CN101875607B - (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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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 inner at insect gall, is difficult to directly tag, and produces the systemic pesticide controls such as medium-term and long-term use thiophos, monocrotophos, the result causes the pesticide residue severe overweight, chrysanthemum cecidomyiia resistance improves constantly, and the natural enemy population quantity falls sharply, and the 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 the 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, have at present 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 identified synthetic, 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 (2S, 8Z) shown in the formula I-2-butyryl acyloxy-8-17 alkene and preparation method thereof.
The structural formula of compound provided by the present invention (2S, 8Z)-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 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 provides the application of described chrysanthemum gall midge sex attractant in the following arbitrary middle product of preparation:
1) application in the product that occurs for the preparation of monitoring chrysanthemum cecidomyiia situation occurred and/or the insect pest of prediction chrysanthemum cecidomyiia;
2) for the preparation of disturbing chrysanthemum cecidomyiia mating and/or trapping, killing the application in the product of chrysanthemum cecidomyiia;
3) for the preparation of the application in the product that detects the insect pest of chrysanthemum cecidomyiia.
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: take rubber plug as carrier, the solution of claim 2 or 3 described chrysanthemum gall midge sex attractant is added described rubber plug recess, after solvent evaporates, 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, with chrysanthemum cecidomyiia gyplure provided by the invention in time and accurately monitoring and prediction chrysanthemum cecidomyiia emergence period, generating capacity and distributed areas, 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
Deployment chrysanthemum cecidomyiia pheromone trap trapping male worm, cause 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 chrysanthemum cecidomyiia sex pheromone that contains (2S, 8Z)-2-butyryl acyloxy-8-17 alkene of preparation 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 is the synthetic route chart of compound (2S, 8Z)-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; (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 is the polar column GC-MS mass spectrum of compound (2S, 8Z)-2-butyryl acyloxy-8-17 alkene.
Fig. 3 is the non-polar column GC-MS mass spectrum of compound (2S, 8Z)-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.
Embodiment 1, preparation compound (2S, 8Z)-2-butyryl acyloxy-8-17 alkene
(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 route prepares.
The preparation of iodate methyl magnesium:
With methyl iodide (2.84g; 20mM) be dissolved in the dry ether (10ml), then under nitrogen protection, be added drop-wise in (20mM) ether that is placed with (0.6g, 25mM) magnesium chips; the iodate methyl magnesium solution that reaction obtains is through titration, and concentration is 0.76M.
The iodate methyl magnesium solution (7.5ml, 6mM) that makes under ice bath and agitation condition, dropwise is added drop-wise in (the Z)-7-hexadecylene aldehyde (0.83g, 3.5mM) that is dissolved in ether (10ml).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 that the upper step was obtained-2-alcohol (0.254g, 1mM) with butyric acid (0.132g, 1.5mM), N, methylene dichloride (5ml) solution of N-Dimethylamino pyridine (10mg) mixes, then in above-mentioned mixed solution, add N, 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 ether: sherwood oil=2: 98 (v/v).Carry out the product (Z) that obtains after the kugelrohr distillation-2-butyryl acyloxy-8-17 alkene and approximately contain 5% E-isomer (b.p.180 ℃/0.04mm Hg; 0.25g, 78%).
With (Z)-2-butyryl acyloxy-8-17 alkene (0.25g, 0.8mM) and 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.Mixture ether after will reacting: 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 one by one wash-out of 2%～20% sherwood oil mixing solutions with residue (0.25g) with the ether concentration gradient on silica gel chromatography.Through the chirality chromatogram column analysis, (2S, the 8Z) that unreacted ester moiety contains-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 (2R, 8Z)-2-butyryl acyloxy-8-17 alkene (0.12g) of 99.1%.
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), without 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.
GC-MS analyzes and also adopts HP 6890 (Agilent) and HP 5973MSD (EI, 70eV) combined system, and chromatographic column is Supelco SPB-1 (non-polar column, 30m * 0.32mm), helium is carrier gas (1.0ml/min), without split stream sampling, and 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. 3.
Embodiment 2, compound (2S, 8Z)-2-butyryl acyloxy-8-17 alkene are tested the trap effect of chrysanthemum cecidomyiia
In Qi Ju field, Anguo City, Hebei province, carry out gyplure on May 4,1 day to 2007 May in 2007 to the trap effect test of chrysanthemum cecidomyiia.
(2S, 8Z)-2-butyryl acyloxy-8-17 alkene 10 micrograms are dissolved in the normal hexane, then are added drop-wise on the rubber plug partition, after the normal hexane volatilization, drip 200 microlitre methylene dichloride, after methylene dichloride volatilization, lure the core sealing of packing in the aluminium foil for subsequent use 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 processed 3 repetitions is set.Test-results sees Table 1.
Table 1 (2S, the 8Z)-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)
(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, obtained (Z)-2-butyryl acyloxy-8-17 alkene; (Z)-2-butyryl acyloxy-8-17 alkene that then will obtain are hydrolyzed by the antarctic candida esterase B, obtain the compound shown in the formula (I).
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| CN105724380B (en) * | 2016-04-18 | 2018-02-23 | 中国农业大学 | A kind of pachydiplosis oryzae sex attractant and its application |
| CN111838152B (en) * | 2020-06-19 | 2021-06-29 | 中国医学科学院药用植物研究所 | Lycium barbarum gallmidge attractant composition, lure and application |
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| CN1846496A (en) * | 2005-02-25 | 2006-10-18 | 贝多吉恩研究公司 | Method and compositions for attracting mosquitoes employing (R)-(-) isomers of 1-alken-3-ols |
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| CN1846496A (en) * | 2005-02-25 | 2006-10-18 | 贝多吉恩研究公司 | Method and compositions for attracting mosquitoes employing (R)-(-) isomers of 1-alken-3-ols |
Non-Patent Citations (4)
| Title |
|---|
| (S)-2-Acetoxy-5-Undecanone, Female Sex Pheromone of the Raspberry Cane Midge, Resseliella theobaldi (Barnes);David R. Hall, et al;《J. Chem. Ecol.》;20090124;第35卷;230-242 * |
| David R. Hall, et al.(S)-2-Acetoxy-5-Undecanone, Female Sex Pheromone of the Raspberry Cane Midge, Resseliella theobaldi (Barnes).《J. Chem. Ecol.》.2009,第35卷230-242. |
| 李红军 等.瘿蚊性信息素的研究进展.《华北农学报》.2008,第23卷278-281. |
| 瘿蚊性信息素的研究进展;李红军 等;《华北农学报》;20081231;第23卷;278-281 * |
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| CN101856021B (en) | 2013-03-13 |
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