CN108570008A - Pyrazole analog derivative, preparation method and application - Google Patents
Pyrazole analog derivative, preparation method and application Download PDFInfo
- Publication number
- CN108570008A CN108570008A CN201710306758.1A CN201710306758A CN108570008A CN 108570008 A CN108570008 A CN 108570008A CN 201710306758 A CN201710306758 A CN 201710306758A CN 108570008 A CN108570008 A CN 108570008A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- hydrogen
- nitro
- haloalkyl
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000003217 pyrazoles Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims description 24
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims description 145
- 229910052739 hydrogen Inorganic materials 0.000 claims description 145
- 150000002431 hydrogen Chemical group 0.000 claims description 140
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 117
- 229910052736 halogen Inorganic materials 0.000 claims description 100
- 150000002367 halogens Chemical group 0.000 claims description 100
- -1 thiophenolyl Chemical group 0.000 claims description 79
- 125000000217 alkyl group Chemical group 0.000 claims description 76
- 125000001188 haloalkyl group Chemical group 0.000 claims description 68
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 61
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 60
- 125000004995 haloalkylthio group Chemical group 0.000 claims description 59
- 125000004414 alkyl thio group Chemical group 0.000 claims description 57
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 57
- 125000005347 halocycloalkyl group Chemical group 0.000 claims description 57
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 46
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 39
- 239000000460 chlorine Chemical group 0.000 claims description 37
- 229910052801 chlorine Inorganic materials 0.000 claims description 37
- 150000002825 nitriles Chemical group 0.000 claims description 37
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 35
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 35
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 34
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- 239000011737 fluorine Chemical group 0.000 claims description 34
- 125000002541 furyl group Chemical group 0.000 claims description 34
- 125000000335 thiazolyl group Chemical group 0.000 claims description 34
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 33
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 30
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 30
- 229910052794 bromium Inorganic materials 0.000 claims description 30
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 30
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical group [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims description 29
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 27
- 125000004737 (C1-C6) haloalkoxy group Chemical group 0.000 claims description 26
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 26
- 125000006771 (C1-C6) haloalkylthio group Chemical group 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 125000004076 pyridyl group Chemical group 0.000 claims description 26
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 24
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 23
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 239000011593 sulfur Substances 0.000 claims description 21
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 20
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 125000006643 (C2-C6) haloalkenyl group Chemical group 0.000 claims description 14
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 14
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 14
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 14
- 235000009518 sodium iodide Nutrition 0.000 claims description 13
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 12
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 229930192474 thiophene Natural products 0.000 claims description 12
- 241000238876 Acari Species 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims description 11
- 230000000895 acaricidal effect Effects 0.000 claims description 10
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 8
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000642 acaricide Substances 0.000 claims description 8
- 150000001350 alkyl halides Chemical class 0.000 claims description 8
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 7
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 241001124076 Aphididae Species 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 235000013601 eggs Nutrition 0.000 claims description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- PZIDJKOIMRBQLL-UHFFFAOYSA-N $l^{2}-azanylidenemethane Chemical compound [N]=C PZIDJKOIMRBQLL-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 241000244206 Nematoda Species 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 125000005257 alkyl acyl group Chemical group 0.000 claims description 5
- 125000005360 alkyl sulfoxide group Chemical group 0.000 claims description 5
- 239000002917 insecticide Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000005227 alkyl sulfonate group Chemical group 0.000 claims description 4
- 241000239223 Arachnida Species 0.000 claims description 3
- 241001427559 Collembola Species 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000005157 alkyl carboxy group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 230000003071 parasitic effect Effects 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- 241000258963 Diplopoda Species 0.000 claims description 2
- 241001466042 Fulgoromorpha Species 0.000 claims description 2
- 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 2
- 241001149911 Isopoda Species 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 201000010099 disease Diseases 0.000 claims description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000003586 protic polar solvent Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003652 trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 241000341511 Nematodes Species 0.000 claims 1
- 206010039710 Scleroderma Diseases 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
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- 241000894007 species Species 0.000 claims 1
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- 125000001424 substituent group Chemical group 0.000 abstract description 30
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- 238000006243 chemical reaction Methods 0.000 description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
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Classifications
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- 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
- C07D231/12—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon 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
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
技术领域technical field
本发明属于农用杀虫、杀螨领域,具体涉及一类吡唑类衍生物。The invention belongs to the field of agricultural insecticide and acaricide, and specifically relates to a class of pyrazole derivatives.
背景技术Background technique
由于现有农药的长期使用,使得病虫害产生了抗性,从而使得农药使用量显著增加,对环境造成严重的破坏。因此要求不断发现具有新的作用机理的高效新农药,例如对杀虫、杀菌或杀螨具有更高活性的新农药,例如现有的杀螨剂农药品种中,大部分农药只能防治螨卵、若螨、成螨三个阶段中的一阶段,如果能够研究开发出对螨三个阶段都具有防治效果的心的杀螨剂将具有重大意义。Due to the long-term use of the existing pesticides, the pests and diseases have developed resistance, which has significantly increased the use of pesticides and caused serious damage to the environment. Therefore, it is required to continuously discover new efficient pesticides with new mechanisms of action, such as new pesticides with higher activity for killing insects, bacteria or acaricides. For example, among the existing acaricide pesticide varieties, most pesticides can only control mite eggs It is one of the three stages of mites, nymphs, and adults. It will be of great significance to research and develop a new acaricide that has control effects on all three stages of mites.
PCT专利申请WO01/68589公开了杂环丙烯腈醚类化合物,说明书第71页公开了下述化合物8-1、8-2、8-3和8-4,PCT patent application WO01/68589 discloses heterocyclic acrylonitrile ether compounds, and page 71 of the description discloses the following compounds 8-1, 8-2, 8-3 and 8-4,
现有技术未公开本申请所述的吡唑类衍生物。The prior art does not disclose the pyrazole derivatives described in the present application.
发明内容Contents of the invention
本发明提供一类吡唑衍生物,具有如下通式stru-1:The present invention provides a class of pyrazole derivatives, which have the following general formula stru-1:
其中:in:
R1、R2、R3、R4、R5独立地选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷亚砜基、C1-C20烷砜基、C1-C20烷基磺酸酯基,C1-C20烷基羧酸酯、C1-C20烷基酰基、C1-C20卤代烷基酰基;R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 2 -C 20 alkenyl, C 2 - C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio group, C 1 -C 20 haloalkylthio group, C 1 -C 20 alkyl sulfoxide group, C 1 -C 20 alkyl sulfone group, C 1 -C 20 alkyl sulfonate group, C 1 -C 20 alkyl carboxyl group Ester, C 1 -C 20 alkyl acyl, C 1 -C 20 haloalkyl acyl;
R6选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基;R6 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkane Oxygen, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 - Phenyl substituted by at least one of C 20 haloalkylthio and C 1 -C 20 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkane C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C At least one of 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone substituted pyridyl, pyrazolyl, thiophenol, furyl or thiazolyl;
R7选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C1-C20烷氧亚甲基;R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 1 -C 20 alkoxymethylene;
R8选自氢、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧亚甲基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基;R8 is selected from hydrogen, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxymethylene group, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl , C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone phenyl, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halo ring At least one of alkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone One substituted pyridyl, pyrazolyl, thiophenolyl, furyl or thiazolyl;
R9选自氢、卤素、硝基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷砜基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基;R9 is selected from hydrogen, halogen, nitro, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkane Thio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone substituted by at least one phenyl, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C At least one of 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone substituted pyridyl, pyrazolyl, thiophenol, furyl or thiazolyl;
L选自氧、硫、亚甲基、氮;L is selected from oxygen, sulfur, methylene, nitrogen;
Q选自氧、硫;Q is selected from oxygen, sulfur;
R10选自氢、卤素、硝基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷基羧酸酯、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基和C1-C20卤代烷硫基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基和C1-C20卤代烷硫基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。R10 is selected from hydrogen, halogen, nitro, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkyl carboxylate, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C phenyl substituted by at least one of 20 alkylthio and C 1 -C 20 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl , C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio and C 1 -pyridyl, pyrazolyl, thiophenolyl, furyl or thiazolyl substituted by at least one of C 20 haloalkylthio.
本发明提供的通式stru-1所示的吡唑衍生物中,取代基R1、R2、R3、R4、R5独立地选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷亚砜基、C1-C20烷砜基、C1-C20烷基磺酸酯基,C1-C20烷基羧酸酯、C1-C20烷基酰基、C1-C20卤代烷基酰基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl , C 1 -C 20 haloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 Alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkylsulfoxide, C 1 -C 20 alkylsulfone, C 1 -C 20 alkyl sulfonate group, C 1 -C 20 alkyl carboxylate, C 1 -C 20 alkyl acyl group, C 1 -C 20 haloalkyl acyl group.
优选的是,所述取代基R1、R2、R3、R4、R5独立地选自氢、卤素、硝基、腈基、C1-C10烷基、C1-C10卤代烷基、C2-C10烯基、C2-C10卤代烯基、C2-C10炔基、C2-C10卤代炔基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10烷亚砜基、C1-C10烷砜基、C1-C10烷基磺酸酯基,C1-C10烷基羧酸酯、C1-C10烷基酰基、C1-C10卤代烷基酰基。Preferably, the substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 2 - C 10 alkenyl, C 2 -C 10 haloalkenyl, C 2 -C 10 alkynyl, C 2 -C 10 haloalkynyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy , C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 1 -C 10 alkylsulfoxide, C 1 -C 10 alkylsulfone, C 1 -C 10 alkylsulfonate, C 1 -C 10 alkyl carboxylate, C 1 -C 10 alkyl acyl, C 1 -C 10 haloalkyl acyl.
进一步优选的是,所述取代基R1、R2、R3、R4、R5独立地选自氢、卤素、硝基、腈基、C1-C6烷基、C1-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷亚砜基、C1-C6烷砜基、C1-C6烷基磺酸酯基,C1-C6烷基羧酸酯、C1-C6烷基酰基、C1-C6卤代烷基酰基。Further preferably, the substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy C 1 -C 6 Alkylthio, C 1 -C 6 Haloalkylthio, C 1 -C 6 Alkylsulfoxide, C 1 -C 6 Alkylsulfone, C 1 -C 6 Alkylsulfonate , C 1 -C 6 alkyl carboxylate, C 1 -C 6 alkyl acyl, C 1 -C 6 haloalkyl acyl.
再进一步优选的是,所述取代基R1、R2、R3、R4、R5独立地选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、叔丁基、三氟甲基、甲氧基、乙氧基、三氟甲氧基、二氟甲氧基、二氟乙氧基、甲硫基、三氟甲硫基、三氟乙硫基、甲砜基、甲磺基酯。Still further preferably, the substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, tert-butyl , trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, difluoroethoxy, methylthio, trifluoromethylthio, trifluoroethylthio, methylsulfone base, methylsulfonyl ester.
本发明提供的通式stru-1所示的吡唑衍生物中,取代基R6选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R6 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 Haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, selected from hydrogen, halogen, nitro , cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone substituted phenyl, selected from hydrogen, halogen, Nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy , C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone substituted pyridyl, pyrazolyl, thia Phenyl, furyl or thiazolyl.
优选的是,所述取代基R6选自氢、卤素、硝基、腈基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C2-C10烯基、C2-C10卤代烯基、C2-C10炔基、C2-C10卤代炔基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。所示化合物可以为E式、Z式或E式和Z式混合物;Preferably, the substituent R6 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 2 -C 10 alkenyl, C 2 -C 10 haloalkenyl, C 2 -C 10 alkynyl, C 2 -C 10 haloalkynyl, C 1 -C 10 alkoxy radical, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 Alkylthio, C 1 -C 10 haloalkylthio and C 1 -C 10 alkylsulfone substituted phenyl, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkane C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio and C 1 -C 10 alkylsulfone substituted by at least one of pyridyl, pyrazolyl, thiophenol, furyl or thiazolyl. The compound shown can be E formula, Z formula or E formula and Z formula mixture;
进一步优选的是,所述取代基R6选自氢、卤素、硝基、腈基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Further preferably, the substituent R6 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 - C 6 halocycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkane Oxygen, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl , C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 - Phenyl substituted by at least one of C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C 6 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 Alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C At least one of 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C 6 alkylsulfone substituted by pyridyl, pyrazolyl, thiophenol, furyl or thiazolyl.
再进一步优选的是,所述取代基R6选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、环丙基、甲氧基、乙氧基、三氟甲基、二氟甲基、对氯苯基、对氟苯基。Still further preferably, the substituent R6 is selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, cyclopropyl, methoxy, ethoxy, tri Fluoromethyl, difluoromethyl, p-chlorophenyl, p-fluorophenyl.
本发明提供的通式stru-1所示的吡唑衍生物中,取代基R7选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C1-C20烷氧亚甲基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 1 - C20 alkoxymethylene.
优选的是,所述取代基R7选自氢、卤素、硝基、腈基、C1-C10烷基、C1-C10卤代烷基、C1-C10烷氧亚甲基。Preferably, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 1 -C 10 alkoxymethylene.
进一步优选的是,所述取代基R7选自氢、卤素、硝基、腈基、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧亚甲基。Further preferably, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxymethylene.
再进一步优选的是,所述取代基R7选自氢、卤素、硝基、腈基、C1-C5烷基、C1-C5卤代烷基、C1-C5烷氧亚甲基。Still further preferably, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 5 alkyl, C 1 -C 5 haloalkyl, and C 1 -C 5 alkoxymethylene.
本发明提供的通式stru-1所示的吡唑衍生物中,取代基R8选自氢、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧亚甲基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R8 is selected from hydrogen, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxymethylene, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl , C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -Phenyl substituted by at least one of C 20 haloalkylthio and C 1 -C 20 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 Haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, At least one of C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone substituted pyridyl, pyrazolyl, thiophene, furyl or thiazolyl.
优选的是,所述取代基R8选自氢、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧亚甲基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Preferably, the substituent R8 is selected from hydrogen, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxymethylene, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio and C 1 -C 10 At least one substituted phenyl in the alkylsulfone group is selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio and C 1 - At least one substituted pyridyl, pyrazolyl, thiophenolyl, furyl or thiazolyl in the C 10 alkylsulfone group.
进一步优选的是,所述取代基R8选自氢、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧亚甲基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Further preferably, the substituent R8 is selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxymethylene, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C At least one substituted phenyl group in 6 alkylsulfone groups is selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl , C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -pyridyl, pyrazolyl, thiophenolyl, furyl or thiazolyl substituted by at least one of C 6 alkylsulfone groups.
再进一步优选的是,所述取代基R8选自氢、甲基、乙基、一氟甲基、二氟甲基、三氟甲基、甲氧基亚甲基、乙氧基亚甲基。Still further preferably, the substituent R8 is selected from hydrogen, methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, methoxymethylene, ethoxymethylene.
本发明提供的通式stru-1所示的吡唑衍生物中,取代基R9选自氢、卤素、硝基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷砜基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R9 is selected from hydrogen, halogen, nitro, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkyne C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkylsulfone, selected from Hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C phenyl substituted by at least one of 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone substituted pyridyl , pyrazolyl, thiophenolyl, furyl or thiazolyl.
优选的是,所述取代基R9选自氢、卤素、硝基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C2-C10烯基、C2-C10卤代烯基、C2-C10炔基、C2-C10卤代炔基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10烷砜基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Preferably, the substituent R9 is selected from hydrogen, halogen, nitro, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halo Cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 10 haloalkenyl, C 2 -C 10 alkynyl, C 2 -C 10 haloalkynyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 1 -C 10 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy A phenyl group substituted by at least one of C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio and C 1 -C 10 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl , C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 At least one substituted pyridyl, pyrazolyl , thiophenolyl , furyl or Thiazolyl.
进一步优选的是,所述取代基R9选自氢、卤素、硝基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷砜基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Further preferably, the substituent R9 is selected from hydrogen, halogen, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halo Cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkane Oxygen, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C 6 alkylsulfone substituted phenyl, selected from hydrogen, halogen, nitro, cyano , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C At least one of 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C 6 alkylsulfone substituted pyridyl, pyrazolyl, thiophene, furyl or thiazolyl.
再进一步优选的是,所述取代基R9选自氢、氟、氯、溴、硝基、甲基、乙基、丙基、异丙基、二氟甲基、环丙基、甲硫基亚甲基、苯基、对氯苯基、对氟苯基、苄基。Still further preferably, the substituent R9 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, propyl, isopropyl, difluoromethyl, cyclopropyl, methylthio Methyl, phenyl, p-chlorophenyl, p-fluorophenyl, benzyl.
本发明提供的通式stru-1所示的吡唑衍生物中,取代基L选自氧、硫、亚甲基、氮。In the pyrazole derivative represented by the general formula stru-1 provided by the present invention, the substituent L is selected from oxygen, sulfur, methylene, and nitrogen.
优选的是,所述取代基L选自氧、硫、亚甲基。Preferably, the substituent L is selected from oxygen, sulfur and methylene.
本发明提供的通式stru-1所示的吡唑衍生物中,取代基Q选自氧、硫。In the pyrazole derivative represented by the general formula stru-1 provided by the present invention, the substituent Q is selected from oxygen and sulfur.
本发明提供的通式stru-1所示的吡唑衍生物中,取代基R10选自氢、卤素、硝基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷基羧酸酯、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基和C1-C20卤代烷硫基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基和C1-C20卤代烷硫基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R10 is selected from hydrogen, halogen, nitro, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkyne C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkyl carboxylate, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio and C 1 -C 20 haloalkylthio substituted phenyl, selected from hydrogen, halogen, nitric acid group, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, At least one of C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio and C 1 -C 20 haloalkylthio is substituted with pyridyl, pyrazolyl, thiophene, furyl or thiazolyl.
优选的是,所述取代基R10选自氢、卤素、硝基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C2-C10烯基、C2-C10卤代烯基、C2-C10炔基、C2-C10卤代炔基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10烷基羧酸酯、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基和C1-C10卤代烷硫基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基和C1-C10卤代烷硫基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Preferably, the substituent R10 is selected from hydrogen, halogen, nitro, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halo Cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 10 haloalkenyl, C 2 -C 10 alkynyl, C 2 -C 10 haloalkynyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 1 -C 10 alkyl carboxylate, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl , C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 Haloalkoxy, C 1 -C 10 alkylthio and C 1 -C 10 haloalkylthio substituted phenyl, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl , C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 - At least one of C 10 alkylthio and C 1 -C 10 haloalkylthio is substituted with pyridyl, pyrazolyl, thiophene, furyl or thiazolyl.
进一步优选的是,所述取代基R10选自氢、卤素、硝基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基羧酸酯、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基和C1-C6卤代烷硫基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基和C1-C6卤代烷硫基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Further preferably, the substituent R10 is selected from hydrogen, halogen, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halo Cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkyl carboxylate, selected from hydrogen, halogen, nitro, cyano , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio and C 1 -C 6 haloalkylthio substituted phenyl, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkane C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 Pyridyl, pyrazolyl, thiophene, furyl or thiazolyl substituted by at least one of -C 6 alkylthio and C 1 -C 6 haloalkylthio.
再进一步优选的是,所述取代基R10选自氢、氟、氯、硝基、C1-C6烷基、C3-C6环烷基、C3-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基羧酸甲酯、C1-C6烷基羧酸乙酯、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、三氟乙氧基和甲硫基中至少一个取代的苯基、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、三氟乙氧基和甲硫基中至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Still further preferably, the substituent R10 is selected from hydrogen, fluorine, chlorine, nitro, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 haloalkyl, C 2 - C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy , C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 methyl carboxylate, C 1 -C 6 ethyl carboxylate, selected from hydrogen, fluorine, Phenyl substituted by at least one of chlorine, bromine, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy and methylthio, selected from hydrogen , fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy and methylthio substituted pyridyl, pyridyl Azolyl, thiophenolyl, furyl or thiazolyl.
本发明提供的通式stru-1所示的吡唑衍生物,作为一种比较优选的方式,所述通式stru-1中:The pyrazole derivatives represented by the general formula stru-1 provided by the present invention, as a more preferred mode, in the general formula stru-1:
R1、R2、R3、R4、R5独立地选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、叔丁基、三氟甲基、甲氧基、乙氧基、三氟甲氧基、二氟甲氧基、二氟乙氧基、甲硫基、三氟甲硫基、三氟乙硫基、甲砜基、甲磺基酯;R1, R2, R3, R4, R5 are independently selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, methoxy, Ethoxy, trifluoromethoxy, difluoromethoxy, difluoroethoxy, methylthio, trifluoromethylthio, trifluoroethylthio, methylsulfonyl, methylsulfonyl ester;
R6选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、环丙基、三氟甲基、二氟甲基、甲氧基、乙氧基、对氯苯基、对氟苯基;R6 is selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, para Chlorophenyl, p-fluorophenyl;
R7选自氢、卤素、硝基、腈基、C1-C5烷基、C1-C5卤代烷基、C1-C5烷氧亚甲基;R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 5 alkyl, C 1 -C 5 haloalkyl, C 1 -C 5 alkoxymethylene;
R8选自甲基、乙基;R8 is selected from methyl, ethyl;
R9选自氢、氟、氯、溴、硝基、甲基、乙基、丙基、异丙基、二氟甲基、环丙基、甲硫基亚甲基、苯基、对氯苯基、对氟苯基、苄基;R9 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, propyl, isopropyl, difluoromethyl, cyclopropyl, methylthiomethylene, phenyl, p-chlorophenyl , p-fluorophenyl, benzyl;
L选自氧、硫、亚甲基;L is selected from oxygen, sulfur, methylene;
Q选自氧、硫;Q is selected from oxygen, sulfur;
R10选自氢、氟、氯、硝基、C1-C6烷基、C3-C6环烷基、C3-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基羧酸甲酯、C1-C6烷基羧酸乙酯、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、三氟乙氧基和甲硫基中至少一个取代的苯基、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、三氟乙氧基和甲硫基中至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。R10 is selected from hydrogen, fluorine, chlorine, nitro, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 methyl carboxylate, C 1 -C 6 ethyl carboxylate, selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, A phenyl group substituted by at least one of methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy and methylthio, selected from hydrogen, fluorine, chlorine, bromine, nitro, Pyridyl, pyrazolyl, thiophene, furyl or Thiazolyl.
本发明提供的通式stru-1所示的吡唑衍生物,作为另一种比较优选的方式,所述通式stru-1中:The pyrazole derivatives represented by the general formula stru-1 provided by the present invention, as another preferred mode, in the general formula stru-1:
R1、R2、R4、R5选自氢;R1, R2, R4, R5 are selected from hydrogen;
R3选自叔丁基;R3 is selected from tert-butyl;
R6选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、环丙基、三氟甲基、二氟甲基、甲氧基、乙氧基、对氯苯基、对氟苯基;R6 is selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, para Chlorophenyl, p-fluorophenyl;
R7选自氢、卤素、硝基、腈基、C1-C5烷基、C1-C5卤代烷基、C1-C5烷氧亚甲基;R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 5 alkyl, C 1 -C 5 haloalkyl, C 1 -C 5 alkoxymethylene;
R8选自甲基、乙基;R8 is selected from methyl, ethyl;
R9选自氢、氟、氯、溴、硝基、甲基、乙基、丙基、异丙基、二氟甲基、环丙基、甲硫基亚甲基、苯基、对氯苯基、对氟苯基、苄基;R9 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, propyl, isopropyl, difluoromethyl, cyclopropyl, methylthiomethylene, phenyl, p-chlorophenyl , p-fluorophenyl, benzyl;
L选自氧、硫、亚甲基;L is selected from oxygen, sulfur, methylene;
Q选自氧、硫;Q is selected from oxygen, sulfur;
R10选自氢、氟、氯、硝基、C1-C6烷基、C3-C6环烷基、C3-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基羧酸甲酯、C1-C6烷基羧酸乙酯、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、甲氧基、乙氧基、三氟甲基、三氟乙氧基和甲硫基中至少一个取代的苯基、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、甲氧基、乙氧基、三氟甲基、三氟乙氧基和甲硫基中至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。R10 is selected from hydrogen, fluorine, chlorine, nitro, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 methyl carboxylate, C 1 -C 6 ethyl carboxylate, selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, A phenyl group substituted by at least one of methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoroethoxy and methylthio, selected from hydrogen, fluorine, chlorine, bromine, nitro, Pyridyl, pyrazolyl, thiophene, furyl or Thiazolyl.
本发明提供的通式stru-1所示的吡唑衍生物,作为最为优选的方式,所述吡唑衍生物选自以下结构式所示化合物中的至少一种:The pyrazole derivatives represented by the general formula stru-1 provided by the present invention, as the most preferred mode, the pyrazole derivatives are selected from at least one of the compounds represented by the following structural formulas:
以上编号表示的吡唑衍生物,优选的是,所述化合物为E式吡唑衍生物,即E式异构体。For the pyrazole derivatives represented by the above numbers, it is preferred that the compound is an E-form pyrazole derivative, that is, an E-form isomer.
本发明提供的通式stru-1所示的吡唑衍生物,所述吡唑衍生物包括选自E式吡唑衍生物和Z式吡唑衍生物中的至少一种。当所述吡唑衍生物包括E式吡唑衍生物和Z式吡唑衍生物时,所述E式吡唑衍生物和Z式吡唑衍生物之间可以以任何比例存在。The present invention provides pyrazole derivatives represented by general formula stru-1, wherein the pyrazole derivatives include at least one selected from E-form pyrazole derivatives and Z-form pyrazole derivatives. When the pyrazole derivatives include E-form pyrazole derivatives and Z-form pyrazole derivatives, the E-form pyrazole derivatives and Z-form pyrazole derivatives may exist in any ratio.
本发明提供的通式stru-1所示的吡唑衍生物,当取代基R1、R2、R4、R5为氢和Q为氧时,作为示例,当所述通式stru-1所示的吡唑衍生物为E式化合物时,所述通式stru-1所示的吡唑衍生物可以是表1所示化合物。For the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, when the substituents R1, R2, R4, R5 are hydrogen and Q is oxygen, as an example, when the pyrazole derivatives represented by the general formula stru-1 When the azole derivative is a compound of formula E, the pyrazole derivative represented by the general formula stru-1 may be a compound shown in Table 1.
表1Table 1
本发明提供的通式stru-1所示的吡唑衍生物,当取代基R1、R2、R4、R5为氢和Q为氧时,作为示例,当所述通式stru-1所示的吡唑衍生物为Z式化合物时,所述通式stru-1所示的吡唑衍生物可以是表2所示化合物。For the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, when the substituents R1, R2, R4, R5 are hydrogen and Q is oxygen, as an example, when the pyrazole derivatives represented by the general formula stru-1 When the azole derivative is a compound of formula Z, the pyrazole derivative represented by the general formula stru-1 may be a compound shown in Table 2.
表2Table 2
本发明提供的部分化合物的物性数据如下表3。The physical data of some compounds provided by the present invention are shown in Table 3 below.
表3table 3
本发明还提供了通式stru-1所示的吡唑衍生物的制备方法,所述方法包括:The present invention also provides a method for preparing pyrazole derivatives represented by the general formula stru-1, the method comprising:
所述X选自卤素。Said X is selected from halogen.
本发明提供的制备方法,所述碱:优选的是,选自有机碱和无机碱中的至少一种;进一步优选的是,选自碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠、氢氧化钾、氢化钠、醇钠和醇钾中的至少一种。In the preparation method provided by the invention, the base: preferably, at least one selected from organic bases and inorganic bases; more preferably, selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, hydrogen At least one of sodium oxide, potassium hydroxide, sodium hydride, sodium alcoholate and potassium alcoholate.
本发明提供的制备方法,所述酸:优选的是,选自有机酸和无机酸中的至少一种;进一步优选的是,选自盐酸、硫酸和乙酸中的至少一种。In the preparation method provided by the present invention, the acid: preferably, at least one selected from organic acids and inorganic acids; more preferably, at least one selected from hydrochloric acid, sulfuric acid and acetic acid.
本发明提供的制备方法,所述溶剂:优选的是,独立地选自质子性溶剂和非质子性溶剂中的至少一种;进一步优选的是,独立地选自丙酮、甲基乙基酮、四氢呋喃、乙腈、N、N-二甲基甲酰胺、甲苯和氯苯中的至少一种。In the preparation method provided by the invention, the solvent: preferably, independently selected from at least one of protic solvents and aprotic solvents; further preferably, independently selected from acetone, methyl ethyl ketone, At least one of tetrahydrofuran, acetonitrile, N,N-dimethylformamide, toluene and chlorobenzene.
本发明提供的制备方法,所述X选自卤素,优选的是,所述X选自氯、溴或碘。In the preparation method provided by the present invention, said X is selected from halogen, preferably, said X is selected from chlorine, bromine or iodine.
本发明提供的制备方法,所述催化剂选自碘化钾、碘化钠和相转移催化剂中的至少一种。In the preparation method provided by the invention, the catalyst is selected from at least one of potassium iodide, sodium iodide and phase transfer catalysts.
本发明还提供一种农用杀虫、杀螨剂,所述杀虫、杀螨剂含有0.1~99%质量百分含量的通式stru-1所示吡唑衍生物。所述杀虫、杀螨剂中,除通式stru-1所示吡唑衍生物外,还可以进一步包括本行业常用的载体和助剂。The present invention also provides an agricultural insecticide and acaricide, which contains 0.1-99% by mass of the pyrazole derivative represented by the general formula stru-1. In the insecticide and acaricide, in addition to the pyrazole derivative represented by the general formula stru-1, it may further include carriers and auxiliaries commonly used in this industry.
本发明提供的通式stru-1所示的吡唑衍生物,适合用于防治害虫,特别适合用于防治作物上的成螨、若螨、螨卵、蚜虫和飞虱中的至少一种。所述吡唑衍生物很适合用于防治藤蔓植物、水果、园艺、农业、动物康、森林、贮藏产品和材料和卫生领域中的动物害虫。The pyrazole derivatives represented by the general formula stru-1 provided by the present invention are suitable for controlling pests, especially for controlling at least one of adult mites, nymphs, mite eggs, aphids and planthoppers on crops. The pyrazole derivatives are very suitable for controlling animal pests in the fields of vines, fruit, horticulture, agriculture, animal health, forestry, stored products and materials and hygiene.
优选的是,所述吡唑衍生物用于防治选自等足目、倍足目、唇足目、综合目、缨尾目、弹尾目、直翅目、蜚蠊目、革翅目、等翅目、虱目、缨翅目、异翅目、同翅目、鳞翅目、鞘翅目、膜翅目、双翅目、蚤目、蛛形纲和植物寄生线虫中的至少一种。Preferably, the pyrazole derivatives are used for the prevention and treatment of At least one of the order, Lepidoptera, Thysanoptera, Heteroptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Fleaorder, Arachnida and plant parasitic nematodes.
所述等足目(Isopoda),例如栉水虱(Oniscus asellus)、鼠(Armadillidiumvulgare)、球鼠妇(Porcellio scaber)。From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare, and Porcellio scaber.
所述倍足目(Diplopoda),例如,Blaniulus guttulatus。From the order of the Diplopoda, for example, Blaniulus guttulatus.
所述唇足目(Chilopoda),例如,Geophilus carpophagus、Scutigera spp.。From the order of the Chilopoda, for example, Geophilus carpophagus, Scutigera spp.
所述综合目(Symphyla),例如,白松虫(Scutigerella immaculata)。Said Symphyla, for example, white pine worms (Scutigerella immaculata).
所述缨尾目(Thysanura),例如,衣鱼(Lepisma saccharina)。From the order of Thysanura, for example, silverfish (Lepisma saccharina).
所述弹尾目(Collembola),例如,武装棘跳虫(Onychiurus armatus)。From the order of the Collembola, for example, Onychiurus armatus.
所述直翅目(Orthoptera),例如,家蟋(Acheta domesticus)、蝼蛄属(Gryllotalpa spp.)、非洲飞蝗(Locusta migratoria)、黑蝗(Melanoplus spp.)、沙漠蝗(Schistocer cagregaria)。The Orthoptera includes, for example, house cricket (Acheta domesticus), mole cricket (Gryllotalpa spp.), African migratoria (Locusta migratoria), black locust (Melanoplus spp.), desert locust (Schistocer cagregaria).
所述蜚蠊目(Blattaria),例如,东方蟑螂(Blatta orientalis)、美洲蟑(Periplanet aamericana)、佛罗里达蟑螂(Leucophae amaderae)、德国蟑螂(Blattellagermanica)。From the order of the Blattaria, for example, Oriental cockroach (Blatta orientalis), American cockroach (Periplanet aamericana), Florida cockroach (Leucophae amaderae), German cockroach (Blattella germanica).
所述革翅目(Dermaptera),例如,欧洲球螋(Forficula auricularia)。From the order of the Dermaptera, for example, Forficula auricularia.
所述等翅目(Isoptera),例如,散白蚁属(Reticulitermes spp.)。From the order of the Isoptera, for example, Reticulitermes spp.
所述虱目(Phthiraptera),例如,人体虱(Pediculus humanuscorporis)、血虱属(Haematopinus spp.)、毛虱属(Linognathus spp.)、嚼虱属(Trichodectes spp.)、畜虱属(Damalinia spp.)。From the order of the Phthiraptera, for example, Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp. ).
所述缨翅目(Thysanoptera),例如,温室条篱蓟马(Hercinothrips femoralis)、烟蓟马(Thrips tabaci)、棕榈蓟马(Thrips palmi)、西花蓟马(Frankliniellaoccidentalis)。The Thysanoptera includes, for example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.
所述异翅目(Heteroptera),例如,扁盾蝽属(Eurygaster spp.)、居间棉红蝽(Dysdercus intermedius)、方背皮蝽(Piesma quadrata)、温带臭虫(Cimexlectularius)、长红锥蝽(Rhodnius prolixus)、锥蝽属(Triatoma spp.)。The Heteroptera (Heteroptera), for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimexlectularius, triatomine longum ( Rhodnius prolixus), Triatoma spp.
所述同翅目(Homoptera),例如,白粉虱(Aleurodes brassicae)、烟粉(Bemisiatabaci)、温室粉虱(Trialeurodes vaporariorum)、棉蚜(Aphis gossypii)、甘蓝蚜(Brevicoryne brassicae)、茶藨隐瘤蚜(Cryptomyzus ribis)、黑豆蚜(Aphis fabae)、苹果黄蚜(Aphis pomi)、苹果绵蚜(Eriosoma lanigerum)、梅大尾蚜(Hyalopterusarundinis)、葡萄根瘤蚜(Phylloxera vastatrix)、瘿绵蚜属(Pemphigus spp.)、麦长管蚜(Macrosiphum avenae)、瘤蚜属(Myzus spp.)、忽布疣蚜(Phorodon humuli)、禾谷缢管蚜(Rhopalosiphum padi)、小绿叶蝉属(Empoasca spp.)、Euscelis bilobatus、稻黑尾叶蝉(Nephotettix cincticeps)、介壳虫(Lecanium corni)、榄珠蜡蚧(Saissetia oleae)、灰飞虱(Laodelphax striatellus)、褐飞虱(Nilaparvatalugens)、红圆蚧(Aonidiellaaurantii)、常春藤圆盾蚧(Aspidiotus hederae)、粉蚧属种(Pseudococcus spp.)、木虱属种(Psylla spp.)。From the order of the Homoptera, for example, whitefly (Aleurodes brassicae), tobacco powder (Bemisiatabaci), greenhouse whitefly (Trialeurodes vaporariorum), cotton aphid (Aphis gossypii), cabbage aphid (Brevicoryne brassicae), tea currant aphid Aphid (Cryptomyzus ribis), black bean aphid (Aphis fabae), apple yellow aphid (Aphis pomi), apple aphid (Eriosoma lanigerum), plum tail aphid (Hyalopterus arundinis), grape phylloxera (Phylloxera vastatrix), gall aphid ( Pemphigus spp.), Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp. ), Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvatalugens, Aonidiellaaurantii , Aspidiotus hederae, Pseudococcus spp., Psylla spp.
所述鳞翅目(Lepidoptera),例如,红铃麦蛾(Pectinophora gossypiella)、松尺蠖(Bupalus piniarius)、冬尺蛾(Cheimatobia brumata)、苹细蛾(Lithocolletisblancardella)、苹果巢蛾(Hyponomeuta padella)、菜蛾(Plutella xylostella)、黄褐天幕毛虫(Malacosoma neustria)、黄毒蛾(Euproctis chrysorrhoea)、毒蛾属(Lymantriaspp.)、棉潜蛾(Bucculatrix thurberiella)、桔潜蛾(Phyllocrnistis citrella)、地老虎属(Agrotis spp.)、切根虫属(Euxoa spp.)、脏切夜蛾属(Feltia spp.)、埃及金刚钻(Earias insulana)、实夜蛾属(Heliothis spp.)、甘蓝夜蛾(Mamestra brassicae)、小眼夜蛾(Panolis flammea)、灰翅夜蛾属(Spodoptera spp.)、粉纹夜蛾(Trichoplusia ni)、苹果小卷蛾(Carpocap sapomonella)、菜粉蝶属(Pieris spp.)、禾草螟属(Chilo spp.)、玉米螟(Pyrausta nubilalis)、地中海粉斑螟(Ephestia kuehniella)、大蜡螟(Galleriamellonella)、幕谷蛾(Tineola bisselliella)、袋谷蛾(Tinea pellionella)、褐织蛾(Hofmannophilap seudospretella)、亚麻黄卷蛾(Cacoecia podana)、枞色卷蛾(Choristoneura fumiferana)、葡萄果蠹蛾(Clysia ambiguella)、茶长卷蛾(Homonamagnanima)、栎绿卷蛾(Tortrix viridana)、稻纵卷叶螟属种(Cnaphalocerus spp.)、水稻负泥虫(Oulema oryzae)。From the order of Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantrias pp., Bucculatrix thurberiella, Phyllocrnistis citrella, Cutworm ( Agrotis spp.), Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae , Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocap sapomonella, Pieris spp., Grass Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Brown welt moth (Hofmannophilap seudospretella), flax yellow tortrix (Cacoecia podana), fir-colored tortrix (Choristoneura fumiferana), grape fruit beetle (Clysia ambiguella), tea long tortrix (Homonamagnanima), oak green tortrix (Tortrix viridana), rice vertical Cnaphalocerus spp., Oulema oryzae.
所述鞘翅目(Coleoptera),例如,家具窃蠹(Anobium punctatum)、谷蠹(Rhizopertha dominica)、恶条豆象(Bruchidius obtectus)、菜豆象(Acanthoscelidesobtectus)、北美家天牛(Hylotrupes bajulus)、杨树萤叶甲(Agelastica alni)、马铃薯甲虫(Leptinotarsa decemlineata)、辣根猿叶虫(Phaedon cochleariae)、叶甲属(Diabrotica spp.)、油菜金头跳甲(Psylliodes chrysocephala)、墨西哥豆瓢虫(Epilachna varivestis)、Atomaria spp.、锯谷盗(Oryzaephilus surinamensis)、花象属种(Anthonomus spp.)、谷象属(Sitophilus spp.)、黑葡萄耳象(Otiorrhynchussulcatus)、香蕉球茎象甲(Cosmopolites sordidus)、白菜龟象(Ceuthorrhynchusassimilis)、紫苜蓿叶象(Hypera postica)、皮蠹属(Dermestes spp.)、斑皮蠹属(Trogoderma spp.)、圆皮蠹属(Anthrenus spp.)、毛皮蠹属(Attagenus spp.)、粉蠹属(Lyctus spp.)、油菜花露尾甲(Meligethes aeneus)、蛛甲属(Ptinus spp.)、黄蛛甲(Niptus bololeucus)、裸蛛甲(Gibbium psylloides)、拟谷盗属(Tribolium spp.)、黄粉虫(Tenebrio molitor)、叩甲属(Agriotes spp.)、宽胸叩头虫属(Conoderus spp.)、西方五月鳃角金龟(Melolontha melolontha)、马铃薯鳃角金龟(Amphimallon solstitialis)、褐新西兰肋翅鳃角金龟(Costelytra zealandica)、稻根象(Lissorhoptrusoryzophilus)。The Coleoptera (Coleoptera), for example, furniture beetle (Anobium punctatum), grain beetle (Rhizopertha dominica), evil strip bean elephant (Bruchidius obtectus), bean elephant (Acanthoscelides obtectus), North American house beetle (Hylotrupes bajulus), poplar firefly Leaf beetle (Agelastica alni), potato beetle (Leptinotarsa decemlineata), horseradish beetle (Phaedon cochleariae), leaf beetle (Diabrotica spp.), rape beetle (Psylliodes chrysocephala), Mexican bean beetle (Epilachna varivestis ), Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchussulcatus, Cosmopolites sordidus, Cabbage turtle elephant (Ceuthorrhynchus assimilis), alfalfa leaf elephant (Hypera postica), dermestes spp., trogoderma spp., anthrenus spp., attagenus spp.), Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus bololeucus, Gibbium psylloides, Pseudomonas Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Mellontha melolontha, Potato beetle (Amphimallon solstitialis), brown New Zealand ribwing beetle (Costelytra zealandica), rice root elephant (Lissorhoptrusoryzophilus).
所述膜翅目(Hymenoptera),例如,松叶蜂属(Diprion spp.)、实叶蜂属(Hoplocampa spp.)、毛蚁属(Lasius spp.)、小家蚁(Monomorium pharaonis)、胡蜂属(Vespa spp.)。From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa (Vespa spp.).
所述双翅目(Diptera),例如,伊蚊属(Aedes spp.)、按蚊属(Anopheles spp.)、库蚊属(Culex spp.)、黑腹果蝇(Drosophila melanogaster)、家蝇属(Musca spp.)、厕蝇属(Fannia spp.)、红头丽蝇(Calliphora vicina)、绿蝇属(Lucilia spp.)、金蝇属(Chrysomyia spp.)、黄蝇属(Cuterebra spp.)、胃蝇属(Gastrophilus spp.)、虱蝇属(Hyppobosca spp.)、螫蝇属(Stomoxys spp.)、狂蝇属(Oestrus spp.)、皮蝇属(Hypodermaspp.)、虻属(Tabanus spp.)、花园毛蚊(Bibio hortulanus)、瑞典麦秆蝇(Oscinellafrit)、草种蝇属(Phorbia spp.)、藜泉蝇(Pegomyia hyoscyami)、地中海蜡实蝇(Ceratitis capitata)、橄榄大实蝇(Dacus oleae)、欧洲大蚊(Tipula paludosa)、黑蝇属(Hylemyia spp.)、斑潜蝇属(Liriomyza spp.)。The Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp. (Musca spp.), Fannia spp., Calliphora vicina, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypodermas pp., Tabanus spp. ), Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Olive Bacteria ( Dacus oleae), Tipula paludosa, Hylemyia spp., Liriomyza spp.
所述蚤目(Siphonaptera),例如,印鼠客蚤(Xenopsylla cheopis)、角叶蚤属(Ceratophyllus spp.)。Said from the order of Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spp.
所述蛛形纲(Arachnida),例如,中东金蝎(Scorpio maurus)、黑寡妇蜘蛛(Latrodectus mactans)、粗脚粉螨(Acarus siro)、锐缘蜱属种(Argas spp.)、钝缘蜱属(Ornithodoros spp.)、鸡皮刺螨(Dermanyssus gallinae)、茶藨瘿螨(Erio phyesribis)、桔芸锈螨(Phyllocoptruta oleivora)、牛蜱属(Boophilus spp.)、扇头蜱属(Rhipicephalus spp.)、花蜱属(Amblyomma spp.)、璃眼蜱属(Hyalomma spp.)、硬蜱属(Ixodes spp.)、痒螨属(Psoroptes spp.)、皮螨属(Chorioptes spp.)、疥螨属(Sarcoptesspp.)、跗线螨属(Tarsonemus spp.)、苜蓿苔螨(Bryobia praetiosa)、全爪螨属(Panonychus spp.)、叶螨属(Tetranychus spp.)、半跗线螨属(Hemitarsonemus spp.)、短须螨属(Brevipalpus spp.)。Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp. Ornithodoros spp., Dermanyssus gallinae, Erio phyesribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp. ), Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Scabies Sarcoptesspp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp.), Brevipalpus spp.
所述植物寄生线虫包括,例如,短体线虫属(Pratylenchus spp.)、相似穿孔线虫(Radopholus similis)、起绒草茎线虫(Ditylenchus dipsaci)、半穿刺线虫(Tylenchulussemipenetrans)、异皮线虫属(Heterodera spp.)、球异皮线虫属(Globodera spp.)、根结线虫属(Meloidogyne spp.)、滑刃线虫属(Aphelenchoides spp.)、长针线虫属(Longidorus spp.)、剑线虫属(Xiphinema spp.)、毛刺线虫属(Trichodorus spp.)、伞滑刃线虫属(Bursaphelenchus spp.)。The plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp.), Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp.), Trichodorus spp., Bursaphelenchus spp.
附图说明Description of drawings
图1为化合物251的单晶衍射图。Figure 1 is a single crystal diffraction pattern of compound 251.
具体实施方式Detailed ways
下面结合具体实施例来对本发明进行进一步说明,但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到,本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to these specific implementations. Those skilled in the art will realize that the present invention covers all alternatives, modifications and equivalents as may be included within the scope of the claims.
一、化合物制备1. Compound Preparation
实施例1、中间体制备Embodiment 1, intermediate preparation
(1)中间体1-乙基-3-甲基-5-吡唑甲酸乙酯合成(1) Synthesis of intermediate 1-ethyl-3-methyl-5-pyrazole carboxylic acid ethyl ester
将154.1g(1mol)中间体A加入到1000ml的烧瓶中,加入500ml乙腈和138g碳酸钾,然后加入1mol硫酸二乙酯,体系搅拌加热回流反应,板层析跟踪大约3hr反应完成,体系过滤,母液用旋转蒸发仪蒸干,残留物进行减压蒸馏得140g的中间体B,收率为77.0%。154.1g (1mol) intermediate A is added in the flask of 1000ml, add 500ml acetonitrile and 138g potassium carbonate, then add 1mol diethyl sulfate, the system is stirred and heated to reflux reaction, plate chromatography traces about 3hr reaction is completed, system filtration, The mother liquor was evaporated to dryness with a rotary evaporator, and the residue was distilled under reduced pressure to obtain 140 g of Intermediate B with a yield of 77.0%.
(2)中间体1-乙基-3-甲基-4-氯-5-吡唑甲酸乙酯合成(2) Synthesis of intermediate 1-ethyl-3-methyl-4-chloro-5-pyrazole ethyl carboxylate
将18.2g(0.1mol)中间体B加入到100ml的烧瓶中,加入50ml二氯乙烷和138g碳酸钾,然后加入0.11mol磺酰氯,体系搅拌加热回流反应,板层析跟踪大约2.5hr反应完成,母液蒸干,残留物不处理直接用于下一步反应。Add 18.2g (0.1mol) of intermediate B to a 100ml flask, add 50ml of dichloroethane and 138g of potassium carbonate, then add 0.11mol of sulfonyl chloride, the system is stirred and heated to reflux, and the reaction is completed by plate chromatography tracking about 2.5hr , the mother liquor was evaporated to dryness, and the residue was directly used in the next reaction without treatment.
(3)中间体1-乙基-3-甲基-4-甲基-5-吡唑甲酸乙酯合成(3) Synthesis of intermediate 1-ethyl-3-methyl-4-methyl-5-pyrazolecarboxylic acid ethyl ester
中间体D参考JP2001342178A提供方法制得。Intermediate D was prepared by referring to the method provided in JP2001342178A.
(4)中间体1-甲基-3-甲基-4-甲基-5-吡唑甲酸乙酯合成(4) Synthesis of intermediate 1-methyl-3-methyl-4-methyl-5-pyrazole carboxylic acid ethyl ester
中间体D-1参考JP2001342178A提供方法制得。Intermediate D-1 was prepared by referring to the method provided in JP2001342178A.
(5)中间体1-甲基-3-甲基-4-氯-5-吡唑甲酸乙酯合成(5) Synthesis of intermediate 1-methyl-3-methyl-4-chloro-5-pyrazole ethyl carboxylate
中间体C-1制备方法同中间体C。The preparation method of intermediate C-1 is the same as that of intermediate C.
(6)中间体F制备(6) Preparation of Intermediate F
常规操作:将取代醛与催化量氯化锌在反应器中搅拌均匀,在冷却下缓慢滴加取代酰氯,滴加完毕后在低温下继续搅拌1-2hr,然后升温,继续反应5hr,然后通过减压蒸馏方式提纯。Conventional operation: Stir the substituted aldehyde and the catalytic amount of zinc chloride in the reactor evenly, slowly add the substituted acid chloride dropwise under cooling, continue to stir at low temperature for 1-2hr after the dropwise addition, then raise the temperature, continue the reaction for 5hr, and then pass Purification by vacuum distillation.
中间体乙酸氯代甲酯制备:Preparation of intermediate chloromethyl acetate:
在冷却到0℃下将50g(0.6mol)乙酰氯滴加到85g多聚甲醛和1.75g氯化锌混和物中,大约2hr滴加完毕,然后反应体系升至室温,反应1hr,然后加热到90℃继续反应10hr,冷却,过滤去除固体,减压蒸馏得中间体F-1 45g。50g (0.6mol) of acetyl chloride was added dropwise to 85g of paraformaldehyde and 1.75g of zinc chloride mixture under cooling to 0°C, and the dropwise addition was completed in about 2 hours, then the reaction system was raised to room temperature, reacted for 1 hour, and then heated to The reaction was continued at 90°C for 10 hr, cooled, filtered to remove the solid, and distilled under reduced pressure to obtain 45 g of intermediate F-1.
(7)中间体H制备(7) Preparation of Intermediate H
常规操作:在冷却下将氯甲酸氯代酯缓慢滴加到取代醇和三乙胺溶液中,滴加完毕后在低温下继续搅拌1-2hr,然后升温,室温继续反应1hr,然后过滤,蒸出溶剂,然后通过减压蒸馏方式提纯得中间体H。Conventional operation: Slowly add chloroformate chloroformate into the solution of substituted alcohol and triethylamine dropwise under cooling, continue to stir at low temperature for 1-2hr after the dropwise addition, then raise the temperature, continue to react at room temperature for 1hr, then filter and evaporate solvent, and then purified by vacuum distillation to obtain intermediate H.
中间体H-1制备:Preparation of intermediate H-1:
在冷却到0℃下将71.5g(0.5mol)1-氯乙基氯甲酸酯滴加到40g和52.0g三乙胺250ml甲苯溶液中,大约2hr滴加完毕,然后反应体系升至室温,反应1hr,过滤去除固体,减压蒸馏得中间体H-1为78.5g。After cooling to 0°C, 71.5g (0.5mol) of 1-chloroethyl chloroformate was added dropwise to 40g and 52.0g of triethylamine in 250ml of toluene solution, the addition was completed in about 2 hours, and then the reaction system rose to room temperature. After reacting for 1 hr, the solid was removed by filtration, and 78.5 g of intermediate H-1 was obtained by distillation under reduced pressure.
(8)中间体TA-1制备(8) Preparation of intermediate TA-1
将17.3g对叔丁基苯乙腈溶入70ml无水THF中,体系冷却到-5℃加入等摩尔固体甲醇钠,然后在搅拌下滴入等摩尔中间体B,2hr滴加完毕,继续搅拌1.5hr,然后升到室温,继续搅拌反应2hr,反应完成后蒸出THF,残留物用水溶解,用盐酸中和到pH为4左右,用乙酸乙酯萃取,用无水硫酸钠干燥,蒸出乙酸乙酯得中间体TA-1,不需提纯直接用于下一步反应。Dissolve 17.3g of p-tert-butylphenylacetonitrile in 70ml of anhydrous THF, cool the system to -5°C, add equimolar solid sodium methoxide, then drop in equimolar intermediate B under stirring, after 2hr dropwise addition, continue stirring for 1.5 hr, then raised to room temperature, continued to stir for 2 hr, evaporated THF after the reaction was completed, dissolved the residue in water, neutralized with hydrochloric acid to a pH of about 4, extracted with ethyl acetate, dried with anhydrous sodium sulfate, and evaporated acetic acid The intermediate TA-1 was obtained from ethyl ester, which was directly used in the next reaction without purification.
(9)中间体TA-2制备(9) Preparation of intermediate TA-2
将17.3g对叔丁基苯乙腈溶入70ml无水THF中,体系冷却到-5℃加入等摩尔固体叔丁醇钾,然后在搅拌下滴入等摩尔中间体C,2.5hr滴加完毕,继续搅拌2.0hr,然后升到室温,继续搅拌反应2hr,反应完成后蒸出THF,残留物用水溶解,用盐酸中和到pH为4左右,用乙酸乙酯萃取,用无水硫酸钠干燥,蒸出乙酸乙酯得中间体TA-2,不需提纯直接用于下一步反应。Dissolve 17.3g of p-tert-butylphenylacetonitrile into 70ml of anhydrous THF, cool the system to -5°C, add equimolar solid potassium tert-butoxide, and then drop in equimolar intermediate C with stirring, and the addition is completed after 2.5hr. Continue to stir for 2.0hr, then rise to room temperature, continue to stir and react for 2hr, evaporate THF after the reaction is completed, dissolve the residue in water, neutralize with hydrochloric acid to a pH of about 4, extract with ethyl acetate, and dry with anhydrous sodium sulfate. Ethyl acetate was distilled off to obtain intermediate TA-2, which was directly used in the next reaction without purification.
(10)中间体TA-3制备(10) Preparation of intermediate TA-3
将17.3g对叔丁基苯乙腈溶入70ml甲基叔丁基醚中,体系冷却到-5℃加入等摩尔固体叔丁醇钾,然后在搅拌下滴入等摩尔中间体D,3.0hr滴加完毕,继续搅拌2.0hr,然后升到室温,继续搅拌反应2hr,反应完成后蒸出甲基叔丁基醚,残留物用水溶解,用盐酸中和到pH为4左右,用乙酸乙酯萃取,用无水硫酸钠干燥,蒸出乙酸乙酯得中间体TA-3,不需提纯直接用于下一步反应。Dissolve 17.3g of p-tert-butylphenylacetonitrile into 70ml of methyl tert-butyl ether, cool the system to -5°C, add equimolar solid potassium tert-butoxide, and then drop in equimolar intermediate D with stirring, drop for 3.0hr After the addition, continue to stir for 2.0 hr, then rise to room temperature, continue to stir for 2 hr, after the reaction is completed, distill out methyl tert-butyl ether, dissolve the residue in water, neutralize with hydrochloric acid to a pH of about 4, and extract with ethyl acetate , dried with anhydrous sodium sulfate, and distilled off ethyl acetate to obtain intermediate TA-3, which was directly used in the next reaction without purification.
(11)中间体TA-4制备(11) Preparation of intermediate TA-4
将17.3g对叔丁基苯乙腈溶入70ml无水THF中,体系冷却到-5℃加入等摩尔固体甲醇钠,然后在搅拌下滴入等摩尔中间体M,2hr滴加完毕,继续搅拌1.5hr,然后升到室温,继续搅拌反应2hr,反应完成后蒸出THF,残留物用水溶解,用盐酸中和到pH为4左右,用乙酸乙酯萃取,用无水硫酸钠干燥,蒸出乙酸乙酯得中间体TA-1,不需提纯直接用于下一步反应。Dissolve 17.3g of p-tert-butylphenylacetonitrile into 70ml of anhydrous THF, cool the system to -5°C, add equimolar solid sodium methoxide, then drop in equimolar intermediate M with stirring, after 2hr dropwise addition, continue to stir for 1.5 hr, then raised to room temperature, continued to stir for 2 hr, evaporated THF after the reaction was completed, dissolved the residue in water, neutralized with hydrochloric acid to a pH of about 4, extracted with ethyl acetate, dried with anhydrous sodium sulfate, and evaporated acetic acid The intermediate TA-1 was obtained from ethyl ester, which was directly used in the next reaction without purification.
中间体TA-5制备:Preparation of intermediate TA-5:
将17.3g对叔丁基苯乙腈溶入70ml无水THF中,体系冷却到-5℃加入等摩尔固体叔丁醇钾,然后在搅拌下滴入等摩尔中间体C,2.5hr滴加完毕,继续搅拌2.0hr,然后升到室温,继续搅拌反应2hr,反应完成后蒸出THF,残留物用水溶解,用盐酸中和到pH为4左右,用乙酸乙酯萃取,用无水硫酸钠干燥,蒸出乙酸乙酯得中间体TA-5,不需提纯直接用于下一步反应。Dissolve 17.3g of p-tert-butylphenylacetonitrile into 70ml of anhydrous THF, cool the system to -5°C, add equimolar solid potassium tert-butoxide, and then drop in equimolar intermediate C with stirring, and the addition is completed after 2.5hr. Continue to stir for 2.0hr, then rise to room temperature, continue to stir and react for 2hr, evaporate THF after the reaction is completed, dissolve the residue in water, neutralize with hydrochloric acid to a pH of about 4, extract with ethyl acetate, and dry with anhydrous sodium sulfate. Ethyl acetate was distilled off to obtain intermediate TA-5, which was directly used in the next reaction without purification.
中间体TA-6制备:Preparation of intermediate TA-6:
将17.3g对叔丁基苯乙腈溶入70mlTHF中,体系冷却到-5℃加入等摩尔固体叔丁醇钾,然后在搅拌下滴入等摩尔中间体D-1,3.0hr滴加完毕,继续搅拌2.0hr,然后升到室温,继续搅拌反应2hr,反应完成后蒸出甲基叔丁基醚,残留物用水溶解,用盐酸中和到pH为4左右,用乙酸乙酯萃取,用无水硫酸钠干燥,蒸出乙酸乙酯得中间体TA-3,不需提纯直接用于下一步反应。Dissolve 17.3g of p-tert-butylphenylacetonitrile into 70ml of THF, cool the system to -5°C, add equimolar solid potassium tert-butoxide, and then add equimolar intermediate D-1 dropwise under stirring. After 3.0hr dropwise addition, continue Stir for 2.0hr, then rise to room temperature, continue to stir and react for 2hr, evaporate methyl tert-butyl ether after the reaction is completed, dissolve the residue in water, neutralize with hydrochloric acid to a pH of about 4, extract with ethyl acetate, and use anhydrous Dry over sodium sulfate, distill off ethyl acetate to obtain intermediate TA-3, which is directly used in the next reaction without purification.
实施例2、目标化合物制备Embodiment 2, target compound preparation
(1)目标化合物226(1) Target compound 226
将0.31g(0.001mol)中间体TA-1和0.12g(0.0011mol)中间体F-1,0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中,然后加热回流反应7hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,蒸出乙腈,残留物柱层析提纯得产物0.32g,收率为84%。Add 0.31g (0.001mol) of intermediate TA-1 and 0.12g (0.0011mol) of intermediate F-1, 0.15g of sodium carbonate and catalytic amount of sodium iodide into 25ml of acetonitrile, then heat to reflux for 7hrs, and follow the plate chromatography After the reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.32 g of the product with a yield of 84%.
(2)目标化合物251(2) Target compound 251
将31g(0.1mol)中间体TA-1和13g(0.11mol)中间体F-2,15碳酸钠以及催化量碘化钠加入到250ml乙腈中,然后加热回流反应10hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,蒸出乙腈,残留物柱层析提纯得产物35.1g,收率为89%。Add 31g (0.1mol) of intermediate TA-1 and 13g (0.11mol) of intermediate F-2, 15 sodium carbonate and a catalytic amount of sodium iodide into 250ml of acetonitrile, then heat and reflux for 10 hours, and follow the completion of the reaction by plate chromatography , the reaction system was cooled to room temperature, the solid was filtered off, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 35.1 g of the product with a yield of 89%.
(3)目标化合物259(3) Target compound 259
将0.31g(0.001mol)中间体TA-1和0.13g(0.0011mol)中间体F-3,0.15碳酸钠以及催化量碘化钠加入到25ml丙酮中,然后加热回流反应12hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,蒸出乙腈,残留物柱层析提纯得产物0.28g,收率为66%。Add 0.31g (0.001mol) of intermediate TA-1 and 0.13g (0.0011mol) of intermediate F-3, 0.15g of sodium carbonate and catalytic amount of sodium iodide into 25ml of acetone, then heat and reflux for 12hrs, and follow the plate chromatography After the reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.28 g of the product with a yield of 66%.
(4)目标化合物326(4) Target compound 326
将0.34g(0.001mol)中间体TA-2和0.13g(0.0011mol)中间体F-2,0.15碳酸钠以及催化量碘化钠加入到25N,N-二甲基甲酰胺中,然后加热70℃反应4hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,减压蒸出溶剂,残留物柱层析提纯得产物0.24g,收率为56%。0.34g (0.001mol) of intermediate TA-2 and 0.13g (0.0011mol) of intermediate F-2, 0.15 sodium carbonate and catalytic amount of sodium iodide were added to 25N, N-dimethylformamide, then heated for 70 The reaction was carried out at ℃ for 4 hours, and the completion of the reaction was tracked by plate chromatography. The reaction system was cooled to room temperature, the solid was filtered off, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography to obtain 0.24 g of the product, with a yield of 56%.
(5)目标化合物401(5) Target compound 401
将0.32g(0.001mol)中间体TA-2和0.13g(0.0011mol)中间体F-2,0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中,然后加热回流反应11hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,减压蒸出溶剂,残留物柱层析提纯得产物0.29g,收率为71%。Add 0.32g (0.001mol) of intermediate TA-2 and 0.13g (0.0011mol) of intermediate F-2, 0.15g of sodium carbonate and a catalytic amount of sodium iodide into 25ml of acetonitrile, then heat and reflux for 11hr, follow up by plate chromatography After the reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography to obtain 0.29 g of the product with a yield of 71%.
(6)目标化合物105(6) Target compound 105
将0.33g(0.1mol)中间体TA-5和0.18g(0.11mol)中间体F-4,0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中,然后加热回流反应11hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,蒸出乙腈,残留物柱层析提纯得产物0.25g,收率为55%。Add 0.33g (0.1mol) of intermediate TA-5 and 0.18g (0.11mol) of intermediate F-4, 0.15g of sodium carbonate and catalytic amount of sodium iodide into 25ml of acetonitrile, then heat and reflux for 11hr, follow up by plate chromatography After the reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.25 g of the product with a yield of 55%.
(7)目标化合物4(7) Target compound 4
将0.295g(0.1mol)中间体TA-4和0.15g(0.11mol)中间体F-6,0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中,然后加热回流反应5hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,蒸出乙腈,残留物柱层析提纯得产物0.31g,收率为78%。Add 0.295g (0.1mol) of intermediate TA-4 and 0.15g (0.11mol) of intermediate F-6, 0.15g of sodium carbonate and a catalytic amount of sodium iodide into 25ml of acetonitrile, then heat and reflux for 5hrs, and follow the plate chromatography After the reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.31 g of the product with a yield of 78%.
(8)目标化合物91(8) Target compound 91
将0.33g(0.1mol)中间体TA-5和0.18g(0.11mol)中间体F-4,0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中,然后加热回流反应11hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,蒸出乙腈,残留物柱层析提纯得产物0.25g,收率为55%。Add 0.33g (0.1mol) of intermediate TA-5 and 0.18g (0.11mol) of intermediate F-4, 0.15g of sodium carbonate and a catalytic amount of sodium iodide into 25ml of acetonitrile, then heat and reflux for 11hr, and follow the plate chromatography After the reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.25 g of the product with a yield of 55%.
(9)目标化合物548(9) Target compound 548
将0.31g(0.001mol)中间体TA-1和0.16g(0.0011mol)中间体H-1,0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中,然后加热回流反应6hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,蒸出乙腈,残留物柱层析提纯得产物0.33g,收率为78%。Add 0.31g (0.001mol) of intermediate TA-1 and 0.16g (0.0011mol) of intermediate H-1, 0.15g of sodium carbonate and a catalytic amount of sodium iodide into 25ml of acetonitrile, then heat and reflux for 6hr, followed by plate chromatography After the reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.33 g of the product with a yield of 78%.
(10)目标化合物739(10) Target compound 739
将0.34g(0.001mol)中间体TA-2和0.13g(0.0011mol)中间体H-2,0.15碳酸钾以及催化量碘化钠加入到25N,N-二甲基甲酰胺中,然后加热70℃反应5hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,减压蒸出溶剂,残留物柱层析提纯得产物0.28g,收率为65%。0.34g (0.001mol) intermediate TA-2 and 0.13g (0.0011mol) intermediate H-2, 0.15 potassium carbonate and catalytic amount of sodium iodide were added to 25N, N-dimethylformamide, then heated for 70 The reaction was carried out at ℃ for 5 hours, and the completion of the reaction was tracked by plate chromatography. The reaction system was cooled to room temperature, the solid was filtered off, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography to obtain 0.28 g of the product, with a yield of 65%.
(11)目标化合物835(11) Target compound 835
将0.31g(0.001mol)中间体TA-6和0.13g中间体H-3,0.15碳酸钾以及催化量碘化钠加入到25mlTHF中,然后加热回流反应10hr,板层析跟踪反应完成,反应体系冷却到室温,过滤去固体,蒸出乙腈,残留物柱层析提纯得产物0.25g,收率为61%。Add 0.31g (0.001mol) of intermediate TA-6 and 0.13g of intermediate H-3, 0.15 grams of potassium carbonate and a catalytic amount of sodium iodide into 25mlTHF, then heat and reflux for 10 hours, follow the completion of the reaction by plate chromatography, and the reaction system After cooling to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.25 g of the product with a yield of 61%.
二、制剂配制2. Preparation
以下实施例按照质量配比配制。The following examples are prepared according to the mass ratio.
实施例3、30%悬浮剂Embodiment 3, 30% suspending agent
将化合物251及其它组分充分混和,由此得到的30%悬浮剂。用水稀释得到30%悬浮剂可得到任何所需浓度的稀释液。Compound 251 and other components were thoroughly mixed to obtain a 30% suspension concentrate. Dilution with water to give a 30% suspension concentrate can give any desired concentration of dilution.
实施例4、30%乳油Embodiment 4, 30% emulsifiable concentrate
将亚磷酸溶解在甲苯中,加入化合物548和乙氧基化甘油三酸酯,得到透明的溶液,即30%乳油。Phosphorous acid was dissolved in toluene and compound 548 and ethoxylated triglyceride were added to obtain a clear solution, 30% emulsifiable concentrate.
实施例5、60%可湿粉剂Embodiment 5, 60% wettable powder
将化合物91、十二烷基萘磺酸钠、木质素磺酸钠及硅澡土混合在一起,在粉碎机中粉碎,直到颗粒达到标准后即得60%可湿粉剂。Compound 91, sodium dodecyl naphthalene sulfonate, sodium lignin sulfonate and silicon bath soil were mixed together and pulverized in a pulverizer until the particles reached the standard to obtain a 60% wettable powder.
三、生物活性测试3. Biological activity test
实施例6、对朱砂叶螨卵活性测定Embodiment 6, to the determination of the activity of Tetranychus cinnabarinus eggs
根据待测化合物的溶解性,原药用N,N-二甲基甲酰胺溶解,然后用含1‰吐温80水溶液配制成所需浓度的待测液,N,N-二甲基甲酰胺在溶液中的含量不超过10%。According to the solubility of the compound to be tested, the original drug is dissolved with N,N-dimethylformamide, and then prepared with an aqueous solution containing 1‰ Tween 80 to the required concentration of the test solution, N,N-dimethylformamide The content in the solution does not exceed 10%.
采用喷雾法。将蚕豆叶片带柄剪下,插于加水的瓶中。接一定数量的雌成螨,24h后去除成螨,除去成螨24h后进行喷雾处理,试验重复3次,并设空白对照,置于观察室(26±2℃、湿度70%~80%、16h光照/d)内培养,待空白对照孵化后调查结果。调查时以未孵化为死亡。Use the spray method. Cut off the broad bean leaves with handles and insert them into a bottle with water. Connect a certain number of female adult mites, remove the adult mites after 24 hours, and carry out spray treatment after removing the adult mites for 24 hours. The test is repeated 3 times, and a blank control is set up. 16h light/d) cultured within, after the blank control was hatched, the results were investigated. When investigating, it is considered dead as unhatched.
按照上述方法,活性测定发现本发明如下化合物1-17、26-72、76-92、101-117、151-167、176-192、226-242、251-267、301-317、326-342、376-392、401-417、451-454、456、457、458、460、467、468、471、474、476、477、480、481、483-486、488、489、490、492、494、499、500、503、506、508、509、512、513、574-548、549、550、552、553、554、556、558、563、564、567、570、572、573、576、577、579-582、584、585、586、588、590、595、596、599、606、602、604、606、608、609、643-646、648、649、650、652、654、659、660、663、666、668、669、972、673、675-678、680、681、682、684、691、692、695、698、700、701、704、705、739-742、744、745、746、748、750、755、757、759、762、764、765、768、769、771-774、776、777、778、780、782、787、788、791、794、796、797、801、835-838、840、841、842、844、846、851、853、855、858、860、862、864、865、867-870、872、873、874、876、878、883、884、887、890、892、894、896、897、931-934、936、937、938、940、942、947、948、951、956、958、961、960、963-966、968、969、970、972、974、978、980、986、988、983、989、992、993、1158、1172、1293、1318、1323、1468在浓度5mg/L下等于或优于90%杀卵活性。与PCT专利申请WO01/68589相比,PCT专利申请WO01/68589中公开的化合物8-1,8-2,8-3,8-4在浓度5mg/L下杀卵活性小于30%。According to the above method, the activity assay found the following compounds of the present invention 1-17, 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342 , 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494 ,499,500,503,506,508,509,512,513,574-548,549,550,552,553,554,556,558,563,564,567,570,572,573,576,577 ,579-582,584,585,586,588,590,595,596,599,606,602,604,606,608,609,643-646,648,649,650,652,654,659,660 , 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746 ,748,750,755,757,759,762,764,765,768,769,771-774,776,777,778,780,782,787,788,791,794,796,797,801,835 -838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890 , 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974 , 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468 are equal to or better than 90% ovicidal activity at a concentration of 5 mg/L. Compared with PCT patent application WO01/68589, the ovicidal activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 is less than 30% at a concentration of 5 mg/L.
按照上述方法,活性测定发现本发明如下化合物230、234、226、227、251、252、254、255、259、301、302、305、309、326、327、401、402、409、405、547、548、549、550、553、570、579、580、585、602、771、772、780、931、932、933、940、937、963、964和969在浓度2mg/L下等于或优于90%杀卵活性。与PCT专利申请WO01/68589相比,PCT专利申请WO01/68589中公开的化合物8-1,8-2,8-3,8-4在浓度2mg/L下杀卵活性为0%。According to the above method, the activity assay found the following compounds of the present invention: , 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969 are equal to or better than the concentration of 2mg/L 90% ovicidal activity. Compared with PCT patent application WO01/68589, the ovicidal activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 was 0% at a concentration of 2 mg/L.
按照上述方法,选取化合物226、227、230、234、251、252、254、255、301、302、547、585、771、772、931、932和937与PCT专利申请WO01/68589中公开的化合物8-1、8-2、8-3和8-4进行杀卵活性的平行测定,试验结果见表4;According to the above method, select compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 and the compounds disclosed in PCT patent application WO01/68589 8-1, 8-2, 8-3 and 8-4 carried out the parallel determination of ovicidal activity, and the test results are shown in Table 4;
表4Table 4
实施例7、对朱砂叶螨成螨活性的测定Embodiment 7, the mensuration of mite activity to Tetranychus cinnabarinus
根据待测化合物的溶解性,原药用N,N-二甲基甲酰胺溶解,然后用含1‰吐温80水溶液配制成所需浓度的待测液,N,N-二甲基甲酰胺在溶液中的含量不超过10%。According to the solubility of the compound to be tested, the original drug is dissolved with N,N-dimethylformamide, and then prepared with an aqueous solution containing 1‰ Tween 80 to the required concentration of the test solution, N,N-dimethylformamide The content in the solution does not exceed 10%.
取两片真叶菜豆苗,接种朱砂叶螨成螨并调查基数后,用手持喷雾器进行整株喷雾处理,每处理3次重复,处理后置于标准观察室,48h后调查存活螨数,计算死亡率。Take two pieces of true-leaf vegetable bean seedlings, inoculate adult mites with Tetranychus cinnabarinus and investigate the base number, spray the whole plant with a hand-held sprayer, repeat each treatment 3 times, put them in a standard observation room after treatment, investigate the number of surviving mites after 48 hours, and calculate the mortality rate .
按照上述方法,活性测定发现本发明化合物1-17、26-72、76-92、101-117、151-167、176-192、226-242、251-267、301-317、326-342、376-392、401-417、451-454、456、457、458、460、467、468、471、474、476、477、480、481、483-486、488、489、490、492、494、499、500、503、506、508、509、512、513、574-548、549、550、552、553、554、556、558、563、564、567、570、572、573、576、577、579-582、584、585、586、588、590、595、596、599、606、602、604、606、608、609、643-646、648、649、650、652、654、659、660、663、666、668、669、972、673、675-678、680、681、682、684、691、692、695、698、700、701、704、705、739-742、744、745、746、748、750、755、757、759、762、764、765、768、769、771-774、776、777、778、780、782、787、788、791、794、796、797、801、835-838、840、841、842、844、846、851、853、855、858、860、862、864、865、867-870、872、873、874、876、878、883、884、887、890、892、894、896、897、931-934、936、937、938、940、942、947、948、951、956、958、961、960、963-966、968、969、970、972、974、978、980、986、988、983、989、992、993、1158、1172、1293、1318、1323、1468在浓度2.5mg/L下等于或优于90%杀成螨活性。与PCT专利申请WO01/68589相比,PCT专利申请WO01/68589中公开的化合物8-1,8-2,8-3,8-4在浓度2.5mg/L下成螨活性活性小于80%。According to the above method, the activity assay found that the compounds 1-17, 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494, 499, 500, 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835- 838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468 were equal to or better than 90% adult acaricidal activity at a concentration of 2.5mg/L. Compared with PCT patent application WO01/68589, compounds 8-1, 8-2, 8-3, and 8-4 disclosed in PCT patent application WO01/68589 have less than 80% mite-forming activity at a concentration of 2.5 mg/L.
按照上述方法,活性测定发现本发明化合物230、234、226、227、251、252、254、255、259、301、302、305、309、326、327、401、402、409、405、547、548、549、550、553、570、579、580、585、602、771、772、780、931、932、933、940、937、963、964和969在浓度1.25mg/L下等于或优于90%杀成螨活性。与PCT专利申请WO01/68589相比,PCT专利申请WO01/68589中公开的化合物8-1,8-2,8-3,8-4在浓度1.25mg/L下成螨活性低于50%。According to the above method, the activity assay found that the compounds of the present invention 230, 234, 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969 are equal to or better than the concentration of 1.25mg/L 90% adult acaricidal activity. Compared with PCT patent application WO01/68589, compounds 8-1, 8-2, 8-3, and 8-4 disclosed in PCT patent application WO01/68589 have less than 50% acarigenic activity at a concentration of 1.25 mg/L.
按照上述方法,选取化合物226、227、230、234、251、252、254、255、301、302、547、585、771、772、931、932和937与PCT专利申请WO01/68589中公开的化合物8-1、8-2、8-3和8-4进行成螨活性的平行测定,试验结果见表5。According to the above method, select compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 and the compounds disclosed in PCT patent application WO01/68589 8-1, 8-2, 8-3 and 8-4 were used for parallel determination of mite activity, and the test results are shown in Table 5.
表5table 5
实施例8、对朱砂叶螨若螨活性的测定Embodiment 8, to the mensuration of nymph activity of Tetranychus cinnabarinus
根据待测化合物的溶解性,原药用N,N-二甲基甲酰胺溶解,然后用含1‰吐温80水溶液配制成所需浓度的待测液,N,N-二甲基甲酰胺在溶液中的含量不超过10%。According to the solubility of the compound to be tested, the original drug is dissolved with N,N-dimethylformamide, and then prepared with an aqueous solution containing 1‰ Tween 80 to the required concentration of the test solution, N,N-dimethylformamide The content in the solution does not exceed 10%.
将蚕豆叶片带柄剪下,插于加水的小瓶中,接一定数量体色鲜艳、行动活泼的雌成螨,24h后,去除成螨,去除卵量不足的叶片。待卵孵化,长至若螨后进行喷雾处理,试验重复3次,并设空白对照,置于观察室(26±2℃、湿度70%~80%、16h光照/d)内培养,48h后调查结果。调查时轻触虫体,没有反应视为死虫。Cut off broad bean leaves with stalks, insert them into a small bottle with water, and pick up a certain number of brightly colored and active female adult mites. After 24 hours, remove the adult mites and remove the leaves with insufficient eggs. After the eggs hatched and grew to nymphs, spray treatment was carried out. The test was repeated 3 times, and a blank control was set up, and placed in an observation room (26±2°C, humidity 70%-80%, 16h light/d) for cultivation, and after 48h Findings. Lightly touch the worm body during investigation, if there is no response, it is regarded as a dead worm.
按照上述方法,活性测定发现本发明化合物1-17、26-72、76-92、101-117、151-167、176-192、226-242、251-267、301-317、326-342、376-392、401-417、451-454、456、457、458、460、467、468、471、474、476、477、480、481、483-486、488、489、490、492、494、499、500、503、506、508、509、512、513、574-548、549、550、552、553、554、556、558、563、564、567、570、572、573、576、577、579-582、584、585、586、588、590、595、596、599、606、602、604、606、608、609、643-646、648、649、650、652、654、659、660、663、666、668、669、972、673、675-678、680、681、682、684、691、692、695、698、700、701、704、705、739-742、744、745、746、748、750、755、757、759、762、764、765、768、769、771-774、776、777、778、780、782、787、788、791、794、796、797、801、835-838、840、841、842、844、846、851、853、855、858、860、862、864、865、867-870、872、873、874、876、878、883、884、887、890、892、894、896、897、931-934、936、937、938、940、942、947、948、951、956、958、961、960、963-966、968、969、970、972、974、978、980、986、988、983、989、992、993、1158、1172、1293、1318、1323、1468在浓度2.5mg/L下等于或优于95%杀若螨活性。与PCT专利申请WO01/68589相比,PCT专利申请WO01/68589中公开的化合物8-1,8-2,8-3,8-4在浓度2.5mg/L下若螨活性活性小于80%。According to the above method, the activity assay found that the compounds 1-17, 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494, 499, 500, 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835- 838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468 were equal to or better than 95% nymphicidal activity at a concentration of 2.5 mg/L. Compared with PCT patent application WO01/68589, the nymph activity of compounds 8-1, 8-2, 8-3, and 8-4 disclosed in PCT patent application WO01/68589 is less than 80% at a concentration of 2.5 mg/L.
按照上述方法,活性测定发现本发明化合物230、234、226、227、251、252、254、255、259、301、302、305、309、326、327、401、402、409、405、547、548、549、550、553、570、579、580、585、602、771、772、780、931、932、933、940、937、963、964和969在浓度0.5mg/L下等于或优于90%杀若螨活性。与PCT专利申请WO01/68589相比,PCT专利申请WO01/68589中公开的化合物8-1,8-2,8-3,8-4在浓度0.5mg/L下若螨活性低于30%。According to the above method, the activity assay found that the compounds of the present invention 230, 234, 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969 are equal to or better than the concentration of 0.5mg/L 90% nymphicidal activity. Compared with PCT patent application WO01/68589, the nymph activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 is lower than 30% at a concentration of 0.5 mg/L.
按照上述方法,选取化合物226、227、230、234、251、252、254、255、301、302、547、585、771、772、931、932和937与PCT专利申请WO01/68589中公开的化合物8-1、8-2、8-3和8-4进行若螨活性的平行测定,试验结果见表6。According to the above method, select compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 and the compounds disclosed in PCT patent application WO01/68589 8-1, 8-2, 8-3 and 8-4 carried out the parallel determination of nymph activity, and the test results are shown in Table 6.
表6Table 6
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