CN1041936A - Composing method of fly sexual tempting agent - Google Patents
Composing method of fly sexual tempting agent Download PDFInfo
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- CN1041936A CN1041936A CN 88107133 CN88107133A CN1041936A CN 1041936 A CN1041936 A CN 1041936A CN 88107133 CN88107133 CN 88107133 CN 88107133 A CN88107133 A CN 88107133A CN 1041936 A CN1041936 A CN 1041936A
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- mustard
- sulfonyl ester
- mustard alcohol
- solvent
- erucic acid
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Abstract
Muscalure (E-9-tricosene) is a kind of housefly sex pheromone.Utilize this material can manually trap and kill housefly, wherein cis-isomeride has stronger trapping ability than trans-isomer(ide).Compare with other sterilant, it has high specificity, characteristics such as efficient, nontoxic.The invention belongs to the improvement of house fly trapping agent synthetic method, is raw material with erucic acid cheap and easy to get, finishes through alcoholization, sulfonylation, three steps of Yu Geshi reagent react.Overall yield reaches 41.3%, and wherein cis-isomeride is up to 98.4%, and trans-isomer(ide) only puts 1.6%.
Description
The invention belongs to the improvement of composing method of fly sexual tempting agent.
Muscalure is a kind of housefly sex pheromone, be 1971 by Carlson (D, A, Carlson et al, Science 174,76(1971)) at first by separating in the housefly secretion thing, identifying and synthetic E-9-tricosene.Utilize this material, can manually trap and kill housefly,, have high specificity with other sterilant ratio, efficient, characteristics such as nontoxic.Carlson is synthetic is with tetradecyl bromine and aldehyde C-9 through the Wittig reaction and get, product is the mixture of the trans-isomer(ide) of 85% cis-isomeride and 15% according to chromatographic separation.Experiment shows, the effect that cis-isomeride is lured male fly than trans for strong.Afterwards, reported improving one's methods of synthetic this compound successively.Richter (I.Richter et al.Chem.Ph/s.Lipids11(3), 210(1973)) obtain this compound through series reaction with methyl erucate, though productive rate is higher, lose practical value owing to synthetic route is long.With erucic acid be raw material Lidia (Pop Lidia et al.Rev.Roum.Chim.27(4) 545(1982 arranged)) etc. people's several method, but have in the whole bag of tricks since raw material rare, the then severe reaction conditions that has, need with some characteristic reagent, thereby weak point is all arranged.
The objective of the invention is to erucic acid cheap and easy to get (being got through simple process by rape seed oil) is raw material, proposes a kind of simple synthetic route.
The invention is characterized in: with the erucic acid is raw material, uses LiAlH
4(erucic acid and LiAlH
4Weight ratio be 4～1: 1) refluxing in ether solvent is reduced to mustard alcohol with erucic acid; In the presence of organic bases, in solvent, make then weight ratio be 1: 1 mustard alcohol and Tosyl chloride 0～30 ℃ of reaction down, make mustard alcohol sulphonyl turn to mustard alcohol sulfonyl ester; Make mustard alcohol sulfonyl ester Yu Geshi reagent C H at last
3The MgI(weight ratio is 42: 53) containing the Li of 0.1M
2CuCl
4Tetrahydrofuran solution in-78 ℃ down reaction obtain final product E-9-tricosene.
Its reaction formula is:
The raw material erucic acid is by rape seed oil hydrolysis and getting under alkaline condition.With frozen recrystallization method purifying, its purity is 90%.Concrete technology is seen document: (C.R.Noller et al Organie Syntheses Collective Volume II, 258(1943)).
Erucic acid and LiAlH
4Weight ratio be 4: 1,3: 1,2: 1,1: 1 all can, but with 1: 1 best results.Solvent can adopt common ether compounds such as ether, propyl ether, isopropyl ether, phenyl ethyl ether, dichloro six rings, and the present invention is from originating and considering to select for use ether economically.Reaction detects till the reduction fully with thin plate, uses acetone recrystallization then, and handling productive rate routinely is 90%, and molten point is 33-34 ℃.
Solvent can adopt organic bases such as pyridine, triethylamine when mustard alcohol carries out sulfonylation with Tosyl chloride, and the preferred pyridine of the present invention is as solvent.And stir mixing down after the pure and mild Tosyl chloride of mustard will being dissolved in pyridine solvent respectively.Temperature of reaction is 0-30 ℃, and preferred temperature is 10-15 ℃.Reaction times is 3-10 hour.Pour into then and make solution be acid in the refrigerative dilute hydrochloric acid, use ethyl acetate extraction, extraction liquid is washed to neutrality with saturated common salt, obtains the pure sulfonyl ester of mustard after drying.
Mustard alcohol sulfonyl ester Yu Geshi reagent C H
3The reaction of MgI will be carried out at low temperatures.Low-yield is high more more for temperature in general, but corresponding cost (cost) is also high, and the present invention selects for use-78 ℃ to obtain higher productive rate for temperature of reaction.Reaction solvent adopts and contains 0.1M Li
2CuCl
4Tetrahydrofuran (THF).Will be with CH
3MgI is added dropwise under-78 ℃ in the above-mentioned solvent that is dissolved with mustard alcohol sulfonyl ester, slowly reactant is risen to after adding under the room temperature and stirred 12 hours, after the dilute sulphuric acid acidifying, extract with Skellysolve A, washing, the saturated common salt washing is washed to neutrality again, tells organic layer, dry the removing of siccative desolvated, and the cut of 148～150 ℃/0.2mmHg is collected in underpressure distillation.
The present invention does not use any special reagent from erucic acid, under the reaction conditions of gentleness, has only promptly finished the synthetic of E-9-tricosene through three-step reaction, and overall yield reaches 41.3%, and wherein cis-isomeride accounts for 98.4%, and trans-isomer(ide) accounts for 1.6%.So the present invention not only raw material is cheap and easy to get, synthetic route is simple and owing to the height ratio of cis-isomeride in product improved trap effect.
Embodiment:
Get 15g erucic acid (purity 90%) and 15g LiAlH
4Be dissolved in the ether solvent and reflux, reaction detects with thin plate till the reduction fully, with ordinary method extract, washing, dry back acetone recrystallization, get 12.1g mustard alcohol, productive rate is 90%, molten point is 33～34 ℃.
Get 4g mustard alcohol, add the 10ml pyridine and be cooled to 10～15 ℃; Stir and add the tolysulfonyl chlorine solution that 4g is dissolved in the 15ml pyridine down; Reaction is 8 hours under this temperature; Pour in the 10ml refrigerative dilute hydrochloric acid, it is acid that solution is, and uses ethyl acetate extraction; Extraction liquid is washed to neutrality with saturated common salt, removes after drying and desolvates, and gets mustard alcohol sulfonyl ester crude product 4.5g, and productive rate is 76.5%.
Make Grignard reagent with 4.5g methyl iodide (32mmol), 0.8g magnesium (33mmol) 10ml anhydrous diethyl ether and a granule iodine.Splashing into 25ml under-78 ℃ is dissolved with the tetrahydrofuran solution of 4.2g mustard alcohol sulfonyl ester (this solution contains the Li of 0.1m
2CuCl
4); Slowly reactant is risen to room temperature after dripping off, stirred 12 hours; Reactant extracts with Skellysolve A after using the dilute sulphuric acid acidifying, washing, and the saturated common salt washing is washed to neutrality again, tells organic layer, uses MgSO
4Dry back is removed and is desolvated, underpressure distillation, and the cut of 148-150 ℃/0.2mmHg of collection, productive rate is 60%.
Gas Chromatographic Determination:
Used gas chromatograph is SP-09FID, and capillary column is 50M * 0.25mm, OV-1, N
2, 2.0Kg/cm
2, splitting ratio 100: 1, T
Post205 ℃, T
Vapour280 ℃, T
Detect320 ℃, the retention time of cis is 77.96 minutes, and trans retention time is 78.84 minutes, and is suitable/anti-=98.4%/1.6%.
Mass spectrum: m/l 322(M
+).
Claims (5)
1, a kind of synthetic method of muscalure, the chemical name of this material is the E-9-tricosene, it is characterized in that:
-be raw material with the erucic acid, use LiAlH
4(erucic acid and LiAlH
4Weight ratio be 4～1: 1) refluxing in ether solvent is reduced to mustard alcohol with erucic acid;
-in the organic bases solvent, make then weight ratio be 1: 1 mustard alcohol and Tosyl chloride 0-30 ℃ of reaction down, make mustard alcohol sulphonyl turn to mustard alcohol sulfonyl ester;
-make mustard alcohol sulfonyl ester Yu Geshi reagent C H at last
3MgI (weight ratio is 42: 53) is containing the Li of 0.1M
2OuCl
4Tetrahydrofuran solution in obtain final product E-9-tricosene-78 ℃ of reactions.
Its reaction formula is:
2,, it is characterized in that erucic acid is reduced to mustard when alcohol backflow ether material selects ether for use, erucic acid and LiAlH according to the said composing method of fly sexual tempting agent of claim 1
4Preferred weight ratio is 1: 1, and uses acetone recrystallization.
3, according to claim 1 or 2 said composing method of fly sexual tempting agent; the organic bases solvent is selected pyridine for use when it is characterized in that mustard alcohol sulfonylation; and the pure and mild Tosyl chloride of mustard is dissolved in pyridine solvent respectively; mix in the stirring; reacted 3-10 hour down at preferred temperature 10-15 ℃; with using ethyl acetate extraction after the dilute hydrochloric acid acidifying, extraction liquid is washed to neutrality with saturated common salt then, and drying obtains mustard alcohol sulfonyl ester.
4, according to claim 1 or 2 said composing method of fly sexual tempting agent, when it is characterized in that mustard alcohol sulfonyl ester Yu Geshi reagent react with CH
3MgI is added dropwise to the Li that contains that is dissolved with mustard alcohol sulfonyl ester
2CuCl
4Tetrahydrofuran solvent in, slowly reactant is risen to stirring at room 12 hours then, after the dilute sulphuric acid acidifying, extract with Skellysolve A, washing, the saturated common salt washing is washed to neutrality again, tell dry the removing of organic layer siccative and desolvate, the cut of 148～150 ℃/0.2mmHg is collected in underpressure distillation.
5, according to the said composing method of fly sexual tempting agent of claim 3, when it is characterized in that mustard alcohol sulfonyl ester Yu Geshi reagent react with CH
3MgI is added dropwise to the Li that contains that is dissolved with mustard alcohol sulfonyl ester
2CuCl
4Tetrahydrofuran solvent in, slowly reactant is risen to then under the room temperature and to stir 12 hours, after the dilute sulphuric acid acidifying, extract with Skellysolve A, washing, the saturated common salt washing is washed to neutrality again, tell dry the removing of organic layer siccative and desolvate, underpressure distillation is collected, the cut of 148-150 ℃/0.2mmHg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88107133 CN1018176B (en) | 1988-10-21 | 1988-10-21 | Composing method of fly sexual tempting agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88107133 CN1018176B (en) | 1988-10-21 | 1988-10-21 | Composing method of fly sexual tempting agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1041936A true CN1041936A (en) | 1990-05-09 |
| CN1018176B CN1018176B (en) | 1992-09-09 |
Family
ID=4834516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88107133 Expired CN1018176B (en) | 1988-10-21 | 1988-10-21 | Composing method of fly sexual tempting agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1018176B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102511493A (en) * | 2011-12-07 | 2012-06-27 | 杭州市植保土肥总站 | Liriomyza sativae attractant |
| CN102823590A (en) * | 2011-06-17 | 2012-12-19 | 信越化学工业株式会社 | Sex pheromone composition of peach fruit moth and attractant comprising the same |
| CN104970047A (en) * | 2015-06-23 | 2015-10-14 | 潍坊友容实业有限公司 | Liriomyza sativae attractant and application thereof in alfalfa saline-alkali soil planting |
| CN107751198A (en) * | 2016-08-17 | 2018-03-06 | 武汉市拜乐卫生科技有限公司 | A kind of water proof type drosophila lures sustained release agent, preparation method and application |
-
1988
- 1988-10-21 CN CN 88107133 patent/CN1018176B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102823590A (en) * | 2011-06-17 | 2012-12-19 | 信越化学工业株式会社 | Sex pheromone composition of peach fruit moth and attractant comprising the same |
| CN102823590B (en) * | 2011-06-17 | 2015-04-15 | 信越化学工业株式会社 | Sex pheromone composition of peach fruit moth and attractant comprising the same |
| CN102511493A (en) * | 2011-12-07 | 2012-06-27 | 杭州市植保土肥总站 | Liriomyza sativae attractant |
| CN104970047A (en) * | 2015-06-23 | 2015-10-14 | 潍坊友容实业有限公司 | Liriomyza sativae attractant and application thereof in alfalfa saline-alkali soil planting |
| CN107751198A (en) * | 2016-08-17 | 2018-03-06 | 武汉市拜乐卫生科技有限公司 | A kind of water proof type drosophila lures sustained release agent, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1018176B (en) | 1992-09-09 |
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