-the chrysanthemum cecidomyiia sex pheromone of 2-butyryl acyloxy-8-17 alkene lures core, in the field the male mosquito of chrysanthemum cecidomyiia is had strong attracting action;
(2) chrysanthemum cecidomyiia gyplure product price of the present invention is suitable, has good society and ecological benefits, is fit to apply.
Description of drawings
Fig. 1 be compound (2S, 8Z)-synthetic route chart of 2-butyryl acyloxy-8-17 alkene; Wherein, reactant: (i) be dissolved in the MeMgI of ether; (ii) be dissolved in the butyric acid/N of methylene dichloride, N-Dimethylamino pyridine/N, N '-dicyclohexylcarbodiimide; The (iii) esterase of Candida antarctica is dissolved in pH and is in 7 the phosphate buffered saline buffer; (iv) butyryl chloride/pyridine is dissolved in methylene dichloride.
Fig. 2 be compound (2S, 8Z)-the polar column GC-MS mass spectrum of 2-butyryl acyloxy-8-17 alkene.
Fig. 3 be compound (2S, 8Z)-the non-polar column GC-MS mass spectrum of 2-butyryl acyloxy-8-17 alkene.
Embodiment
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
(Z)-preparation of 7-hexadecylene aldehyde:
With the methanol solution hydrolysis of (Z)-7-hexadecylene alcohol acetic ester with salt of wormwood, the alcohol that then hydrolysis is obtained obtains (Z)-7-hexadecylene aldehyde with pyridinium chlorochromate drone the salt oxidation that is dissolved in methylene dichloride.Wherein, synthetic institute (Z)-7-hexadecylene alcohol acetic ester that uses employing standard acetylide path of preparing is come out.
The preparation of iodate methyl magnesium:
With methyl iodide (2.84g 20mM) is dissolved in the exsiccant ether (10ml), under nitrogen protection, be added drop-wise to then and be placed with (0.6g, 25mM) in (20mM) ether of magnesium chips, the iodate methyl magnesium solution that reaction obtains is through titration, concentration is 0.76M.
With the iodate methyl magnesium solution that makes (7.5ml, 6mM) under ice bath and agitation condition, dropwise be added drop-wise to (Z)-7-hexadecylene aldehyde of being dissolved in ether (10ml) (0.83g, 3.5mM) in.With product washing, carry out the kugelrohr distillation, obtain (Z)-8-17 alkene-2-alcohol (b.p.140 ℃, 0.04mm Hg; 0.7g, 80%).
(Z)-8-17 alkene-2-alcohol that the last step was obtained (0.254g, 1mM) with butyric acid (0.132g, 1.5mM), N, methylene dichloride (5ml) solution of N-Dimethylamino pyridine (10mg) mixes, in above-mentioned mixed solution, add N then, and N '-dicyclohexylcarbodiimide (0.3g, 1.4mM).Mixture is at room temperature added ether (5ml) behind the stirring reaction 5h, filter, steam the instrument solvent evaporated with revolving.Revolve residue after the steaming with silica gel chromatography (12g) chromatographic separation, the chromatography agent is an ether: sherwood oil=2: 98 (v/v).Product (Z)-2-butyryl acyloxy-8-17 alkene that carry out obtaining after the kugelrohr distillation contain 5% E-isomer (b.p.180 ℃/0.04mm Hg approximately; 0.25g, 78%).
With (Z)-2-butyryl acyloxy-8-17 alkene (0.25g, 0.8mM) with the dipotassium hydrogen phosphate damping fluid (0.1M, pH 7; 3ml), acrylic resin-Candida antarctica esterase B polymkeric substance (Sigma-Aldrich; 25mg) at room temperature stirring is spent the night.To react back mixture ether: solvent (10ml) extraction of sherwood oil=10: 90 (v/v) 2 times, organic phase with salt solution washing 1 time, is used anhydrous magnesium sulfate drying.Steam on the instrument after the solvent evaporated revolving, (10g) is 2%～20% sherwood oil mixing solutions wash-out one by one with residue (0.25g) with the ether concentration gradient on silica gel chromatography.Through the chirality chromatogram column analysis, unreacted ester moiety contain (2S, 8Z)-2-butyryl acyloxy-8-17 alkene (0.11g) chirality body burdens (ee) are 99.8%.Remaining alcohol moiety (0.11g) is dissolved in the mixed solvent of methylene dichloride and pyridine (50mg), adds butyryl chloride (100mg).At room temperature stir and spend the night, obtain the chirality body burden after the reactant washing and be 99.1% (2R, 8Z)-2-butyryl acyloxy-8-17 alkene (0.12g).
To the compound (2S for preparing, 8Z)-2-butyryl acyloxy-8-17 alkene carry out GC-MS and analyze, GC-MS analyzes and adopts Carlo Erba 5130GC (Thermoelectron) and Finnigan ITD 700 (EI, 70eV) combined system, chromatographic column be Supelco Wax-10 (polar column, 30m * 0.25mm), helium is carrier gas (1.0ml/min), no split stream sampling, sample size 2 μ l.Analysis condition is as follows: 60 ℃ of starting temperatures keep 2min, are warming up to 250 ℃ with the speed of 6 ℃/min.220 ℃ of sampler temperature, 250 ℃ of detector temperatures.Mass spectrum is seen Fig. 2.
HP 6890 (Agilent) is also adopted in the GC-MS analysis, and (chromatographic column is that (non-polar column, 30m * 0.32mm), helium is carrier gas (1.0ml/min) to Supelco SPB-1, no split stream sampling, sample size 2 μ l for EI, 70eV) combined system with HP 5973MSD.Analysis condition is as follows: 60 ℃ of starting temperatures keep 2min, are warming up to 250 ℃ with the speed of 6 ℃/min.220 ℃ of sampler temperature, 250 ℃ of detector temperatures.Mass spectrum is seen Fig. 3.
In Qi Ju field, Anguo City, Hebei province, carry out the trap effect test of gyplure on May 4,1 day to 2007 May in 2007 to the chrysanthemum cecidomyiia.
Will (2S, 8Z)-2-butyryl acyloxy-8-17 alkene 10 micrograms are dissolved in the normal hexane, are added drop-wise to then on the rubber plug partition, after treating the normal hexane volatilization, drip 200 microlitre methylene dichloride, treat methylene dichloride volatilization after, lure the core sealing of packing in the aluminium foil standby the chrysanthemum cecidomyiia gyplure of making.
Adopt trilateral viscose trap on May 4,1 day to 2007 May in 2007, trap is surrounded by palstic corrugated sheet, and the little upper base 2cm of cross section, the cm that goes to the bottom, two length of sides are respectively the isosceles trapezoid of 20cm, and the cardboard that scribbles insect sticker is placed in the bottom.To lure core to place in the middle of the trap, apart from the about 2cm of glue face.Trap is arranged consistent with the chrysanthemum plant height apart from ground, interval 10m between the trap.The female mosquito trap of chrysanthemum cecidomyiia virgin is set simultaneously (to be placed on the female mosquito of virgin in the little sarong, to place in the middle of the trap, apart from the about 2cm of glue face.) and the blank trap.Each test is handled 3 repetitions is set.Test-results sees Table 1.
Table 1 (2S, 8Z)-the male mosquito test-results of 2-butyryl acyloxy-8-17 alkene trapping chrysanthemum cecidomyiia
As shown in Table 1, chrysanthemum cecidomyiia gyplure provided by the present invention has strong attracting action to the male mosquito of chrysanthemum cecidomyiia.
Claims (2)
1. compound shown in the formula I
2. the preparation method of the described compound of claim 1, be with the iodate methyl magnesium with (Z)-7-hexadecylene aldehyde reaction, obtain (Z)-8-17 alkene-2-alcohol; Again (Z)-8-17 alkene-2-alcohol is used the butyric acid esterification, obtain (2S, 8Z)-2-butyryl acyloxy-8-17 alkene; Then will obtain (2S, 8Z)-2-butyryl acyloxy-8-17 alkene are hydrolyzed by the antarctic candida esterase B, obtain the compound shown in the formula I.
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Non-Patent Citations (2)
| Title |
|---|
| DAVID R. HALL, ET AL: "(S)-2-Acetoxy-5-Undecanone, Female Sex Pheromone of the Raspberry Cane Midge, Resseliella theobaldi (Barnes)", 《J. CHEM. ECOL.》, vol. 35, 24 January 2009 (2009-01-24), pages 230 - 242, XP019680865 * |
| 李红军 等: "瘿蚊性信息素的研究进展", 《华北农学报》, vol. 23, 31 December 2008 (2008-12-31), pages 278 - 281 * |
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