CN105130843B - Benzyl hydrazone compounds and preparation method and application - Google Patents
Benzyl hydrazone compounds and preparation method and application Download PDFInfo
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- CN105130843B CN105130843B CN201510388316.7A CN201510388316A CN105130843B CN 105130843 B CN105130843 B CN 105130843B CN 201510388316 A CN201510388316 A CN 201510388316A CN 105130843 B CN105130843 B CN 105130843B
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- -1 Benzyl hydrazone compounds Chemical class 0.000 title claims description 41
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 93
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 23
- 239000003899 bactericide agent Substances 0.000 claims abstract description 18
- 239000002917 insecticide Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Polymers C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 239000007884 disintegrant Substances 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000004996 alkyl benzenes Chemical group 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 230000002528 anti-freeze Effects 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 230000000740 bleeding effect Effects 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000003209 petroleum derivative Substances 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 2
- 241000255789 Bombyx mori Species 0.000 claims description 2
- 229920005682 EO-PO block copolymer Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 235000013871 bee wax Nutrition 0.000 claims description 2
- 239000012166 beeswax Substances 0.000 claims description 2
- CUOZYXPNIFEQTK-UHFFFAOYSA-N benzenesulfonic acid;formaldehyde Chemical compound O=C.OS(=O)(=O)C1=CC=CC=C1 CUOZYXPNIFEQTK-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012241 calcium silicate Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 235000021003 saturated fats Nutrition 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- PYODKQIVQIVELM-UHFFFAOYSA-M sodium;2,3-bis(2-methylpropyl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CC(C)C)C(CC(C)C)=CC2=C1 PYODKQIVQIVELM-UHFFFAOYSA-M 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 1
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical group [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000000025 natural resin Substances 0.000 claims 1
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- 150000003459 sulfonic acid esters Chemical class 0.000 claims 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 21
- 201000010099 disease Diseases 0.000 abstract description 20
- 241000196324 Embryophyta Species 0.000 abstract description 8
- 241000221785 Erysiphales Species 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 6
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 abstract 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract 1
- 235000005822 corn Nutrition 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 230000001151 other effect Effects 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 72
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 41
- 238000005160 1H NMR spectroscopy Methods 0.000 description 41
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 12
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- 239000000463 material Substances 0.000 description 7
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- 238000004440 column chromatography Methods 0.000 description 6
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- 230000003449 preventive effect Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
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- 239000001390 capsicum minimum Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
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- 150000002367 halogens Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
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- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
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- 239000000243 solution Substances 0.000 description 3
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- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
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- OARJXUPBZNUYBG-UHFFFAOYSA-N 2,2-dimethylpropanehydrazide Chemical compound CC(C)(C)C(=O)NN OARJXUPBZNUYBG-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- DMAXMXPDVWTIRV-UHFFFAOYSA-N 2-(2-phenylethyl)phenol Chemical compound OC1=CC=CC=C1CCC1=CC=CC=C1 DMAXMXPDVWTIRV-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- AULWPXHFRBLPAE-UHFFFAOYSA-N 6-chloropyridine Chemical compound ClC1=C=CC=C[N]1 AULWPXHFRBLPAE-UHFFFAOYSA-N 0.000 description 1
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 208000015220 Febrile disease Diseases 0.000 description 1
- 239000005784 Fluoxastrobin Substances 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 235000011430 Malus pumila Nutrition 0.000 description 1
- 235000015103 Malus silvestris Nutrition 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000233622 Phytophthora infestans Species 0.000 description 1
- 241000221696 Sclerotinia sclerotiorum Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- JSCQSBGXKRTPHZ-WMSPMLHYSA-N Strobilurin A Natural products COC=C(/C(=C/C=C/c1ccccc1)/C)C(=O)OC JSCQSBGXKRTPHZ-WMSPMLHYSA-N 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- OWIUPIRUAQMTTK-UHFFFAOYSA-N carbazic acid Chemical compound NNC(O)=O OWIUPIRUAQMTTK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical class C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000009266 disease activity Effects 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229940035423 ethyl ether Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- UFEODZBUAFNAEU-NLRVBDNBSA-N fluoxastrobin Chemical compound C=1C=CC=C(OC=2C(=C(OC=3C(=CC=CC=3)Cl)N=CN=2)F)C=1C(=N/OC)\C1=NOCCO1 UFEODZBUAFNAEU-NLRVBDNBSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940084434 fungoid Drugs 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- KAJNDAVRWHCCQS-UHFFFAOYSA-N methyl 2-methoxyimino-2-phenylacetate Chemical class CON=C(C(=O)OC)C1=CC=CC=C1 KAJNDAVRWHCCQS-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JSCQSBGXKRTPHZ-SYKZHUKTSA-N mucidin Chemical compound CO\C=C(\C(=O)OC)/C(/C)=C\C=C\C1=CC=CC=C1 JSCQSBGXKRTPHZ-SYKZHUKTSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- XUODUUUOIPQCOS-UHFFFAOYSA-N n-hydrazinylformamide Chemical compound NNNC=O XUODUUUOIPQCOS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003583 thiosemicarbazides Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses compound and preparation method and application shown in a kind of Formulas I.In the Formulas I, each substituent is defined in the specification.Preparation method comprises the following steps：In the presence of a catalyst, compound shown in compound shown in formula IV and Formula V is subjected to condensation reaction in organic solvent, obtain compound shown in Formulas I, the preparation method is simple, compound shown in gained Formulas I can be used for preventing and treating in various plants by a variety of germ diseases such as oomycetes, basidiomycetes, sac fungus and Fungi Imperfecti, to wheat powdery mildew, corn rust, watermelon anthrax and other effects it is further preferred that, good prevention effect can be obtained at low concentrations.The part of compounds in compound shown in Formulas I also has good desinsection and acaricidal activity simultaneously, available for the insect and mite prevented and treated in various crop.Therefore can be used as bactericide or insecticide in agriculture and other fields.
Description
Technical field
The invention belongs to the preparation of disinfectant use in agriculture and insecticide and application field, and in particular to a kind of benzyl hydrazone class chemical combination
Thing and preparation method and application.
Background technology
Methoxy acrylic bactericide is derived from one of the natural antibiotics Strobilurin A with bactericidal activity
The remarkable disinfectant use in agriculture of class effect, the series bactericidal agent wide spectrum, efficiently is all shown well to nearly all fungus disease
Activity, important protective effect is served to agricultural production.
Structure of modification on methoxy acrylic ester compounds is very more, these many changes on side chain of transformation,
But structure only has three kinds of two aryl oxide classes, benzyl oxide class and benzaldoxime ethers, structure type and it is of limited application, meanwhile, such chemical combination
Thing also gradually produces serious resistance problem as bactericide.
The content of the invention
It is an object of the invention to provide a kind of benzyl hydrazone compounds and preparation method thereof.
The general structure of benzyl hydrazone compounds provided by the present invention is shown in formula I：
In the Formulas I, X is selected from CH or N；Y is selected from any of O, S and NH；R1Selected from C1-C8Alkyl, pi-allyl,
Propargyl, benzyl, benzoyl, C1-C5Fatty acyl group, C1-C5Alkoxy carbonyl group, cyano group, carbamoyl and sulfo-amino first
Any of acyl group；R2Selected from C1-C12Alkyl, Q1And Q2Any of；R3Selected from hydrogen, C1-C5Alkyl, Q1And Q2In
It is any；
Wherein, the Q1And Q2In, R4And R5It is selected from hydrogen, C1-C5Alkyl, C1-C5Alkoxy, C1-C5Fluoroalkane
Base, C1-C5Fluoroalkyl, halogen, nitro, cyano group, phenoxy group, pyridine epoxide, mesyl and trifyl in
At least one, the halogen is selected from any of fluorine, chlorine, bromine and iodine；M=0-5；N=0-4.
R4Binding site be remaining 5 binding sites at least one, wherein, work as m>When 1, R4Can be identical or not
Together；R5Binding site be at least one in remaining 4 binding sites, wherein, work as n>When 1, R5It may be the same or different, wherein,
Q2In, N can be located at 2, any place in 3 and 4.
The general structure of benzyl hydrazone compounds provided by the present invention shown in formula I, preferably following structure：
In the Formulas I, X is selected from CH or N；Y is selected from O or NH；R1Selected from C1~C4Straight or branched alkoxy carbonyl group, benzene first
Any of acyl group, cyano group, carbamoyl and thiocarbamoyl；R2Selected from Q1Or Q2；R3Selected from hydrogen or C1-C2Alkane
Base；
Wherein, the Q1And Q2In, R4And R5It is selected from C1-C5Alkyl, trifluoromethyl, trifluoromethoxy, phenoxy group, halogen
At least one of element, nitro, cyano group, pyridine epoxide, mesyl and trifyl；M=0-3；N=0-2.
The general structure of benzyl hydrazone compounds provided by the present invention shown in formula I, more preferably following structure：
In the Formulas I, X is selected from CH or N；Y is selected from O or NH；R1Selected from C1~C4Straight or branched alkoxy carbonyl group, cyano group；
R2Selected from Q1Or Q2；R3Selected from hydrogen or methyl；
Wherein, the Q1And Q2In, R4And R5It is selected from trifluoromethyl, trifluoromethoxy, phenoxy group, fluorine, chlorine, nitro, cyanogen
At least one of base, pyridine epoxide, mesyl and trifyl；M=0-3, n=0-2.
Involved term represents following substituent in the definition of the described compound of formula I of the present invention：
Halogen：Refer to fluorine, chlorine, bromine, iodine.
Alkyl：Straight or branched alkyl, for example：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth
Base, tertiary pentyl.
Aryl moiety in aryl and aryloxy group includes phenyl, pyridine radicals, furyl etc..
In addition, in compound of formula I of the present invention, the shape because of carbon-to-carbon double bond or carbon-to-nitrogen double bond connection different substituents
Into geometric isomer (different configurations is represented with Z and E respectively).Compound of formula I of the present invention can be Z-type isomers,
Also can be the mixture of E-isomer, or both any ratio.
The described compound of formula I of the present invention specifically may be selected from the compound numbered as follows：
Note：With (R in upper table5)nN in connected pyridine ring can be located at 2,3 or 4.
The preparation method of benzyl hydrazone compounds (compound shown in Formulas I) provided by the present invention, comprises the following steps：
In the presence of catalyst, compound shown in compound shown in formula IV and Formula V is subjected to condensation reaction in organic solvent, Formulas I is obtained
Shown compound.
In the formula IV, R1、R1And R3The same Formulas I of definition；In the Formula V, X and the Y same Formulas I of definition.
In above-mentioned preparation method, the catalyst is alkali, and the alkali is selected from sodium hydride, Sodamide, lithium amide, diisopropyl
At least one of lithium amide, n-BuLi and phenyl lithium.
The mol ratio of compound shown in the catalyst and formula IV is 1:(1.2~3).
The reaction temperature of the condensation reaction be -5~100 DEG C, preferably 10~50 DEG C, concretely 25 DEG C, during reaction
Between be 2-12h, concretely 4-9h.
The mol ratio of compound shown in compound shown in the formula IV and Formula V is 1：(1-2), concretely 1：(1-1.3).
The organic solvent is selected from N,N-dimethylformamide (DMF), 1-METHYLPYRROLIDONE and glycol dimethyl ether
At least one.
The condensation reaction is preferably carried out as follows：By compound shown in catalyst and formula IV in organic solvent
In, in stirring 0.5-2h at -10-5 DEG C, then compound shown in Formula V is added thereto, in reacting 2-12h at -5~100 DEG C, obtain
Compound shown in Formulas I.
In above-mentioned preparation method, compound shown in formula IV is prepared as follows obtaining：By compound shown in Formula II and formula
Compound is reacted in organic solvent shown in III, obtains compound shown in formula IV,
In the Formula II, R1The same Formulas I of definition；In the formula III, R2And R3The same Formulas I of definition.
Wherein, the mol ratio of compound shown in compound shown in II and formula III is 1：(1-2), concretely 1:1.
The reaction temperature of the reaction is -20~50 DEG C, and the reaction time is 1-6h.
The organic solvent is methanol or ethanol.
The Formula II, formula III and compound shown in Formula V can be bought by commercial sources, such as：Compound shown in Formula II has
Body can be alkyl hydrazine, aryl hydrazines, acid hydrazide, alkoxy carbonyl group hydrazine, semicarbazides, thiosemicarbazides or cyano group hydrazine etc.
It is also another object of the present invention to provide a kind of bactericide and/or insecticides and preparation method thereof, the group
Compound includes benzyl hydrazone compounds (compound shown in Formulas I) and agriculturally acceptable carrier, wherein, benzyl in said composition
The weight percentage of hydrazone compounds (active component) is 0.1~99%, concretely 30~60%.
The preparation method of bactericide and/or insecticides provided by the present invention, comprises the following steps：By benzyl hydrazone
Class compound (compound shown in Formulas I) and agriculturally acceptable carrier mixing can be prepared.
The benzyl hydrazone compounds may be either the single compound of the present invention, or several compounds of the invention is mixed
Compound.
The agriculturally acceptable carrier has following features：1) it is easy to be applied to after preparing with active component pending
Site, for example：Plant, seed or soil；2) be conducive to storing, transport or operating；3) it is solid or liquid that can be, including is led to
Often for gas but the material of liquid has been compressed into it.In a word, the carrier commonly used in agriculturally desinsection used, bactericidal composition is prepared
It can be used.
The agriculturally acceptable carrier specifically may be selected from solid carrier and/or liquid-carrier.
The solid carrier is selected from natural or synthetic silicate, ammonium sulfate, calcium sulfate, oxidation alumina silicate, natural or conjunction
Into at least one of resin, polystream phenol, starch, bentonite and wax, wherein, the natural or synthetic silicate is specific
It may be selected from least one of Attagel, talcum, alumina silicate, diatomite, mica, montmorillonite and calcium silicates, described natural or conjunction
Into resin specifically may be selected from cumarone resin, styrene polymer (molecular weight be 5-20 ten thousand) and styrol copolymer is (such as：
At least one of SB)；The wax specifically may be selected from beeswax and/or paraffin.
The liquid-carrier is selected from water, C1-C4Alcohol, C3-C8Ketone, aromatic hydrocarbons, petroleum distillate and C6-C12Chlorohydrocarbon in
At least one, wherein, the alcohol concretely ethanol and/or ethylene glycol, the ketone concretely acetophenone, acetone, first and second
At least one of ketone and cyclohexanone, the aromatic hydrocarbons concretely at least one of benzene, toluene and dimethylbenzene, the oil evaporate
Point concretely kerosene and/or mineral oil, the chlorohydrocarbon concretely in carbon tetrachloride, dichloromethane and trichloroethanes extremely
Few one kind.
General bactericide and/or insecticides would generally be processed to the form of concentrate, and with this for transporting,
Diluted before administration by user.
In order to which beneficial to dilution, bactericide and/or insecticides provided by the present invention may also include surface-active
Agent.
The addition of the surfactant is agriculturally with acceptable amount in bactericide and/or insecticide.
The surfactant is selected from least one of emulsifying agent, dispersant, wetting agent and bleeding agent.
The emulsifying agent specifically may be selected from agriculture breast 500# (alkylbenzene calcium sulfonate), agriculture breast 600# phosphate (phenyl phenol polyoxies
Ethylether), Nongru-700 # (alkylphenol-formaldehyde resin polyoxyethyl ether), agriculture breast 1600# (phenethyl phenol polyoxyethanyl polypropylene-bases
Ether), at least one of polyoxyalkylenes alkyl aryl ether and ethylene oxide-propylene oxide block copolymer.
The dispersant specifically may be selected from polycarboxylate, lignosulfonates, alkylphenol-polyethenoxy formaldehyde condensation products sulphur
Hydrochlorate, alkyl benzene sulfonate calcium salt, benzene sulfonic acid formaldehyde condensation products sodium salt, sodium lauryl sulfate, sulfonated castor oil sodium salt, sulfonic alkyl
Aryl ester sodium, alkylphenol-polyethenoxy is phonetic, polyoxyethylene carboxylate and ester polyoxyethylene are at least one of phonetic.
The wetting agent specifically may be selected from lauryl sodium sulfate, neopelex, Nekal BX, spaonin powder,
At least one of silkworm excrement and spaonin powder.
The bleeding agent specifically may be selected from polysiloxane polyoxyethylene ether, sulfonic alkyl aromatic ester, alcohol ether succinate and phenolic ether
At least one of succinate.
Certainly, in bactericide and/or insecticides of the present invention, other auxiliary agents can be also properly added.
The addition of other auxiliary agents is agriculturally with acceptable amount in bactericide and/or insecticide.
Other described auxiliary agents may be selected from least one of disintegrant, defoamer, antifreeze and thickener.
The disintegrant is selected from least one of bentonite, urea, ammonium sulfate, aluminium chloride and glucose.
The defoamer is selected from silicone oil, silicone compound, C10-C20 saturated fat acids compound, C8-C10 fat
At least one of alcohol compound.
The antifreeze is selected from least one of ethylene glycol, propane diols, glycerine and polyethylene glycol.
The thickener is selected from least one of xanthan gum, polyvinyl alcohol and polyethylene glycol.
, can be public according to those skilled in the art institute in the preparation-obtained bactericide of the present invention and/or insecticides
The method known, adds corresponding composition, so that wettable powder, pulvis, granule, emulsifiable concentrate, missible oil are prepared, suspending agent,
A variety of formulations such as aerosol or smoke agent.
Meanwhile, the bactericide and/or insecticide composition of the invention of effective dose can be applied according to different crops and disease
Thing, can be implemented with the method for foliar spray, seed treatment or soil treatment.
In some aspects, one or more other kill can be added in the bactericide and/or insecticides of the present invention
Microbial inoculum, makes it produce additional advantage and effect；Also can be by compound shown in Formulas I and other bactericide and/or Mixture Use of Insecticides.
In addition, compound and combinations thereof shown in Formulas I provided by the present invention is preparing bactericide and/or insecticide
In application fall within protection scope of the present invention.
Compound shown in the Formulas I of the present invention has a wide spectrum and excellent bactericidal activity, available for preventing and treating in various crop
By four Mycophytes pathogenic greatly：Sac fungus, basidiomycetes, Fungi Imperfecti and disease caused by oomycetes diseases.Under very low dosage i.e.
Good prevention effect can be obtained.Meanwhile, compound shown in such Formulas I has certain absorbability and can be used as blade face and soil
Bactericide, prevents and treats the disease in various crop.Following disease can specifically be prevented：Capsicum epidemic disease, early blight of tomato, Phytophthora infestans
Disease, rice blast, speckled leaf blotch, ring rot of apple, rice sheath blight disease, rice blast, rice green smut, rice bakanae disease
Disease, wheat powdery mildew, sclerotinia sclerotiorum, cucumber downy mildew, cucumber fusarium axysporum, gray mold of cucumber, powdery mildew of cucumber or apple are white
Powder disease.
In addition, compound also has preferable desinsection and acaricidal activity shown in the segment boundses I of the present invention, such as：Ia-84、Id-
397th, Ih-259 etc., available for preventing and treating insect and mite in various crop.
The side chain that the present invention prepares benzyl hydrazone compounds is benzyl hydrazone structure, the benzyl hydrazone compounds and containing it
Composition can prevent and treat plant (such as under low dose：Crops：Capsicum, tomato, paddy rice, wheat, apple, rape and cucumber
Deng) harmful fungoid and insect are (such as：Mythimna separata, diamondback moth, black peach aphid and Tetranychus cinnabarinus etc.), the sterilization excellent with wide spectrum and desinsection
Effect.
Brief description of the drawings
Fig. 1 is the preparation flow figure of compound shown in Formulas I.
Embodiment
The method of the present invention is illustrated below by specific embodiment, but the invention is not limited in this.
Experimental method described in following embodiments, is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, commercially obtain.
First, the preparation embodiment of compound shown in Formulas I is as follows：Corresponding preparation flow figure is as shown in Figure 1：
Embodiment 1, prepare compound Ia-4：
Added in 100mL there-necked flasks and contain 0.93g (6.9mmol) 1- benzylidene -2- methyl hydrazines (1-
Benzylidene-2-methylhydrazine DMF solution 15mL), is cooled to less than 5 DEG C, adds 0.53g (12mmol) matter
Amount fraction is 70%NaH oil dispersed granulas, is stirred after 1h, adds (E) -2- (2- bromomethyls) phenyl -2- methoxyimino acetic acid
Methyl esters 2.35g (8.2mmol), is warming up to (25 DEG C) of room temperature and continues to react 8h.Add water and be quenched, there is gray solid precipitation, column chromatography
Obtain white powder 2.2g, yield 82%, 78-80 DEG C of fusing point.
1H NMR(300MHz,CDCl3) δ, 2.93 (s, 3H), 3.04 (s, 3H), 3.75 (s, 3H), 3.81 (s, 3H), 3.85
(s,2H),7.22-7.95(m,9H),8.11(s,1H).
13C NMR(75MHz,CDCl3)δ23.0,44.2,50.6,59.1,60.2,104.6,126.2,126.8,127.4,
128.2,128.6,128.9,130.8,133.0,137.5,158.4,164.0,168.5.
Numbering Ia-1~Ia-14 to Id-1~Id-14 compound is prepared by the method in embodiment 1.
Wherein, compound Ia-11：Pale powder, yield is 77%, 77-79 DEG C of fusing point,1H NMR and13C NMR are such as
Under：
1H NMR(300MHz,CDCl3)δ1.23(S,9H),2.95(s,3H),3.77(S,3H),3.80(s,3H),3.81
(s,2H),7.21-7.89(m,9H),8.13(s,1H).
13C NMR(75MHz,CDCl3)δ17.7,28.1,52.5,52.8,60.0,77.2,104.6,126.2,126.8,
127.4,128.4,128.8,128.9,130.5,131.1,133.6,137.2,158.4,164.0,168.8。
Compound Ib-11：White powder, 102-104 DEG C of fusing point, yield is 82%,1H NMR and13C NMR are as follows：
1H NMR(300MHz,CDCl3)δ1.27(s,9H),2.73(s,3H),2.95(s,3H),3.80(s,3H),3.81
(s,2H),7.21-7.95(m,9H),8.01(s,1H).
13C NMR(75MHz,CDCl3)δ17.5,26.3,28.7,51.4,59.8,77.6,104.1,126.1,126.8,
127.9,128.0,128.8,128.9,130.7,131.2,133.4,137.6,158.4,168.2,172.5。
Compound Ic-11：Pale yellow powder, 86-88 DEG C of fusing point, yield is 73%,1H NMR and13C NMR are as follows：
1H NMR(300MHz,CDCl3)δ1.28(s,9H),2.97(s,3H),3.72(s,3H),3.80(s,2H),3.96
(s,3H),7.24-7.96(m,9H)；
13C NMR(75MHz,CDCl3)δ17.3,28.3,52.5,52.7,64.3,77.4,123.0,125.3,127.1,
128.2,128.8,130.8,131.0,131.1,131.7,137.5,149.7,163.7,168.8。
Compound Id-11：White powder, 108-110 DEG C of fusing point, yield is 89%,1H NMR and13C NMR are as follows：
1H NMR(300MHz,CDCl3)δ1.32(s,9H),2.66(s,3H),2.98(s,3H),3.82(s,2H),3.96
(s,3H),7.50-7.93(m,9H)；
13C NMR(75MHz,CDCl3)δ17.8,26.2,28.6,64.4,77.5,123.7,125.0,127.4,128.2,
128.6,130.8,131.2,131.4,131.9,137.1,151.7,164.2,168.8。
Embodiment 2：Prepare compound Ic-109：
In 100ml there-necked flasks add 2- (1- (4- chlorphenyls) ethylidene) diazanyl carboxylic acid, ethyl ester (0.5g,
0.0021mol), DMF 15mL, are cooled to less than 5 DEG C, addition 0.13g (0.00315mol) mass fraction is 70%NaH oils
Shot agent, stirs 1h, rear to add (E) -2- (2- bromomethyls) phenyl -2- methoxyimino methyl acetates 0.72g
(0.0025mol), is warming up to (25 DEG C) of room temperature and continues to react 9h, add water and be quenched, there is solid precipitation, column chromatography obtains faint yellow solid
0.71g, yield 77%, 123-125 DEG C of fusing point,1H NMR and13C NMR are as follows：
1H NMR (300MHz, DMSO) δ 7.80 (d, J=8.6Hz, 2H), 7.50 (d, J=8.6Hz, 2H), 7.39~
7.34 (m, 3H), 7.16~7.15 (m, 1H), 4.62 (s, 2H), 4.08 (q, J=7.0Hz, 2H), 3.93 (s, 3H), 3.66
(s, 3H), 1.99 (s, 3H), 1.17 (t, J=7.1Hz, 3H)
13C NMR(75MHz,DMSO)δ169.65,162.93,152.44,148.94,135.86,135.80,135.61,
130.08,129.42,128.88,128.71,128.65,127.38,63.52,61.89,52.65,52.20,40.62,
40.34,40.07,39.79,39.51,39.23,38.95,16.82,14.56.
Numbering Ia-15~Ia-264 to Id-15~Id-264, Ie-1~Ie-240 to Ih-1~Ih-240 compound is equal
Prepared by the method in embodiment 2.
Wherein, compound Ic-228：White powder, 126-128 DEG C of fusing point, yield is 70%,1H NMR and13C NMR are such as
Under：
1H NMR (300MHz, DMSO) δ 8.26 (d, J=9.1Hz, 2H), 8.01 (d, J=9.1Hz, 2H), 7.42-7.26
(m,3H),7.14(m,1H),4.64(s,2H),3.93(s,3H),3.66(s,3H),2.04(s,3H),1.39(s,9H).
13C NMR(75MHz,DMSO)δ168.25,162.95,151.06,148.96,148.65,143.16,135.95,
130.09,129.37,128.88,128.72,128.27,127.37,123.72,81.12,63.55,52.67,27.99,
17.35.
Compound Ic-259：White solid, 149-151 DEG C of fusing point, yield is 79%,1H NMR and13C NMR are as follows：
1H NMR(300MHz,CDCl3) δ 8.38-8.30 (m, 1H), 8.14~8.12 (m, 1H), 8.02~7.99 (m,
1H), 7.53~7.50 (m, 2H), 7.42-7.29 (m, 2H), 7.17~7.13 (m, 2H), 4.99 (s, 2H), 4.14 (s, 3H),
3.96(s,3H),1.62(s,9H).
13C NMR(75MHz,DMSO)δ163.07,152.96,148.75,148.39,138.12,136.76,133.58,
132.69,130.62,129.93,129.51,128.84,127.47,125.78,123.82,120.84,81.92,63.77,
52.97,45.88,28.02.
Compound If-222：White solid, 162-164 DEG C of fusing point, yield is 76%,1H NMR and13C NMR are as follows：
1H NMR(300MHz,CDCl3)δ1.38(s,9H),2.95(s,3H),3.68(s,3H),3.93(s,3H),6.10
(s,2H),7.10-7.71(m,5H),8.54(d,1H),9.04(d,1H)；
13C NMR(75MHz,DMSO)δ17.3,28.5,51.4,52.8,64.1,84.4,121.5,124.3,125.0,
125.2,126.8,130.0,130.6,136.9,139.1,149.7,152.4,153.4,154.7,163.5,168.8.
Embodiment 3, prepare compound If-283：
(0.5g, 2.3mmol) 2- ((6- chloropyridine -3- bases) methylene) -1- itrile group hydrazines are added in 100ml there-necked flasks,
DMF15mL, is cooled to less than 5 DEG C, addition 0.12g (3.3mmol) mass fraction is 70%NaH oil dispersed granulas, is stirred after 1h
0.79g (2.8mmol) (E) -2- (2- bromomethyls) phenyl -2- methoxyimino methyl acetates are added, room temperature (25 DEG C) is warming up to
Continue to react 5h.Add water and be quenched, there is solid precipitation, column chromatography purifies to obtain yellow powder 0.73g, yield 80%, fusing point 170-172
DEG C,1H NMR and13C NMR are as follows：
1H NMR (300MHz, DMSO) δ 8.69 (d, J=1.9Hz, 1H), 8.12 (dd, J=8.4,2.6Hz, 1H), 7.60
(d, J=8.5Hz, 1H), 7.50-40 (m, 3H), 7.26-7.21 (m, 1H), 4.60 (s, 2H), 3.94 (s, 3H), 3.70 (s,
3H),2.38(s,3H).
13C NMR(75MHz,DMSO)δ162.86,162.06,152.22,148.84,148.43,137.94,132.94,
131.80,130.82,130.23,129.73,129.20,128.65,124.39,112.95,63.72,58.31,52.86,
15.96.
Numbering Ia-265~Ia-330 to Id-265~Id-330, Ie-241~Ie-301 to Ih-241~Ih-301 change
Compound is prepared by the method in embodiment 3.
Wherein, compound Ic-296：White solid, 156-158 DEG C of fusing point, yield is 71%,1H NMR and13C NMR are such as
Under：
1H NMR(300MHz,DMSO)δ7.71-7.58(m,2H),7.54-7.35(m,,6H),7.31–7.14(m,1H),
4.57(s,2H),3.94(s,3H),3.70(s,3H),2.35(s,3H).
13C NMR(75MHz,DMSO)δ165.61,162.85,148.87,136.54,133.09,130.94,130.83,
130.17,129.68,129.19,128.74,128.56,127.03,113.53,63.70,58.18,52.82,16.22.
Compound Ic-315：White solid, 172-174 DEG C of fusing point, yield is 73%,1H NMR and13C NMR are as follows：
1H NMR (300MHz, DMSO) δ 7.91 (d, J=8.3Hz, 2H), 7.80 (d, J=8.3Hz, 2H), 7.55~
(s, the 3H) of 7.49 (m, 3H), 7.29~7.26 (m, 1H), 4.62 (s, 2H), 3.94 (s, 3H), 3.70 (s, 3H), 2.40
13C NMR(75MHz,DMSO)δ163.73,162.85,148.85,140.46,132.96,130.94,130.81,
130.52,130.15,129.71,129.22,128.62,127.85,126.00,125.67,125.62,122.39,112.97,
63.70,58.38,52.65,16.33.
Embodiment 4, prepare compound Ic-361：
The DMF containing 0.41g (2.3mmol) 2- (1- phenyl-ethylenes) diazanyl formamide is added in 100mL there-necked flasks
Solution 15mL, is cooled to less than 5 DEG C, addition 0.12g (3.3mmol) mass fraction is 70%NaH oil dispersed granulas, is stirred after 1h
0.79g (2.8mmol) (E) -2- (2- bromomethyls) phenyl -2- methoxyimino methyl acetates are added, room temperature (25 DEG C) is warming up to
Continue to react 4h.Add water and be quenched, there is a solid precipitation, column chromatography purifies to obtain white powder, yield 65%, 184-186 DEG C of fusing point,1H
NMR and13C NMR are as follows：
1H NMR(300MHz,DMSO)δ2.93(s,3H),3.62(s,3H),3.95(s,3H),5.92(s,2H),7.12-
7.86(m,9H),8.11(bs,2H)；
13C NMR(75MHz,DMSO)δ19.3,51.2,52.8,64.4,122.7,125.6,126.8,128.0,129.0,
130.5,130.8,131.1,136.9,137.4,149.0,155.2,163.3,170.0.
Numbering Ia-331~Ia-394 to Id-331~Id-394, Ie-302~Ie-362 to Ih-302~IH-362 change
Compound is prepared by the method in embodiment 4.
Wherein compound Ia-336：White solid, yield 74%, mp 207-209 DEG C,1H NMR and13C NMR are as follows：
1H NMR(300MHz,DMSO)δ3.23(s,3H),3.76(s,3H),6.31(s,2H),7.18-7.75(m,
10H),8.41(bs,1H)；
13C NMR(75MHz,DMSO)δ49.5,50.6,59.1,104.7,125.6,126.5,127.7,128.2,
129.1,129.8,130.0,130.6,133.5,134.6,143.5,155.4,158.2,164.7.
Compound Ie-331：White solid, yield 56%, mp 241-243 DEG C,1H NMR and13C NMR are as follows：
1H NMR(300MHz,DMSO)δ3.36(s,3H),3.62(s,3H),3.77(s,3H),6.34(s,2H),7.03
(s,1H),7.21-7.74(m,9H),8.49(s,1H)；
13C NMR(75MHz,DMSO)δ49.4,50.3,54.1,59.5,104.2,115.6,116.2,126.2,126.6,
127.7,129.9,134.1,134.6,140.5,146.9,155.3,157.1,158.3,164.5.
Embodiment 5, prepare compound Ic-400：
Added in 100mL there-necked flasks and contain 0.64g (2.3mmol) 2- (1- (4- chlorphenyls) ethylidene) thio first of diazanyl
The DMF 15mL of acid amides, are cooled to less than 5 DEG C, addition 0.12g (3.3mmol) mass fraction is 70%NaH oil dispersed granulas, is stirred
Addition 0.79g (2.8mmol) (E) -2- (2- bromomethyls) phenyl -2- methoxyimino methyl acetates after 1h are mixed, room temperature is warming up to
(25 DEG C) are continued to react 4h.Add water and be quenched, there is white solid precipitation, column chromatography obtains white powder, yield 72%, fusing point 178-
180 DEG C,1H NMR and13C NMR are as follows：
1H NMR(300MHz,DMSO)δ2.90(s,3H),3.58(s,3H),3.63(s,3H),5.69(s,2H),7.21-
7.86(m,8H),8.01(bs,2H)；
13C NMR(75MHz,DMSO)δ20.3,52.0,56.4,64.0,121.4,125.3,126.5,128.1,128.8,
130.0,130.7,135.4,136.8,136.9,149.2,163.6,170.1,176.6.
Numbering Ia-395~Ia-402 to Id-395~Id-402 compound is prepared into by the method in embodiment 5
Arrive.
Wherein compound Ia-400：White solid, yield 70%, mp 211-213 DEG C,1H NMR and13C NMR are as follows：
1H NMR(300MHz,DMSO)δ2.95(s,3H),3.53(s,3H),3.72(s,3H),5.60(s,2H),7.12
(s,1H),7.20-7.94(m,8H),8.41(bs,2H)；
13C NMR(75MHz,DMSO)δ21.1,50.7,57.2,59.6,105.0,126.0,126.4,127.3,128.2,
128.9,129.9,132.5,134.1,135.6,136.6,158.4,164.3,170.0,176.2.
Compound Ic-397：White solid, yield 64%, mp 257-259 DEG C,1H NMR and13C NMR are as follows：
1H NMR(300MHz,DMSO)δ3.64(s,3H),4.00(s,3H),5.85(s,2H),7.23-8.62(m,
11H).
13C NMR(75MHz,DMSO)δ50.7,56.6,64.3,121.5,123.7,124.0,124.9,126.0,
129.6,131.1,136.3,139.3,146.2,149.7,150.0,163.5,176.0.
Embodiment 6, prepare compound Ic-404：
Added in 100ml there-necked flasks and contain 0.58g (2.3mmol) N'- (1- (4- chlorphenyls) ethylidene) pivaloyl hydrazine
MF 15mL, be cooled to less than 5 DEG C, addition 0.12g (3.3mmol) mass fraction is 70%NaH oil dispersed granulas, stirs 1h
0.79g (2.8mmol) (E) -2- (2- bromomethyls) phenyl -2- methoxyimino methyl acetates are added afterwards, are warming up to room temperature (25
DEG C) continue to react 4h.Add water and be quenched, there is white solid precipitation, column chromatography obtains white powder, yield 46%, fusing point 148-150
DEG C,1H NMR and13C NMR are as follows：
1H NMR(300MHz,CDCl3)δ1.24(s,9H),2.90(s,3H),3.65(s,3H),3.88(s,3H),6.04
(s,2H),7.20-7.88(m,8H)；
13C NMR(75MHz,CDCl3)δ20.0,28.6,39.5,50.7,52.7,64.3,122.0,125.3,126.8,
128.2,128.9,130.1,130.8,135.6,136.6,136.9,149.7,163.7,170.1,183.0.
Numbering Ia-403~Ia-405 to Id-403~Id-405 compound is prepared into by the method in embodiment 6
Arrive.
Wherein compound Ic-403：White solid, yield 78%, mp 195-197 DEG C,1H NMR and13C NMR are as follows：
1H NMR(300MHz,CDCl3)δ2.16(s,3H),2.91(s,3H),3.66(s,3H),3.92(s,3H),6.14
(s,2H),7.21-7.954(m,9H).
13C NMR(75MHz,CDCl3)δ20.0,24.6,49.4,52.8,64.5,120.9,125.2,126.5,128.0,
128.4,130.0,130.7,130.9,136.3,136.9,149.1,163.0,168.2,170.3.
Compound Id-403：White solid, yield 68%, mp 207-209 DEG C,1H NMR and13C NMR are as follows：
1H NMR(300MHz,CDCl3)δ2.14(s,3H),2.77(s,3H),3.00(s,3H),3.92(s,3H),6.19
(s,2H),7.28-8.06(m,10H).
13C NMR(75MHz,CDCl3)δ20.2,24.9,26.0,49.8,63.8,120.6,125.0,126.1,128.2,
128.7,130.5,131.1,132.8,136.3,137.2,151.4,163.6,168.7,170.3.
2nd, the embodiment of the composition comprising compound shown in Formulas I is as follows：(following each component is with weight percentage
Meter, active component folding hundred is post-dised)
Embodiment 7, wettable powder of the preparation containing compound shown in 50% Formulas I：
The composition of wettable powder：Compound 50% shown in Formulas I, dispersant polycarboxylate 5%, wetting agent dodecyl sulphur
Sour sodium 3%, solid carrier or disintegrant bentonite 42%；Each component is mixed to get mixture in the ratio, it is carried out
Air-flow crushing, you can 50% wettable powder is made.
Embodiment 8, missible oil of the preparation containing compound shown in 30% Formulas I：
The composition of missible oil：Compound 30% shown in Formulas I, emulsifying agent polyoxyalkylenes alkyl aryl ether 12%, bleeding agent sulphur
Dialkylaminobenzoic acid aromatic ester 10%, liquid-carrier cyclohexanone 48%；Each component is mixed to get the transparent of 30% compound in the ratio
Solution.
Embodiment 9, water dispersible granules of the preparation containing 60% compound of formula I：
The composition of water dispersible granules：Compound 70% shown in Formulas I, dispersant alkyl benzene sulfonate calcium salt 3%, dispersant are wooden
Plain sulfonate 3%, wetting agent lauryl sodium sulfate 4%, solid carrier or filler starch 20%；By each component in the ratio
It is mixed to prepare the water dispersible granules of 70% compound of formula I.
3rd, biological activity determination：
Embodiment 10, bactericidal activity are determined：
The various fungus diseases of plant are tested with formula I, test method is as follows：
Using the potted plant assay method of live body：Compound of formula I active compound (i.e. pure compound of formula I) to be measured is used into a small amount of N, N-
Dimethylformamide dissolves, and is diluted with water to required scale, is related to experimental group and control group：Experimental group is spray pesticide to plant
Try on material, disease inoculation is carried out after 24h；The non-spray pesticide of control group is tried on material to plant, and disease inoculation is carried out after 24h；By two
Group plant examination material is placed in constant temperature and humidity (25 ± 2 DEG C, relative humidity 60%) incubator, is continued infection, is treated control group
Fully after morbidity (being usually one week), investigation is estimated, partial test result is as follows：
When spray pesticide dosage is 500ppm, majority of compounds pair of the Ia-1~Id-1 into Ia-405~Id-405
The preventive effect of capsicum epidemic disease and wheat powdery mildew is 100%, when spray pesticide dosage is 50ppm, Ia-1~Id-1 to Ia-405
~Id-405 compound preventive effect is 70-100%.
When spray pesticide dosage is 100ppm, compound Ia-66, Ia-87, Ib-75, Ic-124, Ic-299, Id-
238th, If182, Ig217, Ih-261, Ij-53 etc. are 100% to the preventive effect of capsicum epidemic disease and wheat powdery mildew, the meter of preventive effect
Calculate formula as follows：
Preventive effect=(disease index/blank control disease index after 1- chemicals treatments) × 100%
Choose Ic-299 and make the experiment of its bactericidal activity respectively with existing product Fluoxastrobin, result of the test is as shown in table 1 below：
Table 1, bactericidal activity comparative test result
When spray pesticide dosage is 50ppm, compound Ia-87, Ic-124, Ih-261 are to early blight of tomato, paddy rice rice
Seasonal febrile diseases, speckled leaf blotch, ring rot of apple, rice sheath blight disease, rice blast, rice green smut, bakanae disease of rice, Sclerotina Sclerotiorum in Winter Rape
Core disease, cucumber downy mildew, the preventive effect of gray mold of cucumber and powdery mildew of cucumber are more than 80%.
Embodiment 11, pesticide and miticide actility are determined：
Insecticidal activity assay is carried out to insect and mite class, method for measuring is as follows：By a small amount of N of compound of formula I, N- bis-
NMF dissolves, and is diluted with water to required scale；
Using mythimna separata, diamondback moth, black peach aphid and Tetranychus cinnabarinus as material to be tested, insecticidal activity survey is carried out with airbrush spray-on processes
Fixed, the pressure of airbrush spraying treatments is 10psi, and spouting liquid is 0.5ml.After processing after 2-3 days, the dead of material to be tested is investigated
Rate is died, partial test result is as follows：
When airbrush spray-on processes dispenser dosage be 500ppm when, compound Ic-315, Ih246, Id-374 to mythimna separata,
Diamondback moth, black peach aphid, the Tetranychus cinnabarinus death rate are more than 60%.
Claims (3)
1. compound shown in Formulas I：
In the Formulas I, X is selected from CH or N；Y is selected from O or NH；R1For cyano group；R2For Q1；R3Selected from methyl；
Wherein, the Q1In, R4Selected from trifluoromethyl, trifluoromethoxy, phenoxy group, fluorine, chlorine, nitro, cyano group, pyridine epoxide, first
At least one of sulfonyl and trifyl, m=0-3；
Wherein, m is worked as>When 1, R4It is identical or different.
2. a kind of composition, including compound shown in Formulas I described in claim 1 and agriculturally acceptable carrier, wherein, should
The weight percentage of compound shown in Formulas I is 0.1~99% in composition；
The agriculturally acceptable carrier is selected from solid carrier and/or liquid-carrier；
The solid carrier is selected from natural or synthetic silicate, ammonium sulfate, calcium sulfate, oxidation alumina silicate, natural or synthetic
At least one of resin, polystream phenol, starch, bentonite and wax, wherein, the natural or synthetic silicate is selected from silicon magnesium
At least one of soil, talcum, alumina silicate, diatomite, mica, montmorillonite and calcium silicates, the natural or synthetic resin choosing
From at least one of cumarone resin, styrene polymer and styrol copolymer；The wax is selected from beeswax and/or stone
Wax；
The liquid-carrier is selected from water, C1-C4Alcohol, C3-C8Ketone, aromatic hydrocarbons, petroleum distillate, carbon tetrachloride, dichloromethane and three
At least one of chloroethanes；Wherein, the alcohol is ethanol and/or ethylene glycol；The ketone be acetophenone, acetone, MEK and
At least one of cyclohexanone；The aromatic hydrocarbons is at least one of benzene, toluene and dimethylbenzene；The petroleum distillate is kerosene
And/or mineral oil；
In the composition, in addition to surfactant；
The surfactant is selected from least one of emulsifying agent, dispersant, wetting agent and bleeding agent；
The emulsifying agent is selected from alkyl benzene calcium sulfonate, phenyl phenol polyoxyethyl ether, alkylphenol-formaldehyde resin polyoxyethyl ether, benzene second
In base phenol polyoxyethanyl polypropylene-base ether, polyoxyalkylenes alkyl aryl ether and ethylene oxide-propylene oxide block copolymer
It is at least one；
The dispersant is selected from polycarboxylate, lignosulfonates, alkylphenol-polyethenoxy formaldehyde condensation products sulfate, alkylbenzene
Sulfonic acid calcium salt, benzene sulfonic acid formaldehyde condensation products sodium salt, sodium lauryl sulfate, sulfonated castor oil sodium salt, alkyl aryl sulfonic acid ester sodium, alkane
At least one of base phenol polyethenoxy ether, polyoxyethylene carboxylate and ester APEO；
The wetting agent is selected from lauryl sodium sulfate, neopelex, Nekal BX, spaonin powder, silkworm excrement and without trouble
At least one of sub- powder；
In the composition, in addition to other auxiliary agents；
Other described auxiliary agents are selected from least one of disintegrant, defoamer, antifreeze and thickener；
The disintegrant is selected from least one of bentonite, urea, ammonium sulfate, aluminium chloride and glucose；
The defoamer is selected from silicone oil, silicone compound, C10-C20 saturated fat acids compound, C8-C10 aliphatic alcohols
At least one of compound；
The antifreeze is selected from least one of ethylene glycol, propane diols, glycerine and polyethylene glycol；
Described thickener is selected from least one of xanthan gum, polyvinyl alcohol and polyethylene glycol.
3. compound shown in the Formulas I described in claim 1 and/or the composition described in claim 2 are preparing bactericide
And/or the application in insecticide.
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