CN1179942C - 具有杀菌活性的含硫不饱和肟醚类化合物及其制备方法 - Google Patents
具有杀菌活性的含硫不饱和肟醚类化合物及其制备方法 Download PDFInfo
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- CN1179942C CN1179942C CNB021396108A CN02139610A CN1179942C CN 1179942 C CN1179942 C CN 1179942C CN B021396108 A CNB021396108 A CN B021396108A CN 02139610 A CN02139610 A CN 02139610A CN 1179942 C CN1179942 C CN 1179942C
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- oily
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- methyl
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- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 71
- 239000002904 solvent Substances 0.000 claims description 30
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000000855 fungicidal effect Effects 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
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- UFHLMYOGRXOCSL-UHFFFAOYSA-N isoprothiolane Chemical compound CC(C)OC(=O)C(C(=O)OC(C)C)=C1SCCS1 UFHLMYOGRXOCSL-UHFFFAOYSA-N 0.000 claims description 2
- PVTHJAPFENJVNC-MHRBZPPQSA-N kasugamycin Chemical compound N[C@H]1C[C@H](NC(=N)C(O)=O)[C@@H](C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H]1O PVTHJAPFENJVNC-MHRBZPPQSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
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- 238000010189 synthetic method Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- 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
- A01N37/44—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 containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—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 containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
- C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了通式(I)所示的具有杀菌活性的含硫不饱和肟醚类化合物及其制备方法。通式(I)中A是氢，卤素，氰基，烷基，烷氧基，卤代烷基，卤代烷氧基；X是CH或N；Y是O，S，NR6；R1，R6是H或烷基；R2，R3，R4，及R5分别是氢，卤素，任意取代的烷基，任意取代的烷氧基，任意取代的烯基，任意取代的炔基，任意取代的芳基，任意取代的杂芳基。n是0，1或2。
Description
一、技术领域：本发明涉及具有杀菌活性的含硫不饱和肟醚类化合物及其制备方法。
二、背景技术：欧州专利EP0472300A2公开了具有肟醚结构的杀真菌剂，描述了具有肟醚结构的化合物用作杀真菌剂。但其有效杀菌谱还不够广泛。
三、发明内容：本发明的目的是提供一类具有通式(I)所示的具有杀菌活性的含硫不饱和肟醚类化合物及其制备方法。这些化合物具有很高的杀菌活性，用于防治在各种作物上由藻菌纲、卵菌纲、子囊菌纲、担子菌纲和半知菌纲等多种真菌引起的病害，在很低的剂量下就可以获得很好的效果。除了对霜霉病、晚疫病、白粉病、稻瘟病、锈病表现出良好的活性外，还对小麦颖枯病、小麦纹枯病、水稻纹枯病、黄瓜炭疽病、灰霉病都有很好的防效。本发明提供的通式(I)如下：
通式(1)中A是氢，卤素，氰基，C1～C6的烷基，C1～C6的烷氧基，C1～C6的卤代烷基，C1～C6的卤代烷氧基；X是CH或N；Y是O，S，NR6；R1，R6是H或C1～C4的烷基；R2是苯基，萘基，呋喃基，吡啶基，嘧啶基，哒嗪基，苯并呋喃基，噻唑基，苯并噻唑基，吡唑基，各基团任选一个或多个下述基团取代：卤素，C1～C4的烷基，C1～C4的烷氧基，C1～C4的卤代烷基、C1～C4的卤代烷氧基，硝基或氰基；R3和R4是H，C1～C4的烷基，C1～C4的卤代烷基；R5是C1～C4的烷基，C2～C6的烯基，C2～C6的炔基，苯基，苯甲基，萘基；n是0，1或2。卤：指氟、氯、溴和碘。
通式(I)包括由于碳-碳双键和碳-氮双键连接不同的取代基形成的Z型和E型几何异构及其任意比例的混和物。
本发明还可用表1中列出的化合物来说明，但并不限定本发明。
表1
| 34 | H | N | O | 0 | 5-Cl-3-吡啶基 | H | H | CH3 | 油状 |
| 35 | H | N | O | 0 | 3-Cl-4-吡啶基 | H | H | CH3 | 油状 |
| 36 | H | N | O | 0 | 1-萘基 | H | H | CH3 | 油状 |
| 37 | H | C | O | 0 | C6H5 | H | H | CH3 | 油状 |
| 38 | H | C | O | 0 | 2-Cl-C6H4 | H | H | CH3 | 油状 |
| 39 | H | C | O | 0 | 3-Cl-C6H4 | H | H | CH3 | 油状 |
| 40 | H | C | O | 0 | 4-Cl-C6H4 | H | H | CH3 | 油状 |
| 41 | H | C | O | 0 | 2-F-C6H4 | H | H | CH3 | 油状 |
| 42 | H | C | O | 0 | 3-F-C6H4 | H | H | CH3 | 油状 |
| 43 | H | C | O | 0 | 4-F-C6H4 | H | H | CH3 | 油状 |
| 44 | H | C | O | 0 | 2，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 45 | H | C | O | 0 | 2，5-diCl-C6H3 | H | H | CH3 | 油状 |
| 46 | H | C | O | 0 | 3，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 47 | H | C | O | 0 | 2-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 48 | H | C | O | 0 | 3-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 49 | H | C | O | 0 | 2-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 50 | H | C | O | 0 | 3-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 51 | H | C | O | 0 | 2-Me-C6H4 | H | H | CH3 | 油状 |
| 52 | H | C | O | 0 | 3-Me-C6H4 | H | H | CH3 | 油状 |
| 53 | H | C | O | 0 | 4-Me-C6H4 | H | H | CH3 | 油状 |
| 54 | H | C | O | 0 | 2-MeO-C6H4 | H | H | CH3 | 油状 |
| 55 | H | C | O | 0 | 3-MeO-C6H | H | H | CH3 | 油状 |
| 56 | H | C | O | 0 | 4-MeO-C6H | H | H | CH3 | 油状 |
| 57 | H | C | O | 0 | 2，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 58 | H | C | O | 0 | 2，5-diMe-C6H3 | H | H | CH3 | 油状 |
| 59 | H | C | O | 0 | 3，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 60 | H | C | O | 0 | 3-CF3-C6H4 | H | H | CH3 | 油状 |
| 61 | H | C | O | 0 | 4-CF3-C6H4 | H | H | CH3 | 油状 |
| 62 | H | C | O | 0 | 4-F2CHO-C6H4 | H | H | CH3 | 油状 |
| 63 | H | C | O | 0 | 2，5-diCl-4-F-C6H2 | H | H | CH3 | 油状 |
| 64 | H | C | O | 0 | 2-吡啶基 | H | H | CH3 | 油状 |
| 65 | H | C | O | 0 | 3-吡啶基 | H | H | CH3 | 油状 |
| 66 | H | C | O | 0 | 4-吡啶基 | H | H | CH3 | 油状 |
| 67 | H | C | O | 0 | 3-Cl-2-吡啶基 | H | H | CH3 | 油状 |
| 68 | H | C | O | 0 | 4-Cl-2-吡啶基 | H | H | CH3 | 油状 |
| 69 | H | C | O | 0 | 4-Cl-3-吡啶基 | H | H | CH3 | 油状 |
| 70 | H | C | O | 0 | 5-Cl-3-吡啶基 | H | H | CH3 | 油状 |
| 71 | H | C | O | 0 | 3-Cl-4-吡啶基 | H | H | CH3 | 油状 |
| 72 | H | C | O | 0 | 1-萘基 | H | H | CH3 | 油状 |
| 73 | H | N | O | 1 | 2-Cl-C6H4 | H | H | CH3 | 油状 |
| 74 | H | N | O | 1 | 3-Cl-C6H4 | H | H | CH3 | 油状 |
| 75 | H | N | O | 1 | 4-Cl-C6H4 | H | H | CH3 | 油状 |
| 76 | H | N | O | 1 | 2-F-C6H4 | H | H | CH3 | 油状 |
| 77 | H | N | O | 1 | 3-F-C6H4 | H | H | CH3 | 油状 |
| 78 | H | N | O | 1 | 4-F-C6H4 | H | H | CH3 | 油状 |
| 79 | H | N | O | 1 | 2，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 80 | H | N | O | 1 | 2，5-diCl-C6H3 | H | H | CH3 | 油状 |
| 81 | H | N | O | 1 | 3，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 82 | H | N | O | 1 | 2-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 83 | H | N | O | 1 | 3-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 84 | H | N | O | 1 | 2-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 85 | H | N | O | 1 | 3-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 86 | H | N | O | 1 | 2-Me-C6H4 | H | H | CH3 | 油状 |
| 87 | H | N | O | 1 | 3-Me-C6H4 | H | H | CH3 | 油状 |
| 88 | H | N | O | 1 | 4-Me-C6H4 | H | H | CH3 | 油状 |
| 89 | H | N | O | 1 | 2-MeO-C6H4 | H | H | CH3 | 油状 |
| 90 | H | N | O | 1 | 3-MeO-C6H | H | H | CH3 | 油状 |
| 91 | H | N | O | 1 | 4-MeO-C6H | H | H | CH3 | 油状 |
| 92 | H | N | O | 1 | 2，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 93 | H | N | O | 1 | 2，5-diMe-C6H3 | H | H | CH3 | 油状 |
| 94 | H | N | O | 1 | 3，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 95 | H | N | O | 1 | 3-CF3-C6H4 | H | H | CH3 | 油状 |
| 96 | H | N | O | 1 | 4-CF3-C6H4 | H | H | CH3 | 油状 |
| 97 | H | N | O | 1 | 4-F2CHO-C6H4 | H | H | CH3 | 油状 |
| 98 | H | N | O | 1 | 2，5-diCl-4-F-C6H2 | H | H | CH3 | 油状 |
| 99 | H | C | O | 1 | 2-Cl-C6H4 | H | H | CH3 | 油状 |
| 100 | H | C | O | 1 | 3-Cl-C6H4 | H | H | CH3 | 油状 |
| 101 | H | C | O | 1 | 4-Cl-C6H4 | H | H | CH3 | 油状 |
| 102 | H | C | O | 1 | 2-F-C6H4 | H | H | CH3 | 油状 |
| 103 | H | C | O | 1 | 3-F-C6H4 | H | H | CH3 | 油状 |
| 104 | H | C | O | 1 | 4-F-C6H4 | H | H | CH3 | 油状 |
| 105 | H | C | O | 1 | 2，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 106 | H | C | O | 1 | 2，5-diCl-C6H3 | H | H | CH3 | 油状 |
| 107 | H | C | O | 1 | 3，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 108 | H | C | O | 1 | 2-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 109 | H | C | O | 1 | 3-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 110 | H | C | O | 1 | 2-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 111 | H | C | O | 1 | 3-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 112 | H | C | O | 1 | 2-Me-C6H4 | H | H | CH3 | 油状 |
| 113 | H | C | O | 1 | 3-Me-C6H4 | H | H | CH3 | 油状 |
| 114 | H | C | O | 1 | 4-Me-C6H4 | H | H | CH3 | 油状 |
| 115 | H | C | O | 1 | 2-MeO-C6H4 | H | H | CH3 | 油状 |
| 116 | H | C | O | 1 | 3-MeO-C6H | H | H | CH3 | 油状 |
| 117 | H | C | O | 1 | 4-MeO-C6H | H | H | CH3 | 油状 |
| 118 | H | C | O | 1 | 2，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 119 | H | C | O | 1 | 2，5-diMe-C6H3 | H | H | CH3 | 油状 |
| 120 | H | C | O | 1 | 3，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 121 | H | C | O | 1 | 3-CF3-C6H4 | H | H | CH3 | 油状 |
| 122 | H | C | O | 1 | 4-CF3-C6H4 | H | H | CH3 | 油状 |
| 123 | H | C | O | 1 | 4-F2CHO-C6H4 | H | H | CH3 | 油状 |
| 124 | H | C | O | 1 | 2，5-diCl-4-F-C6H2 | H | H | CH3 | 油状 |
| 125 | H | N | O | 2 | 2-Cl-C6H4 | H | H | CH3 | 油状 |
| 126 | H | N | O | 2 | 3-Cl-C6H4 | H | H | CH3 | 油状 |
| 127 | H | N | O | 2 | 4-Cl-C6H4 | H | H | CH3 | 油状 |
| 128 | H | N | O | 2 | 2-F-C6H4 | H | H | CH3 | 油状 |
| 129 | H | N | O | 2 | 3-F-C6H4 | H | H | CH3 | 油状 |
| 130 | H | N | O | 2 | 4-F-C6H4 | H | H | CH3 | 油状 |
| 131 | H | N | O | 2 | 2，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 132 | H | N | O | 2 | 2，5-diCl-C6H3 | H | H | CH3 | 油状 |
| 133 | H | N | O | 2 | 3，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 134 | H | N | O | 2 | 2-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 135 | H | N | O | 2 | 3-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 136 | H | N | O | 2 | 2-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 137 | H | N | O | 2 | 3-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 138 | H | N | O | 2 | 3-CF3-C6H4 | H | H | CH3 | 油状 |
| 139 | H | N | O | 2 | 4-CF3-C6H4 | H | H | CH3 | 油状 |
| 140 | H | C | O | 2 | 2-Cl-C6H4 | H | H | CH3 | 油状 |
| 141 | H | C | O | 2 | 3-Cl-C6H4 | H | H | CH3 | 油状 |
| 142 | H | C | O | 2 | 4-Cl-C6H4 | H | H | CH3 | 油状 |
| 143 | H | C | O | 2 | 2-F-C6H4 | H | H | CH3 | 油状 |
| 144 | H | C | O | 2 | 3-F-C6H4 | H | H | CH3 | 油状 |
| 145 | H | C | O | 2 | 4-F-C6H4 | H | H | CH3 | 油状 |
| 146 | H | C | O | 2 | 2，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 147 | H | C | O | 2 | 2，5-diCl-C6H3 | H | H | CH3 | 油状 |
| 148 | H | C | O | 2 | 3，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 149 | H | C | O | 2 | 2-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 150 | H | C | O | 2 | 3-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 151 | H | C | O | 2 | 2-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 152 | H | C | O | 2 | 3-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 153 | H | C | O | 2 | 3-CF3-C6H4 | H | H | CH3 | 油状 |
| 154 | H | C | O | 2 | 4-CF3-C6H4 | H | H | CH3 | 油状 |
| 155 | H | N | O | 0 | C6H5 | H | CH3 | CH3 | 油状 |
| 156 | H | N | O | 0 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 157 | H | N | O | 0 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 158 | H | N | O | 0 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 159 | H | N | O | 0 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 160 | H | N | O | 0 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 161 | H | N | O | 0 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 162 | H | N | O | 0 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 163 | H | N | O | 0 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 164 | H | N | O | 0 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 165 | H | N | O | 0 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 166 | H | N | O | 0 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 167 | H | N | O | 0 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 168 | H | N | O | 0 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 169 | H | N | O | 0 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 170 | H | N | O | 0 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 171 | H | N | O | 0 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
| 172 | H | C | O | 0 | C6H5 | H | CH3 | CH3 | 油状 |
| 173 | H | C | O | 0 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 174 | H | C | O | 0 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 175 | H | C | O | 0 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 176 | H | C | O | 0 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 177 | H | C | O | 0 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 178 | H | C | O | 0 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 179 | H | C | O | 0 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 180 | H | C | O | 0 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 181 | H | C | O | 0 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 182 | H | C | O | 0 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 183 | H | C | O | 0 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 184 | H | C | O | 0 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 165 | H | C | O | 0 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 186 | H | C | O | 0 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 187 | H | C | O | 0 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 188 | H | C | O | 0 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
| 189 | H | N | O | 1 | C6H5 | H | CH3 | CH3 | 油状 |
| 190 | H | N | O | 1 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 191 | H | N | O | 1 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 192 | H | N | O | 1 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 193 | H | N | O | 1 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 194 | H | N | O | 1 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 195 | H | N | O | 1 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 196 | H | N | O | 1 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 197 | H | N | O | 1 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 198 | H | N | O | 1 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 199 | H | N | O | 1 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 200 | H | N | O | 1 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 201 | H | N | O | 1 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 202 | H | N | O | 1 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 203 | H | N | O | 1 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 204 | H | N | O | 1 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 205 | H | N | O | 1 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
| 206 | H | C | O | 1 | C6H5 | H | CH3 | CH3 | 油状 |
| 207 | H | C | O | 1 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 208 | H | C | O | 1 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 209 | H | C | O | 1 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 210 | H | C | O | 1 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 211 | H | C | O | 1 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 212 | H | C | O | 1 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 213 | H | C | O | 1 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 214 | H | C | O | 1 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 215 | H | C | O | 1 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 216 | H | C | O | 1 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 217 | H | C | O | 1 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 218 | H | C | O | 1 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 219 | H | C | O | 1 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 220 | H | C | O | 1 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 221 | H | C | O | 1 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 222 | H | C | O | 1 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
| 223 | H | N | O | 2 | C6H5 | H | CH3 | CH3 | 油状 |
| 224 | H | N | O | 2 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 225 | H | N | O | 2 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 226 | H | N | O | 2 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 227 | H | N | O | 2 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 228 | H | N | O | 2 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 229 | H | N | O | 2 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 230 | H | N | O | 2 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 231 | H | N | O | 2 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 232 | H | N | O | 2 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 233 | H | N | O | 2 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 234 | H | N | O | 2 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 235 | H | N | O | 2 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 236 | H | N | O | 2 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 237 | H | N | O | 2 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 238 | H | N | O | 2 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 239 | H | N | O | 2 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
| 240 | H | C | O | 2 | C6H5 | H | CH3 | CH3 | 油状 |
| 241 | H | C | O | 2 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 242 | H | C | O | 2 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 243 | H | C | O | 2 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 244 | H | C | O | 2 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 245 | H | C | O | 2 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 246 | H | C | O | 2 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 247 | H | C | O | 2 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 248 | H | C | O | 2 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 249 | H | C | O | 2 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 250 | H | C | O | 2 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 251 | H | C | O | 2 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 252 | H | C | O | 2 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 253 | H | C | O | 2 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 254 | H | C | O | 2 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 255 | H | C | O | 2 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 256 | H | C | O | 2 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
| 257 | H | N | NH | 0 | C6H5 | H | H | CH3 | 油状 |
| 258 | H | N | NH | 0 | 2-Cl-C6H4 | H | H | CH3 | 油状 |
| 259 | H | N | NH | 0 | 3-Cl-C6H4 | H | H | CH3 | 油状 |
| 260 | H | N | NH | 0 | 4-Cl-C6H4 | H | H | CH3 | 油状 |
| 261 | H | N | NH | 0 | 2-F-C6H4 | H | H | CH3 | 油状 |
| 262 | H | N | NH | 0 | 3-F-C6H4 | H | H | CH3 | 油状 |
| 263 | H | N | NH | 0 | 4-F-C6H4 | H | H | CH3 | 油状 |
| 264 | H | N | NH | 0 | 2，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 265 | H | N | NH | 0 | 2，5-diCl-C6H3 | H | H | CH3 | 油状 |
| 266 | H | N | NH | 0 | 3，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 267 | H | N | NH | 0 | 2-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 268 | H | N | NH | 0 | 3-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 269 | H | N | NH | 0 | 2-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 270 | H | N | NH | 0 | 3-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 271 | H | N | NH | 0 | 2-Me-C6H4 | H | H | CH3 | 油状 |
| 272 | H | N | NH | 0 | 3-Me-C6H4 | H | H | CH3 | 油状 |
| 273 | H | N | NH | 0 | 4-Me-C6H4 | H | H | CH3 | 油状 |
| 274 | H | N | NH | 0 | 2-MeO-C6H4 | H | H | CH3 | 油状 |
| 275 | H | N | NH | 0 | 3-MeO-C6H | H | H | CH3 | 油状 |
| 276 | H | N | NH | 0 | 4-MeO-C6H | H | H | CH3 | 油状 |
| 277 | H | N | NH | 0 | 2，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 278 | H | N | NH | 0 | 2，5-diMe-C6H3 | H | H | CH3 | 油状 |
| 279 | H | N | NH | 0 | 3，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 280 | H | N | NH | 0 | 3-CF3-C6H4 | H | H | CH3 | 油状 |
| 281 | H | N | NH | 0 | 4-CF3-C6H4 | H | H | CH3 | 油状 |
| 282 | H | N | NH | 0 | 4-F2CHO-C6H4 | H | H | CH3 | 油状 |
| 283 | H | N | NH | 0 | 2，5-diCl-4-F-C6H2 | H | H | CH3 | 油状 |
| 284 | H | N | NH | 0 | 2-吡啶基 | H | H | CH3 | 油状 |
| 285 | H | N | NH | 0 | 3-吡啶基 | H | H | CH3 | 油状 |
| 286 | H | N | NH | 0 | 4-吡啶基 | H | H | CH3 | 油状 |
| 287 | H | N | NH | 0 | 3-Cl-2-吡啶基 | H | H | CH3 | 油状 |
| 288 | H | N | NH | 0 | 4-Cl-2-吡啶基 | H | H | CH3 | 油状 |
| 289 | H | N | NH | 0 | 4-Cl-3-吡啶基 | H | H | CH3 | 油状 |
| 290 | H | N | NH | 0 | 5-Cl-3-吡啶基 | H | H | CH3 | 油状 |
| 291 | H | N | NH | 0 | 3-Cl-4-吡啶基 | H | H | CH3 | 油状 |
| 292 | H | N | NH | 0 | 1-萘基 | H | H | CH3 | 油状 |
| 293 | H | C | NH | 0 | C6H5 | H | H | CH3 | 油状 |
| 294 | H | C | NH | 0 | 2-Cl-C6H4 | H | H | CH3 | 油状 |
| 295 | H | C | NH | 0 | 3-Cl-C6H4 | H | H | CH3 | 油状 |
| 296 | H | C | NH | 0 | 4-Cl-C6H4 | H | H | CH3 | 油状 |
| 297 | H | C | NH | 0 | 2-F-C6H4 | H | H | CH3 | 油状 |
| 298 | H | C | NH | 0 | 3-F-C6H4 | H | H | CH3 | 油状 |
| 299 | H | C | NH | 0 | 4-F-C6H4 | H | H | CH3 | 油状 |
| 300 | H | C | NH | 0 | 2，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 301 | H | C | NH | 0 | 2，5-diCl-C6H3 | H | H | CH3 | 油状 |
| 302 | H | C | NH | 0 | 3，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 303 | H | C | NH | 0 | 2-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 304 | H | C | NH | 0 | 3-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 305 | H | C | NH | 0 | 2-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 306 | H | C | NH | 0 | 3-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 307 | H | C | NH | 0 | 2-Me-C6H4 | H | H | CH3 | 油状 |
| 308 | H | C | NH | 0 | 3-Me-C6H4 | H | H | CH3 | 油状 |
| 309 | H | C | NH | 0 | 4-Me-C6H4 | H | H | CH3 | 油状 |
| 310 | H | C | NH | 0 | 2-MeO-C6H4 | H | H | CH3 | 油状 |
| 311 | H | C | NH | 0 | 3-MeO-C6H | H | H | CH3 | 油状 |
| 312 | H | C | NH | 0 | 4-MeO-C6H | H | H | CH3 | 油状 |
| 313 | H | C | NH | 0 | 2，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 314 | H | C | NH | 0 | 2，5-diMe-C6H3 | H | H | CH3 | 油状 |
| 315 | H | C | NH | 0 | 3，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 316 | H | C | NH | 0 | 3-CF3-C6H4 | H | H | CH3 | 油状 |
| 317 | H | C | NH | 0 | 4-CF3-C6H4 | H | H | CH3 | 油状 |
| 318 | H | C | NH | 0 | 4-F2CHO-C6H4 | H | H | CH3 | 油状 |
| 319 | H | C | NH | 0 | 2，5-diCl-4-F-C6H2 | H | H | CH3 | 油状 |
| 320 | H | C | NH | 0 | 2-吡啶基 | H | H | CH3 | 油状 |
| 321 | H | C | NH | 0 | 3-吡啶基 | H | H | CH3 | 油状 |
| 322 | H | C | NH | 0 | 4-吡啶基 | H | H | CH3 | 油状 |
| 323 | H | C | NH | 0 | 3-Cl-2-吡啶基 | H | H | CH3 | 油状 |
| 324 | H | C | NH | 0 | 4-Cl-2-吡啶基 | H | H | CH3 | 油状 |
| 325 | H | C | NH | 0 | 4-Cl-3-吡啶基 | H | H | CH3 | 油状 |
| 326 | H | C | NH | 0 | 5-Cl-3-吡啶基 | H | H | CH3 | 油状 |
| 327 | H | C | NH | 0 | 3-Cl-4-吡啶基 | H | H | CH3 | 油状 |
| 328 | H | C | NH | 0 | 1-萘基 | H | H | CH3 | 油状 |
| 329 | H | N | NH | 1 | 2-Cl-C6H4 | H | H | CH3 | 油状 |
| 330 | H | N | NH | 1 | 3-Cl-C6H4 | H | H | CH3 | 油状 |
| 331 | H | N | NH | 1 | 4-Cl-C6H4 | H | H | CH3 | 油状 |
| 332 | H | N | NH | 1 | 2-F-C6H4 | H | H | CH3 | 油状 |
| 333 | H | N | NH | 1 | 3-F-C6H4 | H | H | CH3 | 油状 |
| 334 | H | N | NH | 1 | 4-F-C6H4 | H | H | CH3 | 油状 |
| 335 | H | N | NH | 1 | 2，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 336 | H | N | NH | 1 | 2，5-diCl-C6H 3 | H | H | CH3 | 油状 |
| 337 | H | N | NH | 1 | 3，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 338 | H | N | NH | 1 | 2-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 339 | H | N | NH | 1 | 3-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 340 | H | N | NH | 1 | 2-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 341 | H | N | NH | 1 | 3-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 342 | H | N | NH | 1 | 2-Me-C6H4 | H | H | CH3 | 油状 |
| 343 | H | N | NH | 1 | 3-Me-C6H4 | H | H | CH3 | 油状 |
| 344 | H | N | NH | 1 | 4-Me-C6H4 | H | H | CH3 | 油状 |
| 345 | H | N | NH | 1 | 2-MeO-C6H4 | H | H | CH3 | 油状 |
| 346 | H | N | NH | 1 | 3-MeO-C6H | H | H | CH3 | 油状 |
| 347 | H | N | NH | 1 | 4-MeO-C6H | H | H | CH3 | 油状 |
| 348 | H | N | NH | 1 | 2，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 349 | H | N | NH | 1 | 2，5-diMe-C6H3 | H | H | CH3 | 油状 |
| 350 | H | N | NH | 1 | 3，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 351 | H | N | NH | 1 | 3-CF3-C6H4 | H | H | CH3 | 油状 |
| 352 | H | N | NH | 1 | 4-CF3-C6H4 | H | H | CH3 | 油状 |
| 353 | H | N | NH | 1 | 4-F2CHO-C6H4 | H | H | CH3 | 油状 |
| 354 | H | N | NH | 1 | 2，5-diCl-4-F-C6H2 | H | H | CH3 | 油状 |
| 355 | H | C | NH | 1 | 2-Cl-C6H4 | H | H | CH3 | 油状 |
| 356 | H | C | NH | 1 | 3-Cl-C6H4 | H | H | CH3 | 油状 |
| 357 | H | C | NH | 1 | 4-Cl-C6H4 | H | H | CH3 | 油状 |
| 358 | H | C | NH | 1 | 2-F-C6H4 | H | H | CH3 | 油状 |
| 359 | H | C | NH | 1 | 3-F-C6H4 | H | H | CH3 | 油状 |
| 360 | H | C | NH | 1 | 4-F-C6H4 | H | H | CH3 | 油状 |
| 361 | H | C | NH | 1 | 2，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 362 | H | C | NH | 1 | 2，5-diCl-C6H3 | H | H | CH3 | 油状 |
| 363 | H | C | NH | 1 | 3，4-diCl-C6H3 | H | H | CH3 | 油状 |
| 364 | H | C | NH | 1 | 2-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 365 | H | C | NH | 1 | 3-Cl-4-Me-C6H3 | H | H | CH3 | 油状 |
| 366 | H | C | NH | 1 | 2-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 367 | H | C | NH | 1 | 3-F-4-Me-C6H3 | H | H | CH3 | 油状 |
| 368 | H | C | NH | 1 | 2-Me-C6H4 | H | H | CH3 | 油状 |
| 369 | H | C | NH | 1 | 3-Me-C6H4 | H | H | CH3 | 油状 |
| 370 | H | C | NH | 1 | 4-Me-C6H4 | H | H | CH3 | 油状 |
| 371 | H | C | NH | 1 | 2-MeO-C6H4 | H | H | CH3 | 油状 |
| 372 | H | C | NH | 1 | 3-MeO-C6H | H | H | CH3 | 油状 |
| 373 | H | C | NH | 1 | 4-MeO-C6H | H | H | CH3 | 油状 |
| 374 | H | C | NH | 1 | 2，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 375 | H | C | NH | 1 | 2，5-diMe-C6H3 | H | H | CH3 | 油状 |
| 376 | H | C | NH | 1 | 3，4-diMe-C6H3 | H | H | CH3 | 油状 |
| 377 | H | C | NH | 1 | 3-CF3-C6H4 | H | H | CH3 | 油状 |
| 378 | H | C | NH | 1 | 4-CF3-C6H4 | H | H | CH3 | 油状 |
| 379 | H | C | NH | 1 | 4-F2CHO-C6H4 | H | H | CH3 | 油状 |
| 380 | H | C | NH | 1 | 2，5-diCl-4-F-C6H2 | H | H | CH3 | 油状 |
| 381 | H | N | NH | 0 | C6H5 | H | CH3 | CH3 | 油状 |
| 382 | H | N | NH | 0 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 383 | H | N | NH | 0 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 384 | H | N | NH | 0 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 385 | H | N | NH | 0 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 386 | H | N | NH | 0 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 387 | H | N | NH | 0 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 388 | H | N | NH | 0 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 389 | H | N | NH | 0 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 390 | H | N | NH | 0 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 391 | H | N | NH | 0 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 392 | H | N | NH | 0 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 393 | H | N | NH | 0 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 394 | H | N | NH | 0 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 395 | H | N | NH | 0 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 396 | H | N | NH | 0 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 397 | H | N | NH | 0 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
| 398 | H | C | NH | 0 | C6H5 | H | CH3 | CH3 | 油状 |
| 399 | H | C | NH | 0 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 400 | H | C | NH | 0 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 401 | H | C | NH | 0 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 402 | H | C | NH | 0 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 403 | H | C | NH | 0 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 404 | H | C | NH | 0 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 405 | H | C | NH | 0 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 406 | H | C | NH | 0 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 407 | H | C | NH | 0 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 408 | H | C | NH | 0 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 409 | H | C | NH | 0 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 410 | H | C | NH | 0 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 411 | H | C | NH | 0 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 412 | H | C | NH | 0 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 413 | H | C | NH | 0 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 414 | H | C | NH | 0 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
| 415 | H | N | NH | 1 | C6H5 | H | CH3 | CH3 | 油状 |
| 416 | H | N | NH | 1 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 417 | H | N | NH | 1 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 418 | H | N | NH | 1 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 419 | H | N | NH | 1 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 420 | H | N | NH | 1 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 421 | H | N | NH | 1 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 422 | H | N | NH | 1 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 423 | H | N | NH | 1 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 424 | H | N | NH | 1 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 425 | H | N | NH | 1 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 426 | H | N | NH | 1 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 427 | H | N | NH | 1 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 428 | H | N | NH | 1 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 429 | H | N | NH | 1 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 430 | H | N | NH | 1 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 431 | H | N | NH | 1 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
| 432 | H | C | NH | 1 | C6H5 | H | CH3 | CH3 | 油状 |
| 433 | H | C | NH | 1 | 2-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 434 | H | C | NH | 1 | 3-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 435 | H | C | NH | 1 | 4-Cl-C6H4 | H | CH3 | CH3 | 油状 |
| 436 | H | C | NH | 1 | 2-F-C6H4 | H | CH3 | CH3 | 油状 |
| 437 | H | C | NH | 1 | 3-F-C6H4 | H | CH3 | CH3 | 油状 |
| 438 | H | C | NH | 1 | 4-F-C6H4 | H | CH3 | CH3 | 油状 |
| 439 | H | C | NH | 1 | 2，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 440 | H | C | NH | 1 | 2，5-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 441 | H | C | NH | 1 | 3，4-diCl-C6H3 | H | CH3 | CH3 | 油状 |
| 442 | H | C | NH | 1 | 2-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 443 | H | C | NH | 1 | 3-Cl-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 444 | H | C | NH | 1 | 2-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 445 | H | C | NH | 1 | 3-F-4-Me-C6H3 | H | CH3 | CH3 | 油状 |
| 446 | H | C | NH | 1 | 3-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 447 | H | C | NH | 1 | 4-CF3-C6H4 | H | CH3 | CH3 | 油状 |
| 448 | H | C | NH | 1 | 4-F2CHO-C6H4 | H | CH3 | CH3 | 油状 |
在本发明通式(I)中，当Y＝O，n＝0时化合物(VIIII)的制备方法如下：
式中A，R1，R2，R3，R4，R5及X的定义同上；Z是离去基团。
将式(II)化合物与式(III)化合物在适当的溶剂中，在碱性条件下反应得式(VIIII)化合物，所选的溶剂是THF，DMF或DMSO；所选的碱是K2CO3，NaH或NaNH2；反应温度是-10℃～30℃。
式(VIIII)化合物还可用如下方法制备：
式中A，R1，R2，R3，R4，R5及X的定义同上。Z是离去基团。
先由式(II)化合物与羟胺或盐酸羟胺在溶剂乙醇、甲醇或水中，在氢氧化钠、甲醇钠或乙醇钠碱性条件下，反应温度0℃～50℃下反应得到式(IV)化合物，再在适当的溶剂中、碱催化下与式(V)化合物加成即得(VIIII)化合物。优选的溶剂是苯、甲苯或乙醇；优选的碱催化是氢氧化钠或三乙胺；优选的反应温度是50℃～100℃。
在本发明通式(I)中，当Y＝O，n＝0，X＝N或CH时，式(X)和式(XI)化合物可通过以下方法制备：
式中A，R1，R2，R3，R4，R5的定义同上。Z是离去基团。
先将式(III)化合物与式(VI)化合物在适当的溶剂中，在碱性条件下反应得式(VII)化合物。优选的溶剂是THF，DMF或DMSO；优选的碱是K2CO3，NaH或NaNH2；优选反应温度是20℃～80℃。式(VII)化合物在适当的溶剂中催化醇解得式(VIII)化合物。优选的溶剂是甲基特丁基醚，二氯甲烷，三氯甲烷或二氯乙烷；优选的催化剂是干燥的氯化氢；优选反应温度是20℃～80℃。在适当的溶剂中将式(VIII)化合物与甲氧胺或甲氧胺的盐酸盐加成即得式(X)化合物。优选的溶剂是甲醇，乙醇或水；优选反应温度是60℃～100℃。式(VIII)化合物在适当的溶剂中与三苯膦甲氧亚甲基的盐酸盐经Witting反应即得式(XI)化合物，优选的溶剂是THF，DMF或DMSO；优选的碱是特丁基锂，NaH或NaNH2；优选反应温度是-10℃～20℃。us4144269描述了邻甲基苯甲酰腈的合成方法。邻甲基苯甲酰腈在四氯化碳中与NBS在过氧化苯甲酰催化下于80℃下反应即得Z＝Br的(VI)式化合物
在本发明通式(I)中，n＝1或2时，式(XIII)化合物可以通过以下方法来制备：
式中A，R1，R2，R3，R4，R5，X及Y的定义同上。
用式(XII)化合物在适当的溶剂中经过氧化氢或过硼酸钠氧化即可得式(XIII)化合物。
在本发明通式(I)中，当Y＝R6NH时的式(XX)化合物可以通过以下方法来制备：
式中A，R1，R2，R3，R4，R5，R6及X的定义同上。
将式(XIIII)化合物与烷基胺的甲醇或乙醇溶液在碱K2CO3或NaOH作用下于室温下反应即得式(XX)化合物。
本发明的化合物是有效的杀真菌剂，它们具有内吸活性并可用作叶面和土壤杀真菌剂。特别适用于防治下列植物病害：
水稻稻瘟病；大麦和小麦的条锈病、叶锈病、杆锈病及其他作物上的锈病；大麦和小麦的白粉病；黄瓜、甜瓜、丝瓜、南瓜等葫芦科作物上的瓜类白粉病；苹果白粉病、葡萄白粉病及其它植物上的白粉病。
小麦纹枯病和颖枯病；谷物上的长蠕孢属、嘴孢霉、壳针孢属病、核球壳属病、假尾孢属病、顶囊壳属病；落花生尾孢引起的花生褐斑病和球座尾孢引起的花生黑斑病；甜菜、大豆和稻谷上的其它尾孢属病害；番茄、黄瓜、葡萄等蔬菜及水果上的灰霉病害；蔬菜上的胶链孢属病害；黄瓜炭疽病、苹果黑星病；卵菌病害如黄瓜霜霉病、葡萄霜霉病、马铃薯晚疫病、番茄晚疫病；瓜亡革菌引起的立枯病和纹枯病。
通过在组合物中加入其它的一种或多种杀真菌剂，可以扩大杀菌谱，并具有增效杀菌作用。
四、具体实施方式：
以下结合实施例来进一步说明本发明。
实施例1：
2-甲氧亚胺-[2-[2-[1-(4-氟-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯(表1中化合物7)的制备方法
将1.0g(5mmol)的1-对氟苯基-2-甲硫基-乙酮肟与1.43g(5mmol)的(2E)-2-甲氧亚胺基-2-(2’-溴甲基)苯乙酸甲酯于室温下溶于10mlDMF中，控温0～5℃下滴加入0.5gNaH(纯度60％)的10mlDMF悬浮液中，有大量气泡产生。滴毕，将反应混合物倒入100ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶3的混合液冲洗柱层析，得标题化合物0.55g，收率27.2％。
1HNMR：2.02(3H，s)，3.72(2H，s)，3.82(3H，s)，4.04(3H，s)，5.09(2H，s)，7.12～7.70(8H，m)
实施例2：
2-甲氧亚胺-[2-[2-[1-(3-三氟甲基苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯(表
1中化合物24)的制备方法
将1.25g(5mmol)的1-间三氟甲基苯基-2-甲硫基-乙酮肟与1.43g(5mmol)的(2E)-2-甲氧亚胺基-2-(2’-溴甲基)苯乙酸甲酯于室温下溶于10mlDMF中，控温0～5℃下滴加入0.5gNaH(纯度60％)的10mlDMF悬浮液中，有大量气泡产生。滴毕，将反应混合物倒入100ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶3的混合液冲洗柱层析，得标题化合物0.80g，收率34.8％。
1HNMR：2.03(3H，s)，3.76(2H，s)，3.83(3H，s)，4.04(3H，s)，5.13(2H，s)，7.09～7.60(8H，m)
实施例3：
2-甲氧亚胺-[2-[2-[1-(4-二氟甲氧基-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯(表1中化合物26)的制备方法
将1.25g(5mmol)的1-对二氟甲氧基苯基-2-甲硫基-乙酮肟与1.43g(5mmol)的(2E)-2-甲氧亚胺基-2-(2’-溴甲基)苯乙酸甲酯于室温下溶于10mlDMF中，控温0～5℃下滴加入0.5gNaH(纯度60％)的10mlDMF悬浮液中，有大量气泡产生。滴毕，将反应混合物倒入100ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶3的混合液冲洗柱层析，得标题化合物0.50g，收率21.7％。
1HNMR：2.02(3H，s)，3.73(2H，s)，3.82(3H，s)，4.04(3H，s)，5.10(2H，s)，6.26～6.76(1H，t)7.09～7.71(8H，m)
实施例4：
3-甲氧基-[2-[2-[1-(4-氟-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-2-丙烯酸甲酯(表1中化合物43)的制备方法
将1.0g(5mmol)的1-对氟苯基-2-甲硫基-乙酮肟与1.42g(5mmol)的(2E)-3-甲氧基-2-(2’-溴甲基)苯基-2-丙烯酸甲酯于室温下溶于10mlDMF中，控温0～5℃下滴加入0.5gNaH(纯度60％)的10mlDMF悬浮液中，有大量气泡产生。滴毕，将反应混合物倒入100ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶3的混合液冲洗柱层析，得标题化合物0.35g，收率17.5％。1HNMR：2.02(3H，s)，3.64(3H，s)，3.74(2H，s)，3.91(3H，s)，5.15(2H，s)，7.59(1H，s)，7.02～7.72(8H，m)
实施例5：
3-甲氧基-[2-[2-[1-(3-三氟甲基苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-2-丙烯酸甲酯(化合物60)的制备方法
将1.25g(5mmol)的1-间三氟甲基苯基-2-甲硫基-乙酮肟与1.42g(5mmol)的(2E)-3-甲氧基-2-(2’-溴甲基)苯基-2-丙烯酸甲酯于室温下溶于10mlDMF中，控温0～5℃下滴加入0.5gNaH(纯度60％)的10mlDMF悬浮液中，有大量气泡产生。滴毕，将反应混合物倒入100ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶3的混合液冲洗柱层析，得标题化合物0.28g，收率12.2％。1HNMR：2.03(3H，s)，3.68(3H，s)，3.79(2H，s)，3.80(3H，s)，5.17(2H，s)，7.60(1H，s)，7.14～8.01(8H，m)
实施例6：
3-甲氧基-[2-[2-[1-(4-二氟甲氧基-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-2-丙烯酸甲酯(表1中化合物62)的制备方法
将1.25g(5mmol)的1-对二氟甲氧基苯基-2-甲硫基-乙酮肟与1.42g(5mmol)的(2E)-3-甲氧基-2-(2’-溴甲基)苯基-2-丙烯酸甲酯于室温下溶于10mlDMF中，控温0～5℃下滴加入0.5gNaH(纯度60％)的10mlDMF悬浮液中，有大量气泡产生。滴毕，将反应混合物倒入100ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶3的混合液冲洗柱层析，得标题化合物0.40g，收率17.4％。
1HNMR：2.04(3H，s)，3.69(3H，s)，3.77(2H，s)，3.82(3H，s)，5.14(2H，s)，6.25～6.75(1H，t)，7.59(1H，s)，7.08～7.73(8H，m)
实施例7：
2-甲氧亚胺-[2-[2-[1-(4-氯-苯基)-2-甲硫基]-丙亚胺氧甲基]-苯基]-乙酸甲酯(表1中化合物158)的制备方法
将1.15g(5mmol)的1-对氯苯基-2-甲硫基-丙酮肟与1.43g(5mmol)的(2E)-2-甲氧亚胺基-2-(2’-溴甲基)苯乙酸甲酯于室温下溶于10mlDMF中，控温0～5℃下滴加入0.5gNaH(纯度60％)的10mlDMF悬浮液中，有大量气泡产生。滴毕，将反应混合物倒入100ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶3的混合液冲洗柱层析，得标题化合物0.48g，收率21.8％。
1HNMR：1.27～1.29(3H，d)，2.05(3H，s)，3.80(3H，s)，4.04(3H，s)，4.69～4.75(1H，q)5.05(2H，s)，7.29～7.67(8H，m)
实施例8：
3-甲氧基-[2-[2-[1-(4-氯-苯基)-2-甲硫基]-丙亚胺氧甲基]-苯基]-2-丙烯酸甲酯(表1中化合物175)的制备方法
将1.15g(5mmol)的1-对氯苯基-2-甲硫基-丙酮肟与1.42g(5mmol)的(2E)-3-甲氧基-2-(2’-溴甲基)苯基-2-丙烯酸甲酯于室温下溶于10mlDMF中，控温0～5℃下滴加入0.5gNaH(纯度60％)的10mlDMF悬浮液中，有大量气泡产生。滴毕，将反应混合物倒入100ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶3的混合液冲洗柱层析，得标题化合物1.2g，收率59.1％。
1HNMR：1.28～1.31(3H，d)，2.08(3H，s)，3.68(3H，s)，3.81(3H，s)，4.76～4.83(1H，q)5.H(2H，s)，7.16～7.70(8H，m)，7.59(1H，s)
实施例9：
2-甲氧亚胺-[2-[2-[1-(3-三氟甲基苯基)-2-甲基亚磺酰基]-乙亚胺氧甲基]-苯基]-乙酸甲酯(表1中化合物95)的制备方法
将0.45g(1.0mmol)2-甲氧亚胺-[2-[2-[1-(3-三氟甲基苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯(化合物24)溶于10mlCH3OH中，加入H2O20.34g(浓度30％)及2ml冰醋酸，于室温下搅拌2小时。将反应混合物倒入50ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶2的混合液冲洗柱层析，得标题化合物0.35g，收率74.5％。
1HNMR：2.63(3H，s)，3.89(2H，s)，4.03(3H，s)，4.13～4.38(2H，q)，5.19(2H，s)，7.20～8.04(8H，m)
实施例10：
2-甲氧亚胺-[2-[2-[1-(4-二氟甲氧基-苯基)-2-甲基亚磺酰基]-乙亚胺氧甲基]-苯基]-乙酸甲酯(表1中化合物97)的制备方法
将0.45g(1.0mmol)2-甲氧亚胺-[2-[2-[1-(4-二氟甲氧基-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯(化合物26)溶于10mlCH3OH中，加入H2O20.34g(浓度30％)及2ml冰醋酸，于室温下搅拌2小时。将反应混合物倒入50ml水中，乙酸乙酯萃取两次，合并有机层，水洗至中性，无水NaSO4干燥。乙酸乙酯和石油醚1∶2的混合液冲洗柱层析，得标题化合物0.40g，收率85.1％。
1HNMR：2.56(3H，s)，3.81(2H，s)，4.03(3H，s)，4.04～4.25(2H，q)，5.15(2H，s)，6.29～6.78(1H，t)，
7.10～7.76(8H，m)
实施例11：
用本发明的化合物对植物的各种真菌病害进行了试验，试验程序如下：
在温室盆栽植物试材，生长至一定时期备用。化合物原药用少量N，N-二甲基甲酰胺溶解，用水稀释至所需浓度，制剂用水稀释至所需浓度。对植物试材进行喷雾施药处理，以喷清水植物试材为对照，将植物试材放置通风处使植物表面药液风干，24小时后接种病原菌。接种完毕，将植物放在恒温恒湿培养箱中，使病原菌得以继续侵染。接种后数天，当对照充分发病时即可进行各药剂处理的发病指数调查。
活性分级如下：
A级：防效为90％-100％，B级：防效为70％-90％，C级：防效为50-90％，D级：防效为50％以下。
下表为部分测试结果(待测化合物浓度为100ppm)：
| 化合物编号 | 黄瓜灰霉病 | 黄瓜霜霉病 | 水稻纹枯病 | 水稻稻瘟病 | 小麦白粉病 | 小麦颖枯病 | 小麦锈病 | 黄瓜炭疽病 | 番茄晚疫病 |
| 7 | B | B | C | B | A | A | A | B | B |
| 8 | B | B | B | B | A | A | A | B | B |
| 12 | A | B | B | B | B | B | B | B | B |
| 24 | A | A | B | A | A | A | A | B | A |
| 26 | A | B | A | B | B | B | B | B | B |
| 37 | B | B | B | B | A | A | A | B | B |
| 43 | B | B | B | A | A | A | A | B | B |
| 44 | A | B | B | A | A | A | A | B | B |
| 48 | A | B | A | A | A | A | A | B | A |
| 53 | B | B | B | B | A | A | A | B | B |
| 62 | B | B | B | A | A | A | A | B | B |
| 175 | B | B | B | A | A | A | A | B | B |
本发明可与以下杀菌剂组合以增效杀菌作用：烯唑醇、腈菌唑、粉锈灵、苯菌灵、噻菌灵、多菌灵、甲基托布津、百菌清、波尔多液、双胍辛盐、井冈霉素、土菌消、速克灵、富士一号、春雷霉素、代森锰锌、代森锰、代森锌、多氧霉素、甲基代森锌、福美双、十三吗啉、烯酰吗啉、甲霜灵等。
Claims (9)
1、具有杀菌活性的含硫不饱和肟醚类化合物，其特征在于具有通式(I)的化合物及其Z型和E型几何异构体，
通式(I)中A是氢，卤素，氰基，C1～C6的烷基，C1～C6的烷氧基，C1～C6的卤代烷基，C1～C6的卤代烷氧基；X是CH或N；Y是O，S，NR6；R1，R6是氢或C1～C4的烷基；R2是苯基，萘基，呋喃基，吡啶基，嘧啶基，哒嗪基，苯并呋喃基，噻唑基，苯并噻唑基，吡唑基，各基团被任选一个或多个下述基团取代：卤素，C1～C4的烷基，C1～C4的烷氧基，C1～C4的卤代烷基、C1～C4的卤代烷氧基，硝基或氰基；R3和R4是H，C1～C4的烷基，C1～C4的卤代烷基；R5是C1～C4的烷基，C2～C6的烯基，C2～C6的炔基，苯基，苯甲基，萘基；n是0，1或2。
2、根据权利要求1所述具有杀菌活性的含硫不饱和肟醚类化合物，其特征在于化合物是：
2-甲氧亚胺-[2-[2-[1-(3-三氟甲基苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯
2-甲氧亚胺-[2-[2-[1-(4-氟-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯
2-甲氧亚胺-[2-[2-[1-(2，4-二氯-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯
2-甲氧亚胺-[2-[2-[1-(3-氯-4-甲基苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯
2-甲氧亚胺-[2-[2-[1-(4-二氟甲氧基-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-乙酸甲酯
3-甲氧基-[2-[2-[1-(3-三氟甲基苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-2-丙烯酸甲酯
3-甲氧基-[2-[2-[1-(4-氟-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-2-丙烯酸甲酯
3-甲氧基-[2-[2-[1-(2，4-二氯-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-2-丙烯酸甲酯
3-甲氧基-[2-[2-[1-(3-氯-4-甲基苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-2-丙烯酸甲酯
3-甲氧基-[2-2-[1-(4-甲基-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-2-丙烯酸甲酯
3-甲氧基-[2-[2-[1-(4-二氟甲氧基-苯基)-2-甲硫基]-乙亚胺氧甲基]-苯基]-2-丙烯酸甲酯
2-甲氧亚胺-[2-[2-[1-(3-三氟甲基苯基)-2-甲基亚磺酰基]-乙亚胺氧甲基]-苯基]-乙酸甲酯
2-甲氧亚胺-[2-[2-[1-(4-二氟甲氧基-苯基)-2-甲基亚磺酰基]-乙亚胺氧甲基]-苯基]-乙酸甲酯。
3、根据权利要求1所述具有杀菌活性的含硫不饱和肟醚类化合物的制备方法，其特征在于在碱性条件下式(II)化合物与式(III)化合物在溶剂中于-10℃～30℃下反应即得到n＝0，Y＝O的式(I)化合物，所述的碱是K2CO3，NaH或NaNH2，所述的溶剂是THF，DMF或DMSO；
式中A，X，R1，R2，R3，R4及R5具有权利要求1中所给定义；Z是离去基团。
4、根据权利要求1所述具有杀菌活性的含硫不饱和肟醚类化合物的制备方法，其特征在于在碱性条件下用由权利要求3中所述式(II)化合物与羟胺或盐酸羟胺在溶剂中于0～50℃下反应得到式(IV)化合物，所述溶剂是乙醇、甲醇或水，所述碱是氢氧化钠、甲醇钠或乙醇钠；式(IV)化合物再在碱性条件下与式(V)化合物在溶剂中于50～100℃下反应即得n＝0，Y＝O的式(I)化合物，所述碱是氢氧化钠或三乙胺，所述溶剂是苯、甲苯或乙醇。
式中A，X，R1，R2，R3，R4及R5具有权利要求1中所给定义。
5、根据权利要求1所述具有杀菌活性的含硫不饱和肟醚类化合物的制备方法，其特征在于在碱性条件下用由权利要求3中所述式(III)化合物与式(VI)化合物在溶剂中于20～80℃下反应得到式(VH)化合物，所述碱是K2CO3、NaH或NaNH2，所述溶剂是THF、DMF或DMSO；该化合物在干燥的氯化氢催化下在溶剂中于20～80℃下醇解得式(VIII)化合物，所述溶剂是甲基特丁基醚、二氯甲烷、三氯甲烷或二氯乙烷；(VIII)化合物与甲氧胺在溶剂中于60～100℃下反应即得n＝0，X＝N，Y＝O的式(I)化合物，所述溶剂是甲醇、乙醇或水；(VIII)化合物在碱性条件下与Ph3P-CH2OMe在溶剂中于-10～20℃反应即得n＝0，X＝CH，Y＝O的式(I)化合物，所述碱是特丁基锂、NaH或NaNH2，所述溶剂是THF、DMF或DMSO。
式中A，R1，R2，R3，R4及R5具有权利要求1中所给出的定义。
6、根据权利要求1所述具有杀菌活性的含硫不饱和肟醚类化合物的制备方法，其特征在于n＝0的式(I)化合物在醋酸溶液中，经过过氧化氢或过硼酸钠氧化即得n＝1或n＝2的式(I)化合物。
7、根据权利要求1所述具有杀菌活性的含硫不饱和肟醚类化合物的制备方法，其特征在于将Y＝O的式(I)化合物在碱性条件下与烷基胺在溶剂中室温应得Y＝NR6的式(I)化合物，所述碱是K2CO3或NaOH，所述溶剂是甲醇或乙醇。
8、根据权利要求1所述的含硫不饱和肟醚类化合物，其特征在于防治农作物上由藻菌纲、卵菌纲、子囊菌纲、担子菌纲和半知菌纲引起的病害。
9、根据权利要求1所述的具有杀菌活性的含硫不饱和肟醚类化合物的组合物，其特征在于分别与烯唑醇、腈菌唑、粉锈灵、苯菌灵、噻菌灵、多菌灵、甲基托布津、百菌清、波尔多液、双胍辛盐、井冈霉素、土菌消、速克灵、富士一号、春雷霉素、代森锰锌、代森锰、代森锌、多氧霉素、甲基代森锌、福美双、十三吗啉，甲霜灵组合以增效杀菌作用。
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| AU2003297069A AU2003297069A1 (en) | 2002-09-13 | 2003-06-27 | Unsaturated sulfur containing-oxime ether compounds with fungicidal activty and their preparation |
| PCT/CN2003/000502 WO2004024678A1 (fr) | 2002-09-13 | 2003-06-27 | Composes d'oxime-ether contenant du soufre insature, a action fongicide, et leur preparation |
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| DE68928783T2 (de) * | 1988-11-21 | 1998-12-24 | Zeneca Ltd., London | Zwischenverbindungen zur Herstellung von Fungiziden |
| KR100187541B1 (ko) * | 1988-12-29 | 1999-06-01 | 쟝-자크 오가이; 롤란트 보러 | 알디미노-또는 케티미노-옥시-오르토-톨릴아크릴산의 메틸 에스테르,이의 제조방법 및 이를 함유하는 살진균제 |
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