CN111285807A - 一种吡唑酰胺类化合物及其用途 - Google Patents
一种吡唑酰胺类化合物及其用途 Download PDFInfo
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- CN111285807A CN111285807A CN201811496747.5A CN201811496747A CN111285807A CN 111285807 A CN111285807 A CN 111285807A CN 201811496747 A CN201811496747 A CN 201811496747A CN 111285807 A CN111285807 A CN 111285807A
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- -1 Pyrazole amide compound Chemical class 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 230000000855 fungicidal effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- 239000000417 fungicide Substances 0.000 claims description 4
- 244000052769 pathogen Species 0.000 claims description 4
- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical group FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
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- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims 1
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
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- 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 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
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- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 229940125758 compound 15 Drugs 0.000 description 3
- 150000002483 hydrogen compounds Chemical class 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- WIWMMJPXRWAZBB-UHFFFAOYSA-N 5-chloro-1,3-dimethylpyrazole-4-carbonyl chloride Chemical compound CC1=NN(C)C(Cl)=C1C(Cl)=O WIWMMJPXRWAZBB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- 241000235349 Ascomycota Species 0.000 description 2
- 241000221198 Basidiomycota Species 0.000 description 2
- HSNJDMIVSAUKEN-UHFFFAOYSA-N CC1=C(N)C=CC=C1OC(C)CCC Chemical compound CC1=C(N)C=CC=C1OC(C)CCC HSNJDMIVSAUKEN-UHFFFAOYSA-N 0.000 description 2
- 241000760356 Chytridiomycetes Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000221785 Erysiphales Species 0.000 description 2
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 2
- 241001330975 Magnaporthe oryzae Species 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 241000233654 Oomycetes Species 0.000 description 2
- 241001503460 Plasmodiophorida Species 0.000 description 2
- 240000003768 Solanum lycopersicum Species 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
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- 235000004936 Bromus mango Nutrition 0.000 description 1
- 244000250392 Cardamine diphylla Species 0.000 description 1
- 235000001250 Cardamine diphylla Nutrition 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
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- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
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- 235000008434 ginseng Nutrition 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- 238000013537 high throughput screening Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
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- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
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- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明属于杀菌剂领域。涉及一种吡唑酰胺类化合物及其杀菌用途。吡唑酰胺类化合物如通式I所示：
Description
技术领域
本发明属于杀菌剂领域。涉及一种吡唑酰胺类化合物及其杀菌用途。
背景技术
由于杀菌剂在使用一段时间后，病害会对其产生抗性，因此，需要不断发明新型的和改进的具有杀菌活性的化合物和组合物。
吡唑酰胺化合物的杀菌活性已有报道。如CN106187893公开了化合物KC1(专利中化合物4)及其杀菌活性；CN104649973公开了化合物KC2(专利中化合物6)及其杀菌活性。
现有技术中，结构如本发明通式I所示的吡唑酰胺类化合物未见报道。
发明内容
本发明的目的在于提供一种杀菌活性更好的吡唑酰胺类化合物，它可应用于农业上病害的防治。
本发明的技术方案如下：
本发明提供了吡唑酰胺类化合物，如通式I所示：
式中：
R1选自C1-C3的烷基、C1-C3的卤代烷基或C3-C6的环烷基；
R2选自卤素或甲基；
本发明中优选的技术方案为，通式I中：
R1选自C1-C3的烷基或C1-C3的卤代烷基；
R2选自卤素；
本发明中进一步优选的技术方案为，通式I中：
R1选自甲基、乙基、正丙基、异丙基、二氟甲基、三氟甲基、1-氟乙基、五氟乙基、七氟异丙基；
R2选自氟、氯、溴或碘；
本发明中特别优选的技术方案为，通式I中：R1选自甲基、二氟甲基或三氟甲基；
R1选自甲基、二氟甲基或三氟甲基；
R2选自氯；
上面给出的通式I化合物的定义中，汇集所用术语一般定义如下：
烷基是指直链或支链形式，例如甲基、乙基、正丙基、异丙基等。环烷基包括环丙基、环丁基、环丙基甲基、甲基环丙基等。卤代烷基是指烷基被一个或多个卤原子取代的基团，如氯乙基、三氟甲基、二氟甲基、七氟异丙基等。卤素是指氟、氯、溴、碘。
本发明的通式化合物I可由如下方法制备：
方法一：
通式II化合物与通式III化合物在适宜的溶剂中，温度为-10℃到适宜溶剂的沸点下反应0.5-48小时制得目标化合物I。
适宜的溶剂选自二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙腈、四氢呋喃、二氧六环、N,N-二甲基甲酰胺或二甲基亚砜等。
加入适宜的碱对反应有利，适宜的碱包括碱金属如锂、钠或钾的氢化合物如氢化钠，碱金属如锂、钠或钾的氢氧化物如氢氧化钠，还可以是碱金属的碳酸盐如碳酸钠，也可以是有机碱如三乙胺、叔丁醇钠等。
通式II化合物可参考下列文献制备：CN101979375A。
通式III化合物可参考下列文献制备：Bioorganic&Medicinal Chemistry,2012，20(3):1213-1221；农药，2007,46(5):307-309；PCT/CN2014/091998。
方法二：
式中，L代表离去基团、X代表卤素。
通式II化合物与通式IV化合物(市售)在适宜的溶剂中、适宜的碱存在下，温度为-10℃到适宜溶剂的沸点下反应0.5-48小时制得化合物V。
适宜的溶剂选自二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙腈、四氢呋喃、二氧六环、N,N-二甲基甲酰胺或二甲基亚砜等。
适宜的碱包括碱金属如锂、钠或钾的氢化合物如氢化钠，碱金属如锂、钠或钾的氢氧化物如氢氧化钠，还可以是碱金属的碳酸盐如碳酸钠，也可以是有机碱如三乙胺、叔丁醇钠等。
通式V化合物与通式VI化合物(市售)在适宜的溶剂中、适宜的碱存在下，温度为-10℃到适宜溶剂的沸点下反应0.5-48小时制得目标物化合物I。
适宜的溶剂选自二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙腈、四氢呋喃、二氧六环、N,N-二甲基甲酰胺或二甲基亚砜等。
适宜的碱包括碱金属如锂、钠或钾的氢化合物如氢化钠，碱金属如锂、钠或钾的氢氧化物如氢氧化钠，还可以是碱金属的碳酸盐如碳酸钠，也可以是有机碱如三乙胺、叔丁醇钠等。
通式IV化合物为市售试剂。
表1列出了部分通式I化合物的结构和物理性质。
表1部分通式I化合物的结构和物理性质
部分化合物的1H NMR(300MHz,CDCl3)数据如下：
化合物11:7.73(s,1H),7.60(d,1H),6.71(d,1H),4.31-4.40(m,1H),3.85(s,3H),2.52(s,3H),2.20(s,3H),1.37-2.05(m,4H),1.24-1.30(m,3H),0.95(t,3H)。
化合物14:7.69(s,1H),7.58(d,1H),7.16(t,1H),6.71(d,1H),4.30-4.45(m,1H),3.86(s,3H),3.55-3.70(m,1H),2.20(s,3H),1.45-1.73(m,4H),1.29-1.31(m,9H),0.94(t,3H)。
化合物15:7.86(s,1H),7.55(d,1H),7.16(t,1H),7.13(t,1H),6.73(d,1H),4.34-4.40(m,1H),3.96(s,3H),2.18(s,3H),1.39-1.74(m,4H),1.26-1.30(m,3H),0.94(t,3H)。
本发明还包括通式I化合物用于控制病害的用途，以防治卵菌纲(Oomycetes)、子囊菌纲(Ascomycetes)、担子菌纲(Basidiomycetes)、半知菌纲(Deuteromycetes)、根肿菌纲(Plasmodiophoromycetes)、壶菌纲(Chytridiomycetes)和结合菌亚纲(Zygomycetes)病害。
在上面列出的纲名下的某些病害的实例可提及的包括但不限于：
小麦锈病、小麦白粉病、小麦赤霉病、小麦根腐病、小麦纹枯病、小麦全蚀病、小麦颖枯病、黄瓜霜霉病、黄瓜炭疽病、黄瓜枯萎病、黄瓜灰霉病、葡萄霜霉病、番茄早疫病、番茄晚疫病、水稻纹枯病、水稻稻瘟病、西瓜蔓枯病、花生疮痂病、花生黑斑病、柑橘疮痂病、辣椒根腐病、棉花黄萎病、棉花枯萎病、油菜黑茎病、油菜菌核病、梨黑星病、人参锈腐病、玉米锈病、玉米弯孢病、玉米大斑病、芒果蒂腐病、苹果轮纹病、苹果腐菌烂病、香蕉叶斑病。
本发明还包括以通式I化合物作为活性组分的杀菌组合物。该杀菌组合物中作为活性组分的通式I化合物的重量百分含量在1-99％之间。该杀菌组合物中还包括农业上可接受的载体。
本发明的组合物可以制剂的形式施用。通式I化合物作为活性组分溶解或分散于载体中或配制成制剂以便作为杀菌使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂或乳油。在这些组合物中，至少加入一种液体或固体载体，并且当需要时可以加入适当的表面活性剂。
本发明的技术方案还包括防治病害的方法：将本发明的杀菌组合物施于所述的病害或其生长介质上。通常选择的较为适宜的有效量为每公顷10克到1000克。
对于某些应用，例如在农业上可在本发明的杀菌组合物中加入一种或多种其它的杀虫剂、杀菌剂、除草剂、植物生长调节剂或肥料等，由此可产生附加的优点和效果。
本发明所具有的优点：
同已知的吡唑酰胺类化合物相比，本发明化合物结构新颖，并且本发明的吡唑酰胺类化合物具有意想不到的高杀菌活性，在较低剂量下也具有高的杀菌活性，不仅高效，而且减少了农药的使用量，降低了成本，减少了对环境的污染。
具体实施方式
下列合成实施例、生物活性测定实施例可用来进一步说明本发明，但不意味着限制本发明。
合成实施例
实施例1化合物11的合成
反应瓶中加入2-甲基-3-(2-戊氧基)苯胺(260毫克，1.35毫摩尔)、三乙胺(160毫克，1.60毫摩尔)和12毫升二氯甲烷，室温搅拌下滴加1,3-二甲基-5-氯吡唑-4-甲酰氯(310毫克，1.60毫摩尔)的二氯甲烷溶液12毫升。滴毕，室温下反应，3小时后反应完毕。反应液倾入至30毫升水中，取有机层，有机层分别用饱和碳酸氢钠水溶液、饱和食盐水洗涤，无水硫酸镁干燥，减压蒸尽溶剂。残余物通过柱色谱提纯(淋洗液：乙酸乙酯：石油醚＝1：4)，得350毫克化合物11，收率72.1％。
实施例2化合物15的合成
反应瓶中加入2-甲基-3-(2-戊氧基)苯胺(270毫克，1.40毫摩尔)、三乙胺(170毫克，1.68毫摩尔)和12毫升二氯甲烷，室温搅拌下滴加1,3-二甲基-5-氯吡唑-4-甲酰氯(384毫克，1.68毫摩尔)的二氯甲烷溶液10毫升。滴毕，室温下反应，3小时后反应完毕。反应液倾入至30毫升水中，取有机层，有机层分别用饱和碳酸氢钠水溶液、饱和食盐水洗涤，无水硫酸镁干燥，减压蒸尽溶剂。残余物通过柱色谱提纯(淋洗液：乙酸乙酯：石油醚＝1：5)，得230毫克化合物15，收率40.5％。
本发明的其他通式I化合物可参照上述方法合成。
生物活性测定实施例
实施例3杀菌活性的测定
用本发明化合物对植物的多种病害进行了试验。试验的方法如下：
(1)活体保护活性试验
试验采用盆栽幼苗测定法。选择生长一致的两叶期盆栽黄瓜幼苗作为黄瓜霜霉病的试验寄主植物；选择生长一致的两叶期盆栽小麦幼苗作为小麦白粉病的试验寄主植物，选择生长一致的两叶期盆栽玉米幼苗作为玉米锈病的试验寄主植物。用本发明化合物按照设计浓度进行叶面喷雾处理。另设喷清水的空白对照，3次重复，处理后第二天进行病害接种。接种后，将植物放在人工气候室中保湿培养(温度：昼25℃、夜20℃，相对湿度：95-99％)。试验材料培养24h后，移置温室培养，将不需要保湿培养的植物直接在温室内接种并培养。带对照充分发病后(通常为一周时间)进行化合物防病效果评估。结果用100～0来表示，以“100”级代表无病和“0”级代表最严重的发病程度。
部分测试结果如下：
对黄瓜霜霉病的防效：
部分供试的化合物中，下列化合物在浓度为100ppm时防治效果较好，防效≥80％：化合物14。
对玉米锈病的防效：
部分供试的化合物中，下列化合物在浓度为100ppm时防治效果较好，防效≥80％：化合物11、14。
(2)离体抑菌活性试验
测定方法如下：采用高通量筛选方法，即将待测化合物样品用适合的溶剂(溶剂的种类如丙酮、甲醇、DMF等，并依据其对样品的溶解能力而选择)溶剂，配成所需浓度待测液。在超净工作环境下，将待测液加入到96孔培养板的微孔中，再将病原菌繁殖体悬浮液加入其中，处理后的培养板放置在恒温培养箱中培养，24小时后进行调查。调查时目测病原菌繁殖体萌发或生长情况，并根据对照处理的萌发或生长情况，评价化合物抑菌活性。
部分化合物的离体抑菌活性(以抑制率表示)测试结果如下：
水稻稻瘟病菌：
部分供试的化合物中，下列化合物在浓度为25ppm时防治效果较好，防效≥80％：化合物14和15。
水稻稻瘟病菌：
按照以上测试方法，选取本发明化合物15与已知化合物KC1和KC2进行防治水稻稻瘟病菌活性的平行测定(对照化合物均为自制，结构经核磁共振氢谱确认与现有公开文献描述的一致)，试验结果见表2。
表2：部分本发明化合物与已知化合物对水稻稻瘟病菌防效(％)的比较
“/”表示测试未进行。
Claims (7)
1.一种吡唑酰胺类化合物，如通式I所示：
式中：
R1选自C1-C3的烷基、C1-C3的卤代烷基或C3-C6的环烷基；
R2选自卤素或甲基。
2.按照权利要求1所述的化合物，其特征在于，通式I中：
R1选自C1-C3的烷基或C1-C3的卤代烷基；
R2选自卤素。
3.按照权利要求2所述的化合物，其特征在于，通式I中：
R1选自甲基、乙基、正丙基、异丙基、二氟甲基、三氟甲基、1-氟乙基、五氟乙基、七氟异丙基；
R2选自氟、氯、溴或碘。
4.按照权利要求3所述的化合物，其特征在于，通式I中：
R1选自甲基、二氟甲基或三氟甲基；
R2选自氯。
5.一种按照权利要求1所述的通式I化合物用于制备作为农业领域中杀菌剂药物的用途。
6.一种杀菌组合物，含有如权利要求1所述的通式I所示化合物为活性组分和农业上可接受的载体，组合物中作为活性组分的通式I化合物的重量含量为1-99％。
7.一种控制病菌的方法，其特征在于：将权利要求6所述的组合物以每公顷10克到1000克的有效剂量施于需要控制的病菌或其生长的介质上。
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