CN105801409A - Compound and application thereof to preparation of orseolia oryzae wood-mason sex attractant - Google Patents
Compound and application thereof to preparation of orseolia oryzae wood-mason sex attractant Download PDFInfo
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- CN105801409A CN105801409A CN201610239781.9A CN201610239781A CN105801409A CN 105801409 A CN105801409 A CN 105801409A CN 201610239781 A CN201610239781 A CN 201610239781A CN 105801409 A CN105801409 A CN 105801409A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 83
- 241001465818 Orseolia oryzae Species 0.000 title claims abstract description 47
- 239000000877 Sex Attractant Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 acetoxyl group heptanes Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 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 14
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 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
- 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
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 5
- 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 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
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 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
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 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 2
- 230000009467 reduction 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 12
- 241000607479 Yersinia pestis Species 0.000 abstract description 10
- 238000012544 monitoring process Methods 0.000 abstract description 9
- 229960003328 benzoyl peroxide Drugs 0.000 abstract description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract description 3
- 230000013011 mating Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 241000255925 Diptera Species 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 235000007164 Oryza sativa Nutrition 0.000 description 9
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 8
- 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
- 239000012043 crude product Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 240000007594 Oryza sativa Species 0.000 description 5
- 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 5
- 230000027326 copulation Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 241001465828 Cecidomyiidae Species 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 208000035126 Facies Diseases 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 150000003462 sulfoxides Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 239000007832 Na2SO4 Substances 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
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 238000013019 agitation Methods 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
- 238000004440 column chromatography Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 238000000034 method Methods 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 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
- 241001663467 Contarinia tritici Species 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002576 ketones Chemical class 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
- 239000000203 mixture 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
- 239000007787 solid 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 208000000260 Warts Diseases 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid 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
- 238000013329 compounding Methods 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
- 238000001514 detection method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006843 female mating behavior Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000268 heptanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 230000006288 male mating behavior Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 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
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 201000010153 skin papilloma Diseases 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- 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
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
-
- 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
- C07C317/00—Sulfones; Sulfoxides
- C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
- C07C317/46—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
-
- 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
- C07C69/16—Acetic acid esters of dihydroxylic 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (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 application thereof to preparation of orseolia oryzae wood-mason sex attractant. The compound is (2S, 6S)-2, 6-2 acetoxyl group heptanes, and the structural formula of the compound is as shown in the formula I. The compound can be matched with (6S)-6-acetoxyl group-2-heptanone or used independently to serve as the orseolia oryzae wood-mason sex attractant and can be used for conducting population monitoring and comprehensive prevention and control over orseolia oryzae wood-mason. The orseolia oryzae wood-mason sex attractant prepared from the compound and a lure of the sex attractant can be used for population monitoring and predication of orseolia oryzae wood-mason, mass trapping and interference with mating. The sex attractant prepared from sex pheromone (compound) and the lure of the sex attractant can be used for population monitoring and comprehensive prevention and control over orseolia oryzae wood-mason, and the sex attractant is low in cost, high in efficiency and suitable for predicating occurrence regularity 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, wide
West, 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..Mainly suck paddy growth by larva and order juice,
Cause rice seedling base portion of being injured expands, and lobus cardiacus stops growing and formed the Herba Alii fistulosi pipe of light green hollow, Herba Alii fistulosi by the elongation of sheath portion subsequently
Pipe forms mark Herba Alii fistulosi to overhanging.Oryza sativa L. all can be injured from rice shoot to young panicle formation stage, can not earing, nearly all of weight of being injured
Form 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 touch
Killing, in production, main employing systemic pesticide carries out chemical prevention, easily causes pesticide residues severe overweight, have impact on product
Product quality, simultaneously because life-time service insecticide, is easily caused pachydiplosis oryzae Drug resistance and improves constantly, and 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 elder brother
Worm 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 is strong, harmless to natural enemy, do not cause the features such as environmental pollution to receive an acclaim.Additionally, country variant or area
Between be possible with insect sex pheromone trapper and detect, to determine that certain external crushing insect has been invaded.
Known nearly 5000 kinds of the Cecidomyiidae insecticide whole world, has Hessian fly, Semen Pisi sativi cecidomyiia, turnip Caulis et Folium Brassicae capitatae cecidomyiia, star-spangled banner at present
The loosely fruit Cecidomyiidae insecticide such as cecidomyiia, Pinus koraiensis strobile cecidomyiia, gall aphid, wheat midge, Fructus Rubi cecidomyiia, Chrysanthemum Gall Midge
The identified synthesis of sex pheromone chemical constitution, wherein wheat midge and Semen Pisi sativi cecidomyiia synthetic sex pheromone are the most successful
It is 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, described chemical combination
Thing is (2S, 6S)-2,6-diacetoxy heptane, and it can coordinate with (6S)-6-acetoxyl group-2-heptanone or independent
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
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) compound shown in formula 8 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 and described hydrogen peroxide isopropyl
The mol ratio of benzene is 1:1～5, concretely 1:2；
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.
In above-mentioned preparation method, in step (2), compound shown in formula 1 is 1 with the mol ratio of described glutaric anhydride:
1～5；
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 and described tert-butyl chloro-silicane
Mol ratio be 1:1～2；
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 to toluene sulfoxide
Mol ratio is 1:1～2；
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 and described tetrabutyl ammonium fluoride mole
Ratio is 1:1～2；
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 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 used alone or compound with (6S)-6-acetoxyl group-2-heptanone and make
With, 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, interference
Pachydiplosis oryzae copulation and/or trapping, kill pachydiplosis oryzae or detection pachydiplosis oryzae insect pest.
During the use compounding with (6S)-6-acetoxyl group-2-heptanone of compound shown in formula I, can be according to 10:0.5～5
Weight ratio coordinate, concretely 10:1～5,10:1 or 10:5.
A kind of pachydiplosis oryzae can be obtained at pachydiplosis oryzae sex attractant as described on the supported on carriers such as rubber stopper or resin material
Sex attractant lure, specifically can obtain in accordance with the following steps: be configured to by described pachydiplosis oryzae sex attractant with organic solvent
Solution, immerses described carrier in described solution, is taken out by described carrier, obtain 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 use
On the way:
(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 be monitored in time and accurately
With prediction pachydiplosis oryzae emergence period, generating capacity and distributed areas, and pest damage area and Control stage can be estimated.
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, is suitable to popularity and uses.
(2) mass trapping
Trap and kill male worm at deployment pachydiplosis oryzae sex attractant trap, cause female-male proportion numerous imbalances, reduce male and female
Mating behavior, reduce progeny population density, reduce harm.
(3) Insect pest suppression
Pachydiplosis oryzae sex attractant and the lure thereof of the present invention is discharged, at the environment of full female mosquito sex pheromone abnormal smells from the patient in field
In, 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 next
Decline for insect density.
Sex attractant and lure thereof that the application pheromone of the present invention is made can be used for pachydiplosis oryzae is carried out population monitoring
And integrated control, described sex attractant has low cost, efficiency height, is suitable to forecast and hides sending out the internal insect of insect gall
Raw rule.
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)-winestone
Diethyl phthalate 24.8g, and 16.8g tetra isopropyl titanium oxide, be slowly added dropwise 1.08mL water after being subsequently agitated for 10 minutes,
This system stirs 30min at 25 DEG C, is cooled to-20 DEG C subsequently, be slowly added to 4-aminomethyl phenyl methyl sulfide 8.3g and
Cumyl hydroperoxide 18.3g, continues to be stirred overnight, and period is incubated at-20 DEG C.After reaction terminates, add sulphuric acid sub-
Ferrous solution and citric acid solution cancellation reaction, merge organic facies, anhydrous MgSO after ether extraction (200mL × 3)4
It is dried, the crude product that decompression precipitation obtains, column chromatography purification obtains 7.02g compound 1.This product optical purity warp
HPLC analyzes, and optical purity is more than 99%.
2) synthesis of (S)-5-oxo-6-(to toluene sulfenyl) caproic acid (2)
Under nitrogen protection, add in the 500mL Shrek bottle being equipped with mechanical agitation, thermometer and reflux condensing tube
(R)-4-methylphenylmethyl sulfoxide, adds 20mL THF and LDA solution (23mmol) at-78 DEG C, rises subsequently
After temperature stirs 30min to-40 DEG C, after reaction system is cooled to-78 DEG C and is slowly added dropwise glutaric anhydride 1.25g, heating
System temperature is to-60 DEG C and stirs.React 2 hours and terminate to reaction, after adding a small amount of liquor alumini chloridi cancellation reaction,
The a small amount of repeatedly extractive reaction liquid of ethyl acetate, merges organic facies, anhydrous Na2SO4It is dried, after concentration, obtains colorless viscous
Shape liquid, is obtained 2.4g compound 2 by column chromatography purification.
3) synthesis of (S)-5-oxo-6-(to toluene sulfenyl) methyl caproate (3)
It is separately added into 100mL third in the 250mL four-hole bottle being equipped with mechanical agitation, thermometer and reflux condensing tube
Ketone, (S)-5-oxo-6-(to toluene sulfenyl) caproic acid 2.4g and 2g potassium carbonate, be slowly added dropwise 3.3g dimethyl sulfate subsequently
Ester, this system is then raising temperature to return stirring overnight.After reaction terminates, the crude product that decompression precipitation obtains, by post
Chromatogram purification obtains 2.5g compound 3.
4) synthesis of (S)-5-hydroxyl-6-(to toluene sulfenyl) methyl caproate (4)
Under room temperature, in 50mL Shrek flask add (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).Complete
After Biing, this system continues to be cooled to subzero 78 DEG C, adds the DIBAL solution of 10mL (1mol/L), reaction after stirring
3～4 hours terminate to reaction, and reactant liquor methanol (10mL) cancellation is reacted, and merges organic layer, and anhydrous magnesium sulfate is done
After dry, after concentrating under reduced pressure, obtain 2.4g compound 4 through silica gel chromatography.
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 being slowly added dropwise tert-butyl chloro-silicane (1.16g, 10mmol) subsequently, this system continues stirring
Overnight, after reaction terminates, add the saturated NH of 5mL4Cl aqueous solution cancellation is reacted, after ether extraction (40mL × 3)
Merge organic facies, anhydrous Na2SO4It is dried, the crude product that decompression precipitation obtains, direct plunges into next step reaction；Will
To crude product be dissolved in 20mL ethanol, be dividedly in some parts Raney's nickel compound, subsequently room temperature reaction subsequently, middle TLC
Monitoring raw material has converted rear (one hour), filters out the nickel of excess, merges organic layer, through silicagel column color after concentrating under reduced pressure
Spectrum purification obtains 1.8g compound 5.
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, add
The anhydrous tetrahydro furan of 20mL and chirality methyl are to toluene sulfoxide (1.56g), in batches to four after being cooled to-78 DEG C subsequently
Adding LDA solution (10.2mmol) in mouth bottle, start stirring 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 is extremely
Reaction terminates.Reacting 2～3 hours after extremely reacting completely, after adding a small amount of frozen water cancellation reaction, ether the most repeatedly extracts
Extract reaction solution, merge organic facies, anhydrous Na2SO4It is dried, after concentration, obtains colorless viscous shape liquid, pure by column chromatography
Change and 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) to 20mL anhydrous tetrahydro furan
In.Under stirring, add Zinc Bromide Anhydrous (2.48g, 11mmol).After this system continue to be cooled to-78 DEG C, stir
Adding the DIBAL solution of 10mL (1mol/L) after mixing, after reaction terminates, reactant liquor methanol (10mL) is quenched
Going out reaction, merge organic layer, anhydrous magnesium sulfate is dried, obtains 3.4gization through silica gel chromatography after concentrating under reduced pressure
Compound 7.
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 at room temperature continues to stir 3h, and after reaction terminates, decompression precipitation obtains
Crude product, direct plunge into next step reaction；The crude product obtained is dissolved in 20mL ethanol, is dividedly in some parts thunder subsequently
Buddhist nun's nickel compound, subsequently room temperature reaction, middle TLC monitoring raw material has converted rear (one hour), has filtered out excess
Nickel, merges organic layer, obtains 1.2g compound 8 through silica gel chromatography after concentrating under reduced pressure.
9) synthesis of (2S, 6S)-heptyl-2,6-diacetate esters
Under room temperature, 50mL single port flask adds compound 9 (0.65g, 5mol) in 10mL dichloromethane.
Under stirring, add chloroacetic chloride (392mg, 5mmol).React 12 hours and continue stirring to this system after completion of the reaction
Adding 2mL deionized water cancellation reaction after reacting 12 hours, reactant liquor dichloromethane (10mL × 5) extracts,
Merging organic layer, anhydrous magnesium sulfate is dried, obtains white solid 0.99g through silica gel chromatography after concentrating under reduced pressure,
Its mass spectrum is as shown in Figure 2, it is seen that m/z is the base peak of 43, and it is not with higher m/z 41 peak, it is contemplated that
It contains acetyl group, m/z 113 (C7H13O+) it is that molecular ion is left away an acetyl group and aceticoceptor, m/z96
(C7H12 +) it is that molecular ion sloughs bilateral acetyl group, m/z 81 (C6H9 +) it is that the continuation fracture of m/z 96 fragment loses
One methyl.
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, mix according to 10:1
Mixture 10 microgram be dissolved in normal hexane, be then added drop-wise on rubber stopper partition, until normal hexane volatilize after, dropping
200 microlitre dichloromethane, after dichloromethane volatilizees, close in the pachydiplosis oryzae sex attractant lure made is loaded aluminium foil
Seal standby.
On August 24,20 days to 20014 August in 2014 uses triangle viscose trapper, and trapper is by plastic made tile
Stupefied plate surrounds, and the 15cm that goes to the bottom, two length of sides are respectively the isosceles triangle of 20cm, and the paper scribbling insect sticker is placed in bottom
Plate.Lure is placed in the middle of trapper, away from glue surface about 2cm.Trapper arranges distance ground and rice plant height one
Cause, between trapper, be spaced 15m.Arrange the non-copulation of pachydiplosis oryzae to cross female mosquito trapper and (non-copulation is crossed female mosquito put simultaneously
Put in little sarong, be placed in the middle of trapper, distance glue surface about 2cm) and blank trapper.At each test
Reason 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 rice containing (2S, 6S)-2,6-diacetoxy heptane and (6S)-6-acetoxyl group-2-heptanone of the present invention
Gall midge sex attractant lure, is better than non-copulation in field to pachydiplosis oryzae hero mosquito attracting action and crosses female mosquito, have and preferably lure
Kill 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 the 20th, and bottom placement scribbles viscous
The cardboard of Lac.By (2S, 6S)-2,6-diacetoxy heptane (A) and (6S)-6-acetoxyl group-2-heptanone (B)
Two components are configured to lure, lure 1 (containing only component A), lure 2 (A:B=10:1), lure 3 by different proportion
(A:B=10:5).Lure is placed in the middle of trapper, away from glue surface about 2cm.Trapper arranges that distance ground is planted with Oryza sativa L.
Strain is highly consistent, 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 rice wart containing (2S, 6S)-2,6-diacetoxy heptane and (6S)-6-acetoxyl group-2-heptanone of the present invention
Mosquito sex attractant lure, can obtain preferable trapping effect, (2S, 6S)-2,6-when weight ratio is 10:1 and 10:5
Diacetoxy heptane is used alone also has certain trapping effect, but the male mosquito head number of trapping decreases, but remains to
Enough use as pachydiplosis oryzae sex attractant.
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) compound shown in formula 8 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；
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 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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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856021A (en) * | 2009-06-19 | 2010-10-13 | 中国农业大学 | Application of (2S,8Z)-2-butyryl acyloxy-8-heptadecene |
-
2016
- 2016-04-18 CN CN201610239781.9A patent/CN105801409A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856021A (en) * | 2009-06-19 | 2010-10-13 | 中国农业大学 | Application of (2S,8Z)-2-butyryl acyloxy-8-heptadecene |
Non-Patent Citations (5)
| Title |
|---|
| DAVID R.HALL, ET AL.: "The Chemical Ecology of Cecidomyiid Midges (Diptera:Cecidomyiidae", 《J CHEM ECOL》 * |
| GUY SOLLADIE AND NATHALIE HUSER: "Asymmetric synthesis of both enantiomers of 2.5-hexane diol and 2.6-heptane diol induced by chiral sulfoxides", 《TETRAHEDRON LETTERS》 * |
| GUY SOLLADIE, ET AL.: "Asymmetric synthesis of (S)-zearalenone dimethyl ether, an orsellinic acid type macrolide", 《J. ORG. CHEM.》 * |
| JEAN-MICHEL BRUNEL, ET AL.: "Highly Enantioselective Oxidation of Sulfides Mediated by a Chiral Titanium Complex", 《J. ORG. CHEM.》 * |
| 张月琴 等: "环糊精接枝聚硅氧烷气相色谱固定相的手性拆分性能", 《分析测试学报》 * |
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Application publication date: 20160727 |