CN1018176B - Synthetic method of housefly sex attractant - Google Patents
Synthetic method of housefly sex attractantInfo
- Publication number
- CN1018176B CN1018176B CN 88107133 CN88107133A CN1018176B CN 1018176 B CN1018176 B CN 1018176B CN 88107133 CN88107133 CN 88107133 CN 88107133 A CN88107133 A CN 88107133A CN 1018176 B CN1018176 B CN 1018176B
- Authority
- CN
- China
- Prior art keywords
- mustard
- sulfonyl ester
- mustard alcohol
- erucic acid
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000010189 synthetic method Methods 0.000 title claims 2
- 241000257159 Musca domestica Species 0.000 title abstract description 9
- 239000000877 Sex Attractant Substances 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims abstract description 15
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 8
- IGOWHGRNPLFNDJ-HTXNQAPBSA-N (e)-tricos-9-ene Chemical compound CCCCCCCCCCCCC\C=C\CCCCCCCC IGOWHGRNPLFNDJ-HTXNQAPBSA-N 0.000 claims abstract description 6
- 230000006103 sulfonylation Effects 0.000 claims abstract description 3
- 238000005694 sulfonylation reaction Methods 0.000 claims abstract description 3
- 241000219198 Brassica Species 0.000 claims description 27
- 235000003351 Brassica cretica Nutrition 0.000 claims description 27
- 235000003343 Brassica rupestris Nutrition 0.000 claims description 27
- 235000010460 mustard Nutrition 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- -1 mustard alcohol sulfonyl ester Chemical class 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- 229910010082 LiAlH Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000001568 sexual effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- IGOWHGRNPLFNDJ-ZPHPHTNESA-N (z)-9-tricosene Chemical compound CCCCCCCCCCCCC\C=C/CCCCCCCC IGOWHGRNPLFNDJ-ZPHPHTNESA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- IGOWHGRNPLFNDJ-UHFFFAOYSA-N tricos-9t-ene Natural products CCCCCCCCCCCCCC=CCCCCCCCC IGOWHGRNPLFNDJ-UHFFFAOYSA-N 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 abstract description 4
- 239000007818 Grignard reagent Substances 0.000 abstract description 2
- 150000004795 grignard reagents Chemical class 0.000 abstract description 2
- 239000003139 biocide Substances 0.000 abstract 1
- 239000002917 insecticide Substances 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000343203 Lidia Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZYNDJIBBPLNPOW-UHFFFAOYSA-N eurucic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- ZYNDJIBBPLNPOW-KHPPLWFESA-N methyl erucate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-KHPPLWFESA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The housefly sex attractant (E-9-tricosene) is a housefly sex pheromone, and the housefly can be artificially trapped and killed by utilizing the housefly sex pheromone. Wherein the cis isomer has stronger trapping and killing capability than the trans isomer. Compared with other insecticides, it has the advantages of high specificity, high efficiency and no toxicity. The present invention relates to an improvement on the synthesis method of housefly trapping and killing agent, and is characterized by that it uses low-cost easily-available erucic acid as raw material, and adopts three steps of alcoholization, sulfonylation and reaction with Grignard reagent. The total yield reaches 41.3 percent, wherein the cis isomer is up to 98.4 percent, and the trans isomer only accounts for 1.6 percent.
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, Soience174,76(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.Inys Lipids II (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.Organic 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 with thin plate till the reduction fully, then with acetone recrystallization, to handle productive rate routinely be 90%, 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 ℃, and the 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 0.1MLi
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 15gLiAIH
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 (32m mol), 0.3g magnesium (33m mol) 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: 1,205 ℃ on T post, 280 ℃ of T vapour, T detects 320 ℃, and the retention time of cis is 77.96 minutes, and trans retention time is 78.84 minutes,
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:
--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 organic bases solvent, make then weight ratio be 1: 1 mustard alcohol and Tosyl chloride 0～30 ℃ of reaction 3～10 hours 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
2CuCl
4Tetrahydrofuran solution in-78 ℃ of reactions, lentamente reactant is risen to then under the room temperature and to stir 12 hours, obtain final product E-9 tricosene:
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; in 10～15 ℃ of reactions down of preferred temperature; 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
2Mg1 is added dropwise to the Li that contains that is dissolved with mustard alcohol sulfonyl ester
2In the tetrahydrofuran solution of CuCl, after the dilute sulphuric acid acidifying, extract with Skellysolve A, washing, the saturated common salt washing is washed to neutrality again, tells organic layer, and the siccative drying is removed and is desolvated, and 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
3Mg1 is added dropwise to the Li that contains that is dissolved with mustard alcohol sulfonyl ester
2CuCl
4Tetrahydrofuran solution in, after the dilute sulphuric acid acidifying, extract with Skellysolve A, washing, the saturated common salt washing is washed to neutrality again, tells organic layer, the siccative drying is removed and is desolvated, the cut of 148～150 ℃/0.2mmHg is collected in underpressure distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88107133 CN1018176B (en) | 1988-10-21 | 1988-10-21 | Synthetic method of housefly sex attractant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88107133 CN1018176B (en) | 1988-10-21 | 1988-10-21 | Synthetic method of housefly sex attractant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1041936A CN1041936A (en) | 1990-05-09 |
| CN1018176B true 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 | Synthetic method of housefly sex attractant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1018176B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120321588A1 (en) * | 2011-06-17 | 2012-12-20 | Shin-Etsu Chemical Co., Ltd. | Sex pheromone composition of peach fruit moth and attractant comprising the same |
| CN102511493B (en) * | 2011-12-07 | 2014-06-18 | 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 |
| CN117682942B (en) * | 2023-11-28 | 2025-09-16 | 安徽师范大学 | Host mark pheromone of gypsy moth egg flat-abdomen wasp and application and identification method thereof |
-
1988
- 1988-10-21 CN CN 88107133 patent/CN1018176B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1041936A (en) | 1990-05-09 |
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