CN105884613A - Compound and application of compound in preparation of orseolia oryzae sex attractant - Google Patents
Compound and application of compound in preparation of orseolia oryzae sex attractant Download PDFInfo
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- CN105884613A CN105884613A CN201610239768.3A CN201610239768A CN105884613A CN 105884613 A CN105884613 A CN 105884613A CN 201610239768 A CN201610239768 A CN 201610239768A CN 105884613 A CN105884613 A CN 105884613A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 95
- 241001465818 Orseolia oryzae Species 0.000 title claims abstract description 50
- 239000000877 Sex Attractant Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- -1 toluene sulfoxide Chemical class 0.000 claims description 10
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 9
- SBMPBXFNKYJNIC-UHFFFAOYSA-N (4-methylsulfanylphenyl)methanamine Chemical compound CSC1=CC=C(CN)C=C1 SBMPBXFNKYJNIC-UHFFFAOYSA-N 0.000 claims description 8
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 8
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 8
- 229940102001 zinc bromide Drugs 0.000 claims description 8
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 6
- 238000003379 elimination reaction Methods 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 5
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 5
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 5
- PXDRFTPXHTVDFR-UHFFFAOYSA-N propane;titanium(4+) Chemical compound [Ti+4].C[CH-]C.C[CH-]C.C[CH-]C.C[CH-]C PXDRFTPXHTVDFR-UHFFFAOYSA-N 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- YSAVZVORKRDODB-PHDIDXHHSA-N diethyl (2r,3r)-2,3-dihydroxybutanedioate Chemical compound CCOC(=O)[C@H](O)[C@@H](O)C(=O)OCC YSAVZVORKRDODB-PHDIDXHHSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- RUZLIIJDZBWWSA-INIZCTEOSA-N methyl 2-[[(1s)-1-(7-methyl-2-morpholin-4-yl-4-oxopyrido[1,2-a]pyrimidin-9-yl)ethyl]amino]benzoate Chemical group COC(=O)C1=CC=CC=C1N[C@@H](C)C1=CC(C)=CN2C(=O)C=C(N3CCOCC3)N=C12 RUZLIIJDZBWWSA-INIZCTEOSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims 1
- 241000238631 Hexapoda Species 0.000 abstract description 15
- 241000607479 Yersinia pestis Species 0.000 abstract description 11
- 238000012544 monitoring process Methods 0.000 abstract description 9
- ANYRCIZNXMJVBC-QMMMGPOBSA-N [(2S)-6-oxoheptan-2-yl] acetate Chemical compound C(C)(=O)O[C@H](CCCC(C)=O)C ANYRCIZNXMJVBC-QMMMGPOBSA-N 0.000 abstract 2
- 230000013011 mating Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 241000255925 Diptera Species 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 240000007594 Oryza sativa Species 0.000 description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- MJHILYFKDYGKMZ-IUCAKERBSA-N [(2S,6S)-6-acetyloxyheptan-2-yl] acetate Chemical compound C(C)(=O)O[C@@H](C)CCC[C@H](C)OC(C)=O MJHILYFKDYGKMZ-IUCAKERBSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000003462 sulfoxides Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 5
- 229960003328 benzoyl peroxide Drugs 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 230000027326 copulation Effects 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 241001465828 Cecidomyiidae Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000013019 agitation Methods 0.000 description 3
- 150000001793 charged compounds Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 C[N+](*)(CC(CCCC(*)=O)=O)[O-] Chemical compound C[N+](*)(CC(CCCC(*)=O)=O)[O-] 0.000 description 2
- 241001663467 Contarinia tritici Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- 235000000540 Brassica rapa subsp rapa Nutrition 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 240000005250 Chrysanthemum indicum Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241001582888 Lobus Species 0.000 description 1
- 241001422926 Mayetiola hordei Species 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
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- NKLCNNUWBJBICK-UHFFFAOYSA-N dess–martin periodinane Chemical compound C1=CC=C2I(OC(=O)C)(OC(C)=O)(OC(C)=O)OC(=O)C2=C1 NKLCNNUWBJBICK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007758 mating behavior Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-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
- 239000003016 pheromone Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/14—Acetic acid esters of monohydroxylic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a compound and an application of the compound in preparation of an orseolia oryzae sex attractant. The compound is (6S)-6-acetoxyl-2-heptanone, and a structural formula of the compound is represented as a formula I. The compound can cooperate with (6S)-6-acetoxyl-2-heptanone to be taken as the orseolia oryzae sex attractant or can be independently taken as the orseolia oryzae sex attractant, and the compound can be used for performing population monitoring and comprehensive control of orseolia oryzae. The orseolia oryzae sex attractant prepared from the compound and a lure of the orseolia oryzae sex attractant can be applied to: (1) orseolia oryzae population monitoring and prediction; (2), mass trapping; (3), mating disruption. The sex attractant prepared from the sex pheromone (namely, the compound) and the lure of the sex attractant can be used for performing population monitoring and comprehensive control on the orseolia oryzae, and the sex attractant has the advantages of low cost and high efficiency and is suitable for predicting the occurrence rule of pests hiding in insect galls.
Description
Technical field
The present invention relates to a kind of compound and the application in preparation pachydiplosis oryzae sex attractant thereof.
Background technology
Pachydiplosis oryzae, Orseoia oryzae (Wood-Mason), Diptera, Cecidomyiidae, now it is distributed in China Guangdong, Guangxi, Fujian, Yunnan, Guizhou, Hainan, Jiangxi, Hunan, Taiwan, and the Southeast Asian countries such as Vietnam, Burma.It is a kind of common insect pests, generation more than a year, generation overlap on Oryza sativa L..Main sucking paddy growth by larva and order juice, the rice seedling base portion that causes to be injured expands, and lobus cardiacus stops growing and formed the Herba Alii fistulosi pipe of light green hollow by the elongation of sheath portion subsequently, and Herba Alii fistulosi pipe marks Herba Alii fistulosi to overhanging formation.Oryza sativa L. all can be injured from rice shoot to young panicle formation stage, can not earing of weight of being injured, and nearly all forms mark Herba Alii fistulosi or distortion solid can not cause Oryza sativa L. not ear.Owing to larva is hidden inside mark Herba Alii fistulosi, it is difficult to directly tag, in production, main employing systemic pesticide carries out chemical prevention, easily cause pesticide residues severe overweight, have impact on product quality, simultaneously because life-time service insecticide, be easily caused pachydiplosis oryzae Drug resistance and improve constantly, natural enemy populations quantity falls sharply, and the problem such as environmental pollution.
Efficiently, new method nontoxic, unpollution control methods pachydiplosis oryzae has certain scientific meaning and application prospect.Application insect sex pheromone carry out detecting and reporting pest information, Insect pest suppression and mass trapping preventing and treating agriculture and forestry injurious insect, due to its have highly sensitive, selectivity strong, harmless to natural enemy, do not cause the features such as environmental pollution to receive an acclaim.Detect additionally, be possible with insect sex pheromone trapper between country variant or area, to determine that certain external crushing insect has been invaded.Known nearly 5000 kinds of the Cecidomyiidae insecticide whole world, having the Cecidomyiidae identified synthesis of insect sex pheromone chemical constitution such as Hessian fly, Semen Pisi sativi cecidomyiia, turnip Caulis et Folium Brassicae capitatae cecidomyiia, Pseudotsuga menziesii (Mirbel) Franco strobile cecidomyiia, Pinus koraiensis strobile cecidomyiia, gall aphid, wheat midge, Fructus Rubi cecidomyiia, Chrysanthemum Gall Midge at present, wherein wheat midge and Semen Pisi sativi cecidomyiia synthetic sex pheromone have been successfully applied to detecting and reporting pest information.
Summary of the invention
It is an object of the invention to provide a kind of compound and the application in preparation pachydiplosis oryzae sex attractant thereof, described compound is (6S)-6-acetoxyl group-2-heptanone, it can be with ((2S, 6S)-2,6-diacetoxy heptane coordinates as pachydiplosis oryzae sex attractant, can be used for pachydiplosis oryzae is carried out population monitoring and integrated control.
The structural formula of compound provided by the present invention shown in formula I,
Present invention also offers the preparation method of compound shown in Formulas I, comprise the steps:
(1) under conditions of (R, R)-diethyl tartrate. and tetra isopropyl titanium oxide exist, 4-aminomethyl phenyl methyl sulfide and cumyl hydroperoxide carry out reaction and obtain compound shown in formula 1；
(2) under the catalysis of lithium diisopropylamine, compound shown in formula 1 and glutaric anhydride carry out reaction and obtain compound shown in formula 2；
In formula 2, p-Tol represents p-methylphenyl；
(3) under the effect of base catalyst, compound shown in formula 2 and dimethyl sulfate carry out reaction and obtain compound shown in formula 3；
In formula 3, p-Tol represents p-methylphenyl；
(4) under the catalysis of zinc bromide and diisobutyl aluminium hydride, shown in formula 3, compound obtains compound shown in formula 4 through reduction reaction；
(5) compound shown in formula 4 and tert-butyl chloro-silicane carry out reacting products therefrom, obtain compound shown in formula 5 through Raney's nickel reduction；
In formula 5, TBS represents fert-butyidimethylsilyl；
(6) under the catalysis of lithium diisopropylamine, compound shown in formula 5 and (S)-methyl carry out reaction to toluene sulfoxide and obtain compound shown in formula 6；
In formula 6, TBS represents that fert-butyidimethylsilyl, p-Tol represent p-methylphenyl；
(7) under the catalysis of zinc bromide and diisobutyl aluminium hydride, shown in formula 6, compound obtains compound shown in formula 7 through reduction reaction；
In formula 7, TBS represents that fert-butyidimethylsilyl, p-Tol represent p-methylphenyl；
(8) product after compound shown in formula 7 carries out elimination reaction under the catalysis of tetrabutyl ammonium fluoride, obtains compound shown in formula 8 through Raney's nickel reduction；
(9) under the oxidation of Dai Si-Martin's oxidant, the oxidized reaction of compound shown in formula 8 obtains compound shown in formula 9；
(10) compound shown in formula 9 and chloroacetic chloride carry out esterification, obtain compound shown in Formulas I.
In above-mentioned preparation method, in step (1), described 4-aminomethyl phenyl methyl sulfide is 1:1～5 with the mol ratio of described cumyl hydroperoxide；
Described 4-aminomethyl phenyl methyl sulfide is 1:1～5 with the mol ratio of described (R, R)-diethyl tartrate.；
Described 4-aminomethyl phenyl methyl sulfide is 1:1～5, concretely 1:1 with the mol ratio of described tetra isopropyl titanium oxide；
The temperature stating reaction is-20 DEG C～-10 DEG C；
The time of described reaction is 24～48 hours.
In above-mentioned preparation method, in step (2), compound shown in formula 1 is 1:1～5 with the mol ratio of described glutaric anhydride；
The temperature of described reaction is-78 DEG C～-50 DEG C；
The time of described reaction is 1～6 hour.
In above-mentioned preparation method, in step (3), described base catalyst is potassium carbonate；
Compound shown in formula 2 is 1:1～5 with the mol ratio of described dimethyl sulfate；
The temperature of described reaction is 30～50 DEG C；
The time of described reaction is 24～48 hours.
In above-mentioned preparation method, in step (4) and step (7),
Compound shown in compound shown in formula 3 or formula 6 is 1:1～2 with the mol ratio of described zinc bromide；
Compound shown in compound shown in formula 3 or formula 6 is 1:1～2 with the mol ratio of described diisobutyl aluminium hydride；
The temperature of described reduction reaction is-78 DEG C～-50 DEG C；
The time of described reduction reaction is 1～6 hour.
In above-mentioned preparation method, in step (5), compound shown in formula 4 is 1:1～2 with the mol ratio of described tert-butyl chloro-silicane；
The temperature of described reduction reaction is 20～25 DEG C；
The time of described reduction reaction is 1～5 hour.
In above-mentioned preparation method, in step (6), compound shown in formula 5 and described (S)-methyl are 1:1～2 to the mol ratio of toluene sulfoxide；
Compound shown in formula 5 is 1:1～2 with the mol ratio of described lithium diisopropylamine；
The temperature of described reaction is-78 DEG C～-50 DEG C；
The time of described reaction is 1～5 hour.
In above-mentioned preparation method, in step (8), compound shown in formula 7 is 1:1～2 with the mol ratio of described tetrabutyl ammonium fluoride；
The temperature of shown elimination reaction is 20～25 DEG C；
The time of described elimination reaction is 1～5 hour；
In step (9), compound shown in formula 8 is 1:1～2 with the mol ratio of described Dai Si-Martin's oxidant；
The temperature of shown oxidation reaction is 0～5 DEG C；
The time of described oxidation reaction is 0.5～5 hour；
In step (10), compound shown in formula 9 is 1:1～2 with the mol ratio of described chloroacetic chloride；
The temperature of shown esterification is 20～25 DEG C；
The time of described esterification is 12～20 hours.
Compound shown in the Formulas I that the present invention provides can be with (2S, 6S)-2, and 6-diacetoxy heptane is compounding to be used, as pachydiplosis oryzae sex attractant；
Described pachydiplosis oryzae sex attractant can be used for monitoring pachydiplosis oryzae situation occurred and/or prediction pachydiplosis oryzae insect pest occurs, disturbs pachydiplosis oryzae copulation and/or trapping, kills pachydiplosis oryzae or detect pachydiplosis oryzae insect pest.
Compound shown in formula I and (2S, 6S)-2,6-diacetoxy heptane is compounding when using, and can coordinate according to the weight ratio of 0.5～5:10, and concretely 1～5:10,1:10 or 5:10.
A kind of pachydiplosis oryzae sex attractant lure can be obtained at pachydiplosis oryzae sex attractant as described on the supported on carriers such as rubber stopper or resin material, specifically can obtain in accordance with the following steps: with organic solvent, described pachydiplosis oryzae sex attractant is configured to solution, described carrier is immersed in described solution, described carrier is taken out, obtains pachydiplosis oryzae sex attractant lure.
Pachydiplosis oryzae sex attractant prepared by compound shown in Formulas I provided by the present invention and lure thereof can be used for following purposes:
(1) pachydiplosis oryzae population monitoring forecast
In 1 year number generation of pachydiplosis oryzae, the pachydiplosis oryzae sex attractant and the lure thereof that provide by the present invention can monitor and predict pachydiplosis oryzae emergence period, generating capacity and distributed areas in time and accurately, and can estimate pest damage area and Control stage.Pachydiplosis oryzae sex attractant and lure thereof by the present invention observe and predict insect pest situation, have highly sensitive, and accuracy is good, easy to use, low cost, are suitable to popularity and use.
(2) mass trapping
Trap and kill male worm at deployment pachydiplosis oryzae sex attractant trap, cause female-male proportion numerous imbalances, reduce the mating behavior of male and female, reduce progeny population density, reduce harm.
(3) Insect pest suppression
Discharge pachydiplosis oryzae sex attractant and the lure thereof of the present invention in field, in the environment of full female mosquito sex pheromone abnormal smells from the patient, male mosquito loses the capacity of orientation to female mosquito, causes the copulation probability between the male and female of field to be greatly reduced, so that insect density of future generation declines.
Sex attractant and lure thereof that the application pheromone of the present invention is made can be used for carrying out pachydiplosis oryzae population monitoring and integrated control, and described sex attractant has low cost, efficiency height, are suitable to forecast the pests occurrence rule hidden the internal insect of insect gall.
Accompanying drawing explanation
Fig. 1 is the equation equation of compound shown in formula I.
Fig. 2 is the mass spectrum of compound shown in Formulas I.
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
The preparation of compound shown in embodiment 1, Formulas I
It is prepared according to the synthetic route chart shown in Fig. 1.
1) synthesis of (R)-4-methylphenylmethyl sulfoxide (1)
Under nitrogen protection; 500mL Shrek bottle is separately added into 200mL anhydrous methylene chloride, (R.R)-diethyl tartrate. 24.8g; and 16.8g tetra isopropyl titanium oxide; 1.08mL water it is slowly added dropwise after being subsequently agitated for 10 minutes; this system stirs 30min at 25 DEG C, is cooled to-30 DEG C subsequently, is slowly added to 4-aminomethyl phenyl methyl sulfide 8.3g and cumyl hydroperoxide 18.3g; continuing to be stirred overnight, period is incubated at-30 DEG C.After reaction terminates, add copperas solution and citric acid solution cancellation reaction, after ether extraction (200mL × 3), merge organic facies, anhydrous MgSO4It is dried, the crude product that decompression precipitation obtains, column chromatography purification obtains 7.02g compound 1.This product optical purity is analyzed through HPLC, and optical purity is more than 99%.
2) synthesis of (S)-5-oxo-6-(to toluene sulfenyl) caproic acid (2)
Under nitrogen protection; (R)-4-methylphenylmethyl sulfoxide is added in the 500mL Shrek bottle being equipped with mechanical agitation, thermometer and reflux condensing tube; 20mL THF and LDA solution (23mmol) is added at-78 DEG C; after then raising temperature to-40 DEG C of stirring 30min; after reaction system is cooled to-78 DEG C and is slowly added dropwise glutaric anhydride 1.25g, heating systems temperature is to-60 DEG C and stirs.React 2 hours after terminating to add a small amount of liquor alumini chloridi cancellation reaction to reaction, ethyl acetate the most repeatedly extractive reaction liquid, merge organic facies, anhydrous Na2SO4It is dried, obtains colorless viscous shape liquid after concentration, column chromatography purification obtain 2.4g compound 2.
3) synthesis of (S)-5-oxo-6-(to toluene sulfenyl) methyl caproate (3)
It is separately added into 100mL acetone, (S)-5-oxo-6-(to toluene sulfenyl) caproic acid 2.4g and 2g potassium carbonate in the 250mL four-hole bottle being equipped with mechanical agitation, thermometer and reflux condensing tube, being slowly added dropwise 3.3g dimethyl sulfate subsequently, this system is then raising temperature to return stirring overnight.After reaction terminates, the crude product that decompression precipitation obtains, column chromatography purification obtain 2.5g compound 3.
4) synthesis of (S)-5-hydroxyl-6-(to toluene sulfenyl) methyl caproate (4)
Under room temperature, 50mL Shrek flask adds (S)-5-oxo-6-(to toluene sulfenyl) methyl caproate (2.95g, 10mmol) in 20mL anhydrous tetrahydro furan.Under stirring, add Zinc Bromide Anhydrous (2.48g, 11mmol).After this system continue to be cooled to subzero 78 DEG C, the DIBAL solution of 10mL (1mol/L) is added after stirring, during reaction hour 3～4, reaction terminates, reactant liquor methanol (10mL) cancellation is reacted, merge organic layer, anhydrous magnesium sulfate is dried, obtains 2.4g compound 4 through silica gel chromatography after concentrating under reduced pressure.
5) synthesis of methyl (S)-5-((t-Butyldimethylsilyl) epoxide) alkyl caproate (5)
Under nitrogen protection; 100mL flask is separately added into 30mL dry DMF, compound 5 (2.4g; 8mmol) and 1.65g imidazoles; it is slowly added dropwise tert-butyl chloro-silicane (1.16g subsequently; 10mmol); this system continues to be stirred overnight, and after reaction terminates, adds the saturated NH of 5mL4Cl aqueous solution cancellation is reacted, and merges organic facies, anhydrous Na after ether extraction (40mL × 3)2SO4It is dried, the crude product that decompression precipitation obtains, direct plunges into next step reaction；The crude product obtained is dissolved in 20mL ethanol, is dividedly in some parts Raney's nickel compound, subsequently room temperature reaction subsequently, middle TLC monitoring raw material has converted rear (one hour), filter out the nickel of excess, merge organic layer, after concentrating under reduced pressure, obtain 1.8g compound 5 through silica gel chromatography.
6) (S)-6-((t-Butyldimethylsilyl) epoxide)-1-((R)-to toluene sulfenyl) heptyl-2-ketone) synthesis of (6)
Under nitrogen protection; in the 100mL four-hole bottle being equipped with mechanical agitation, thermometer and reflux condensing tube; the anhydrous tetrahydro furan of addition 20mL and chirality methyl are to toluene sulfoxide (1.56g); in four-hole bottle, add LDA solution (10.2mmol) after being cooled to-78 DEG C subsequently in batches; stirring is started after dropping; period allows reaction system to rise to-30 DEG C; after continuing stirring 0.5h; after reaction bulb temperature is reduced to-78 DEG C and is slowly added dropwise ester 6 (2.60g), stirring terminates to reaction.React 2～3 hours after extremely reacting completely, after adding a small amount of frozen water cancellation reaction, ether the most repeatedly extractive reaction liquid, merge organic facies, anhydrous Na2SO4It is dried, obtains colorless viscous shape liquid after concentration, column chromatography purification obtain 3.64g compound 6.
7) synthesis of (S)-6-((t-Butyldimethylsilyl) epoxide)-1-((R)-to toluene sulfenyl) heptyl-2-hydroxyl (7)
Under room temperature, 50mL Shrek flask adds ketone 7 (3.95g, 10mmol) in 20mL anhydrous tetrahydro furan.Under stirring, add Zinc Bromide Anhydrous (2.48g, 11mmol).After this system continue to be cooled to-78 DEG C, the DIBAL solution of 10mL (1mol/L) is added after stirring, after reaction terminates, reactant liquor methanol (10mL) cancellation is reacted, merge organic layer, anhydrous magnesium sulfate is dried, obtains 3.4g compound 7 through silica gel chromatography after concentrating under reduced pressure.
8) synthesis of (2S, 6S)-normal heptane-2,6-glycol (8)
Under nitrogen protection, 100mL flask is separately added into the anhydrous THF of 30mL, compound 8 (3.98g, 10mmol) and the TBAF solution of 10mmol; this system continues stirring 3h in room temperature; after reaction terminates, the crude product that decompression precipitation obtains, direct plunge into next step reaction；The crude product obtained is dissolved in 20mL ethanol, is dividedly in some parts Raney's nickel compound, subsequently room temperature reaction subsequently, middle TLC monitoring raw material has converted rear (one hour), filter out the nickel of excess, merge organic layer, after concentrating under reduced pressure, obtain 1.2g compound 8 through silica gel chromatography.
9) synthesis of (S)-6-Hydroxyheptyl-2-ketone (10)
Under nitrogen protection; 100mL Shrek pipe is separately added into 30mL anhydrous methylene chloride, glycol 8 (1.3g; 10mmol); it is cooled to subsequently when 0 DEG C be slowly added dropwise and the Dess-martin reagent of 4.24g; this system stirs 30min at 0 DEG C; then raise temperature to 30 DEG C, after continuing stirring 3h.After reaction terminates, add the saturated NH of 5mL4Cl aqueous solution cancellation is reacted, and merges organic facies, anhydrous Na after dichloromethane extraction (40mL × 3)2SO4It is dried, the crude product that decompression precipitation obtains, column chromatography purification obtains 1.1g compound 9.
10) synthesis of (S)-6-oxo heptyl-2-acetas
Under room temperature, 50mL single port flask adds compound 9 (0.65g, 5mol) in 10mL dichloromethane.Under stirring, add chloroacetic chloride (392mg, 5mmol).This system adds 2mL deionized water cancellation reaction after continuing stirring reaction 12 hours, reactant liquor dichloromethane (10mL × 5) extracts, merge organic layer, anhydrous magnesium sulfate is dried, white solid 0.77g is obtained through silica gel chromatography after concentrating under reduced pressure, its mass spectrum is as in figure 2 it is shown, 195.1 is [M+Na]+Peak, m/z 57 (C2H5CO+) it is residual group after carbonyl fracture, m/z 165.1 sloughs [M+Na] after two methyl for molecular ion+Peak, m/z 137.1 sloughs [the M+Na]+peak after an acetoxyl group for molecular ion, and m/z 111.2 leaves away one the acetoxyl group after resetting for molecular ion, and m/z 83.2 is that the peak of m/z 111.2 continues fracture and loses two methylene.
Identified structure is correct.
Shown in embodiment 2, Formulas I, compound is as the application of pachydiplosis oryzae sex attractant
Following embodiment is to carry out in Oryza sativa L. field, Yueye County, Guangxi province in May, 2012～2015 to October.
By (2S, 6S)-2,6-diacetoxy heptane and (6S)-6-acetoxyl group-2-heptanone, it is dissolved in normal hexane according to mixture 10 microgram of 10:1 mixing, then it is added drop-wise on rubber stopper partition, after normal hexane volatilizees, drips 200 microlitre dichloromethane, after dichloromethane volatilizees, seal standby in the pachydiplosis oryzae sex attractant lure made is loaded aluminium foil.
On August 24,20 days to 20014 August in 2014 uses triangle viscose trapper, and trapper is surrounded by palstic corrugated sheet, and the 15cm that goes to the bottom, two length of sides are respectively the isosceles triangle of 20cm, and the cardboard scribbling insect sticker is placed in bottom.Lure is placed in the middle of trapper, away from glue surface about 2cm.Trapper arranges that distance ground is highly consistent with rice plant, is spaced 15m between trapper.The non-copulation of pachydiplosis oryzae is set simultaneously and crosses female mosquito trapper (non-copulation is crossed female mosquito be placed in little sarong, be placed in the middle of trapper, distance glue surface about 2cm) and blank trapper.Each test processes and arranges 3 repetitions.Result of the test is shown in Table 1.
Table 1 pachydiplosis oryzae gyplure lure trapping pachydiplosis oryzae hero mosquito result of the test
Data from table 1:
The present invention's contains (2S, 6S)-2,6-diacetoxy heptane and the pachydiplosis oryzae sex attractant lure of (6S)-6-acetoxyl group-2-heptanone, in field, pachydiplosis oryzae hero mosquito attracting action is better than non-copulation and crosses female mosquito, there is preferable trapping effect, and the pachydiplosis oryzae gyplure product price of the present invention is suitable, has good society and ecological benefits, is suitable for popularization and application.
Shown in embodiment 3, Formulas I, compound is as the application of pachydiplosis oryzae sex attractant
10 days to 2015 JIUYUE of JIUYUE in 2015 use triangle viscose trapper on 20th, and the cardboard scribbling insect sticker is placed in bottom.By (2S, 6S)-2,6-diacetoxy heptane (A) and (6S)-6-acetoxyl group-2-heptanone (B) two component is configured to lure, lure 1 (A:B=10:1) and lure 2 (A:B=10:5) by different proportion.Lure is placed in the middle of trapper, away from glue surface about 2cm.Trapper arranges that distance ground is highly consistent with rice plant, is spaced 15m between trapper.Each test processes and arranges 3 repetitions.Result of the test is shown in Table 2.
Table 2 pachydiplosis oryzae gyplure lure trapping pachydiplosis oryzae hero mosquito result of the test
Data from table 2:
The present invention's contains (2S, 6S)-2,6-diacetoxy heptane and the pachydiplosis oryzae sex attractant lure of (6S)-6-acetoxyl group-2-heptanone, can obtain preferable trapping effect, have stronger trapping capability when weight ratio is 10:1 and 10:5.
Claims (10)
1. compound shown in Formulas I,
2. the preparation method of compound shown in Formulas I, comprises the steps:
(1) under conditions of (R, R)-diethyl tartrate. and tetra isopropyl titanium oxide exist, 4-aminomethyl phenyl methyl sulfide
Carry out reaction with cumyl hydroperoxide and obtain compound shown in formula 1；
(2) under the catalysis of lithium diisopropylamine, compound shown in formula 1 and glutaric anhydride carry out reaction and obtain formula 2
Shown compound；
In formula 2, p-Tol represents p-methylphenyl；
(3) under the effect of base catalyst, compound shown in formula 2 and dimethyl sulfate carry out reaction and obtain formula 3
Shown compound；
In formula 3, p-Tol represents p-methylphenyl；
(4) under the catalysis of zinc bromide and diisobutyl aluminium hydride, shown in formula 3, compound obtains formula 4 through reduction reaction
Shown compound；
(5) compound shown in formula 4 and tert-butyl chloro-silicane carry out reacting products therefrom, reduce through Raney's nickel
To compound shown in formula 5；
In formula 5, TBS represents fert-butyidimethylsilyl；
(6) under the catalysis of lithium diisopropylamine, toluene sulfoxide is carried out instead by compound shown in formula 5 and (S)-methyl
Compound shown in formula 6 should be obtained；
In formula 6, TBS represents that fert-butyidimethylsilyl, p-Tol represent p-methylphenyl；
(7) under the catalysis of zinc bromide and diisobutyl aluminium hydride, shown in formula 6, compound obtains formula 7 through reduction reaction
Shown compound；
In formula 7, TBS represents that fert-butyidimethylsilyl, p-Tol represent p-methylphenyl；
(8) product after compound shown in formula 7 carries out elimination reaction under the catalysis of tetrabutyl ammonium fluoride, through Raney's nickel
Reduction obtains compound shown in formula 8；
(9) under the oxidation of Dai Si-Martin's oxidant, the oxidized reaction of compound shown in formula 8 obtains formula 9 shownization
Compound；
(10) compound shown in formula 9 and chloroacetic chloride carry out esterification, obtain compound shown in Formulas I.
Preparation method the most according to claim 2, it is characterised in that: in step (1), described 4-methylbenzene
Base methyl sulfide is 1:1～5 with the mol ratio of described cumyl hydroperoxide；
Described 4-aminomethyl phenyl methyl sulfide is 1:1～5 with the mol ratio of described (R, R)-diethyl tartrate.；
Described 4-aminomethyl phenyl methyl sulfide is 1:1～5 with the mol ratio of described tetra isopropyl titanium oxide；
The temperature of described reaction is-20 DEG C～-10 DEG C；
The time of described reaction is 24～48 hours.
4. according to the preparation method described in Claims 2 or 3, it is characterised in that: in step (2), shown in formula 1
Compound is 1:1～5 with the mol ratio of described glutaric anhydride；
The temperature of described reaction is-78 DEG C～-50 DEG C；
The time of described reaction is 1～6 hour.
5. according to the preparation method according to any one of claim 2-4, it is characterised in that: in step (3), institute
Stating base catalyst is potassium carbonate；
Compound shown in formula 2 is 1:1～5 with the mol ratio of described dimethyl sulfate；
The temperature of described reaction is 30～50 DEG C；
The time of described reaction is 24～48 hours.
6. according to the preparation method according to any one of claim 2-5, it is characterised in that: step (4) and step
(7) in,
Compound shown in compound shown in formula 3 or formula 6 is 1:1～2 with the mol ratio of described zinc bromide；
Compound shown in compound shown in formula 3 or formula 6 is 1:1～2 with the mol ratio of described diisobutyl aluminium hydride；
The temperature of described reduction reaction is-78 DEG C～-50 DEG C；
The time of described reduction reaction is 1～5 hour.
7. according to the preparation method according to any one of claim 2-6, it is characterised in that: in step (5), formula
Compound shown in 4 is 1:1～2 with the mol ratio of described tert-butyl chloro-silicane；
The temperature of described reduction reaction is 20～25 DEG C；
The time of described reduction reaction is 1～5 hour.
8. according to the preparation method according to any one of claim 2-7, it is characterised in that: in step (6), formula
Compound shown in 5 and described (S)-methyl are 1:1～2 to the mol ratio of toluene sulfoxide；
Compound shown in formula 5 is 1:1～2 with the mol ratio of described lithium diisopropylamine；
The temperature of described reaction is-78 DEG C～-50 DEG C；
The time of described reaction is 1～5 hour.
9. according to the preparation method according to any one of claim 2-7, it is characterised in that: in step (8), formula
Compound shown in 7 is 1:1～2 with the mol ratio of described tetrabutyl ammonium fluoride；
The temperature of shown elimination reaction is 20～25 DEG C；
The time of described elimination reaction is 1～5 hour；
In step (9), compound shown in formula 8 is 1:1～2 with the mol ratio of described Dai Si-Martin's oxidant；
The temperature of shown oxidation reaction is 0～5 DEG C；
The time of described oxidation reaction is 0.5～5 hour；
In step (10), compound shown in formula 9 is 1:1～2 with the mol ratio of described chloroacetic chloride；
The temperature of shown esterification is 20～25 DEG C；
The time of described esterification is 12～20 hours.
10. the application in preparation pachydiplosis oryzae sex attractant of the compound shown in Formulas I.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111838152A (en) * | 2020-06-19 | 2020-10-30 | 中国医学科学院药用植物研究所 | Lycium barbarum gallmidge attractant composition, lure and 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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