CN1046513C - 取代的吡唑基吡唑衍生物,其制备方法及其作除草剂的用途 - Google Patents
取代的吡唑基吡唑衍生物,其制备方法及其作除草剂的用途 Download PDFInfo
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- CN1046513C CN1046513C CN95195220A CN95195220A CN1046513C CN 1046513 C CN1046513 C CN 1046513C CN 95195220 A CN95195220 A CN 95195220A CN 95195220 A CN95195220 A CN 95195220A CN 1046513 C CN1046513 C CN 1046513C
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 239000002837 defoliant Substances 0.000 description 1
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 description 1
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- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000004503 fine granule Substances 0.000 description 1
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- XNXVOSBNFZWHBV-UHFFFAOYSA-N hydron;o-methylhydroxylamine;chloride Chemical class Cl.CON XNXVOSBNFZWHBV-UHFFFAOYSA-N 0.000 description 1
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- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000002480 mineral oil Substances 0.000 description 1
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- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229940115128 sebex Drugs 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 1
- 229960000278 theophylline Drugs 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/38—Nitrogen 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- 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
- C07D405/14—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 three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D411/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- General Health & Medical Sciences (AREA)
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- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明涉及通式(Ⅰ)的新的取代吡唑衍生物,
式中R1,R2,R3,R4,R5和R6具有说明书中所给含意,涉及具有除草作用的试剂,它们含有至少一种式(Ⅰ)的化合物,还涉及其作除草剂的用途。
Description
本发明涉及新的取代的吡唑基吡唑衍生物,其制备方法和用于其制备的中间产物,以及其作除草剂的用途。
已知吡唑类具有除草性能(WO9408999)。然而经常发生的是这些已知化合物的除草作用不够充分或在主要农作物中的相关除草作用发生选择性问题。
本发明的问题是制备不具有这些缺点且生物性能优于目前已知的化合物的新的取代的吡唑衍生物。
现已发现通式(Ⅰ)的取代的吡唑衍生物具有优异的除草作用:(Ⅰ)式中:R1=C1-C4烷基,R2=C1-C4烷基,C1-C4烷硫基,C1-C4烷氧基;或被卤素取代一次或多次的C1-C4烷基,C1-C4烷硫基,C1-C4烷氧基,R1和R2一起形成基团-(CH2)m-,R3=氢或卤素,R4=氢或C1-C4烷基,R5=氢,硝基,氰基或基团-COOR7,或
R7,R8和R9相互独立地为氢或C1-C4烷基,R8和R9与相邻氮原子一起形成5或6员饱和杂环,R10=氢,C1-C4烷基,或被卤素取代一次或多次的C1-C4烷基,R11=氢,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;或被卤素、羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;或被氧间断一次或多次的C2-C8烷基,C3-C6环烷基,C3-C8链烯基,C3-C6炔基;或基团OR12,R12=氢,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被卤素,羟基或C1-C4烷氧羰基,C1-C4烷基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,Y=氧,硫,-N-OR13和
R13=氢,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被卤素,氰基,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被氧间断一次或多次的C2-C8烷基,C3-C8环烷基,C3-C8链烯基,C3-C8炔基;可任选地被卤原子取代的C1-C4烷氧羰基-C1-C4烷基;可任选地被卤原子取代的C1-C4烷氧羰基-C2-C4链烯基;C1-C4烷氧羰基,R14和R15相互独立地为氢,卤素,氰基,羧基,甲酰基,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被卤素,氰基,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被氧间断一次或多次的C2-C8烷基,C3-C8环烷基,C3-C8链烯基,C3-C8炔基;可任选地被卤原子取代的C1-C4烷氧羰基-C1-C4烷基;可任选地被卤原子取代的C1-C4烷氧羰基-C2-C4链烯基;C1-C4烷氧羰基,C1-C4烷氧基或C1-C4烷硫基,R14和R15与碳原子一起形成可被氧或硫间断一次或多次的饱和碳环C3-C6环,R16=氢或C1-C4烷基,R17=氢,C1-C4烷基或卤素-C1-C4烷基,R18,R19,R20,R21,R22和R23各自独立地为氢,卤素,C1-C4烷基,C2-C4链烯基或C3-C4炔基;被卤素,氰基,硝基,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C4烷基,C2-C4链烯基,C3-C4炔基、羧基或C1 C4烷氧羰基,R24=C1-C4烷基或被卤素取代一次或多次的C1-C4烷基,m=3或4,n=0,1,2或3,p=0或1,X=氧或硫,Z=氧,硫或N-R25,R25=氢或C1-C4烷基,W=氧,硫或碳。
术语“卤素”包括氟,氯和碘。
术语“烷基”,“链烯基”和“炔基”指可以是支化或未支化的碳链。
优选的式(Ⅰ)化合物是这样一些化合物,其中:R1=甲基,R2=甲硫基或二氟甲氧基,R1和R2一起形成基团-(CH2)4-,R3=氢,氯或溴,R4=氢,R5=氢,硝基,氰基或基团-COOR7或-CXR10,或下式基团之一R7=氢或C1-C4烷基,R10=氢,C1-C4烷基,被卤素取代一次或多次的C1-C4烷基,R11=氢,C1-C6烷基或基团-OR12,R12=C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被卤素,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,Y=氧,硫,-N-OR13和
R13=氢,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被氧间断一次或多次的C2-C8烷基,C3-C8环烷基,C3-C8链烯基,C3-C8炔基;可任选地被卤原子取代的C1-C4烷氧羰基-C1-C4烷基;可任选地用卤原子取代的C1-C4烷氧羰基-C2-C4链烯基;C1-C4烷氧羰基,R14和R15各自独立地为氢,卤素,氰基,羧基,甲酰基,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;可任选被卤原子取代的C1-C4烷氧羰基-C1-C4烷基;C1-C4烷氧羰基,C1-C4烷氧基或C1-C4烷硫基,R16=氢或C1-C4烷基,R17=氢,C1-C4烷基或卤素-C1-C4烷基,R18,R19,R20,R21,R22和R23各自独立地为氢,卤素,C1-C4烷基,C2-C4链烯基或C3-C4炔基;被卤素,氰基,硝基,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C4烷基,C2-C4链烯基,C3-C4炔基、羧基或C1-C4烷氧羰基,R24=C1-C4烷基或被卤素取代一次或多次的C1-C4烷基,m=3或4,n=0,1,2或3,p=0或1,X=氧或硫,Z=氧,硫或N-R25,R25=氢或C1-C4烷基,W=氧,硫或碳。
尤其优选这样的式(Ⅰ)化合物,其中:R1=甲基,R2=二氟甲氧基,R1和R2一起形成基团-(CH2)4-,R3=氯,R4=氢,R5=硝基或氰基,或基团
R11=氢或基团-OR12,R12=C1-C6烷基,Y=氧,-N-OR13和
R13=C1-C6烷基,R14和R15相互独立地为氢,卤素或C1-C4烷氧基,R16=氢,R17=氢,R18,R19,R20,R21,R22和R23相互独立地为氢,卤素,C1-C4烷基,C1-C4烷氧羰基-C1-C4烷基,或C1-C4卤代烷基,n=0,p=0或1,以及X=氧。
本发明的通式(Ⅰ)化合物可按如下制备:A)使通式(Ⅱ)化合物Ⅱ式中R1,R2和R3具有通式(Ⅰ)中所给含意,与通式(Ⅲ)化合物反应,Ⅲ式中R5代表基团-COOR7或基团
其中R7,R8和R9具有通式(Ⅰ)中所给含意,X代表氧,R6具有通式(Ⅰ)中所给含意,但不包含甲酰基,而B代表基团-OR26或
,其中R26,R27和R28相互独立地为C1-C4烷基,或B)当R6表示甲酰基时,使通式(Ⅰa)化合物与适当氧化剂反应:Ⅰa式中R1,R2,R3,R4和R5具有通式(Ⅰ)中所给含意,而A表示氢,卤素,羟基,烷基-或芳基-磺酰基,或C)当R6表示基团-CYR11(其中R11具有通式(Ⅰ)中所给含意,而Y代表氧)时,使通式(Ⅰb)化合物Ⅰb式中R1,R2,R3,R4和R5具有通式(Ⅰ)中所给含意,用合适的碱金属化,然后与通式ⅠⅤ或Ⅴ的酰基化合物反应:式中R11具有通式(Ⅰ)中所给含意,而D代表氯,溴,-OR29或
,其中R29,R30和R31代表C1-C4烷基。若R11代表氢,则D的含意限制在-OR29和
,或D)当R6代表基团
(其中R11具有通式(Ⅰ)中所给含意,而Y代表硫)时,使通式(Ⅰc)化合物与Lawessons试剂反应ⅠC式中R1,R2,R3,R4, R5和R11具有通式(Ⅰ)中所给含意,或E)当R6代表基团
(其中R11具有通式(Ⅰ)中所给含意,而Y代表基团-N-OR13,其中R13具有通式(Ⅰ)中所给含意)时,使通式(Ⅰc)化合物
ⅠC式中R1,R2,R3,R4,R5和R11具有通式(Ⅰ)中所给含意,与通式Ⅵ化合物反应
H2N-OR13 Ⅵ式中R13具有通式(Ⅰ)中所给含意,或(F)当R6代表基团
(其中R11具有通式(Ⅰ)中所给含意,而Y代表
,其中R14和R15具有通式(Ⅰ)中所给含意)时,使通式(Ⅰc)化合物ⅠC式中R1,R2,R3,R4,R5和R5具有通式(Ⅰ)中所给含意,与通式ⅤⅡ或Ⅷ化合物反应Ⅷ式中R14和R15具有通式(Ⅰ)中所给含意,x且R32代表C1-C4烷基,或G)当R6代表卤素时,使通式(Ⅰd)化合物与合适的卤化试剂反应Ⅰd式中R1,R2,R3,R4,R5和R6具有通式(Ⅰ)中所给含意,或H)当R6代表下式基团之一时,式中R16,R17,R18,R19,R20,R21,R22,R23,R24,n,p和W具有通式(Ⅰ)中所给含意,使通式(Ⅰe)化合物Ⅰe式中R1,R2,R3,R4,R5,R16,R17和n具有通式(Ⅰ)中所给含意,与通式Ⅸ,Ⅹ或Ⅺ化合物反应式中R18,R19,R20,R21,R22,R23,R24,p和W具有通式(Ⅰ)中所给含意,或I)当R6代表下式基团时式中R16,R18,R19,R20,R21,R22,R23,n和p具有通式(Ⅰ)中所给含意,使通式(Ⅰf)化合物Ⅰf式中R1,R2,R3,R4,R5,R16和n具有通式(Ⅰ)中所给含意,与通式Ⅻ化合物反应Ⅻ式中R18,R19,R20,R21,R22,R23,Z和p具有通式(Ⅰ)中所给含意,或J)首先使通式(Ⅰg)化合物重氮化,Ⅰg式中R1,R2,R3,R4和R5具有通式(Ⅰ)中所给含意,得到通式(Ⅰh)化合物式中R1,R2,R3,R4和R5具有通式(Ⅰ)中所给含意,然后与通式ⅩⅢ的Michael受体反应,式中R33和R34各自独立地为氢,C1-C4烷基或卤素,而R35为C1-C4烷基,或K)用通式ⅩⅣ的醇酯化通式(Ⅰf)的化合物
R12-OH ⅩⅣ式中R12具有通式(Ⅰ)中所给含意。
其中R5代表基团-COOR7或-CXNR8R9的本发明通式(Ⅰ)化合物可由Bisagni等在四面体(Tetrahedron),29,435(1973)中所述方法制备。
方法变型B)的氧化可由例如在Houben-Wehl,Vol VⅡ,1,第135页及以下(1954)或Vol E3,第231页及以下(1983)中所述方法进行。用作原料的通式(Ⅰa)化合物是已知的(WO9408999)
方法变型C)通过如下方法有效进行:使通式(Ⅰb)的原料在合适溶剂中于-100至+40℃的温度下与合适的碱反应得到通式(Ⅰi)化合物Ⅰi式中R1,R2,R3,R4和R5具有通式(Ⅰ)中所给含意,而金属代表金属阳离子如锂,钠或钾。式(Ⅰi)的中间体化合物直接,即不需任何其他处理,与通式Ⅳ或Ⅴ化合物在-100至+100℃的温度下反应。
可以列举醚类如***,四氢呋喃或1,4-二噁烷作合适溶剂。
可以列举丁基锂,二异丙基氨化锂,氢化钠或叔丁醇钾作碱。
用作原料的通式(Ⅰb)化合物是已知的。它们的制备在WO9408999中有述。
方法变型D)例如可按化学学会公报(BuH Soc Chim Belg),87,223,229,299或525(1978)中所述方法进行。
在方法变型E)中形成肟-醚可按已知方法如Houben-Wehl,Vol X4,第55页及以下(1968)中所述方法进行。
在方法变型F)中所涉及化合物可由“高等有机化学(Advanced Organic Chemistry)”,1985,第864页及以下和其中所引用文献中所述的方法制备。
磺酰氯,次氯酸钠,N-氯代琥珀酰亚胺,N-溴代琥珀酰亚胺,氯气或溴是可使用的卤化试剂实例。
缩醛或缩酮可由T W Greene在“有机合成中的保护基团(Protective Groups in Organic Synthesis)”,1980,第116页及以下中所述方法制备。
根据方法变型I)的本发明化合物可由A I Meyers在美国化学会志(J Am Chem Soc),92,6644(1970)中所述方法制备。
根据方法变型J)的化合物可按美国专利5250504中所述方法制备。
根据最后一种方法的酯化本身已知且可按常规方法如在Houben-Wehl,Vol E5,第659页及以下(1985)中所述方法进行。
该制备可使用或不使用溶剂进行,因而若需要可使用对各反应物呈惰性的溶剂或稀释剂。此类溶剂或稀释剂的实例分别是脂族和芳族烃类,它们各自可任选被氯化,例如己烷,环己烷,石油醚,石油溶剂,苯,甲苯,二甲苯,二氯甲烷,氯仿,四氯化碳,氯化乙烯,三氯乙烯和氯苯;醚类如***,甲***,甲基叔丁基醚,二异丙醚,二丁醚,二噁烷和四氢呋喃;酮类如丙酮,甲乙酮,甲基异丙基酮,甲基异丁基酮;腈类如乙腈和丙腈;醇类如甲醇,乙醇,异丙醇,丁醇,缩丁醇,叔戊醇和乙二醇;酯类如乙酸乙酯和乙酸戊酯;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜类如二甲亚砜,砜类如环丁砜,碱类如吡啶和三乙胺,羧酸类如乙酸,以及无机酸类如硫酸和盐酸。
使用常用方法来处理本发明化合物。纯化用结晶或柱色谱法进行。
本发明化合物通常为无色或稍呈黄色的晶体或粘稠物质,它们大部分能易溶于氯代烃类如二氯甲烷或氯仿,醚类如***或四氢呋喃,醇类如甲醇或乙醇,酮类如丙酮或丁酮,酰胺类如二甲基甲酰胺以及亚砜类如二甲亚砜中。
本发明化合物对阔叶杂草和禾本科植物具有良好的除草作用。选择性施用对各种如下作物是可能的:油菜,甜菜,大豆,棉花,水稻,玉米,大麦,小麦和其他种类的禾谷类。个别化合物也适用作甜菜,棉花,大豆,玉米和禾谷类的选择性除草剂。此外,这些化合物可在长期栽培期间如在森林,装饰性树木,果树,葡萄,柑桔,坚果,香焦,咖啡,茶,橡胶,油棕,可可,浆果和啤酒花种植中用于除草。
本发明化合物例如可用于下列植物品种:如下各属的双子叶杂草:欧白芥属,独行菜属,拉拉藤属,繁缕属,母菊属,春黄菊属,牛膝菊属,藜属,芸苔属,荨麻属,千里光属,苋属,马齿苋属,苍耳属,旋花属,番薯属,蓼属,田菁属,豚草属,蓟属,苦苣菜属,茄属,野芝麻属,婆婆纳属,苘麻属,曼陀罗属,堇菜属,鼬瓣花属,罂粟属,矢车菊属和菊属;如下各属的单子叶杂草:燕麦属,看麦娘属,稗属,Sataria,黍属,马唐属,早熟禾属,
属,臂形草属,毒麦属,雀麦属,莎草属,披硷草属,慈姑属,雨久花属,飘拂草属,荸荠属,鸭嘴草属和Apera。
施用量取决于使用类型和生长阶段而在O.001-5kg/ha之间变化。
本发明活性剂也可用作脱叶剂,干燥剂和除草剂。
作用强度和作用速度的提高例如可通过使用扩大该效果的添加剂如有机溶剂,润湿剂和油类而达到。因此这类添加剂的使用任选地导致活性物质的剂量降低。
本发明活性剂或其混合物理想的是以制剂如粉剂,喷雾剂,颗粒剂,溶液,乳液或悬浮液形式使用,各自加入液体和/或固体载体或稀释剂且任选地加入粘合剂,润湿剂,乳化剂和/或分散助剂。
合适的液态载体例如是脂族和芳族烃类如苯,甲苯,二甲苯,环己酮,异佛尔酮,二甲亚砜,二甲基甲酰胺和矿物油馏分及植物油。
合适的固态载体是例如膨润土,硅胶,滑石,高岭土,硅镁土,白垩和植物产品如面粉。
表面活性剂的实例是木素磺酸钙,聚乙二醇烷基苯基醚,萘磺酸及其盐,苯酚磺酸及其盐,甲醛的缩合物,脂肪醇硫酸盐以及取代的苯磺酸及其盐。
在各种制剂中各活性剂的量可在宽范围内变化。例如该材料含有约l0-90wt%活性剂,约90-lOwt%液体或固体载体和任选的至多20wt%表面活性荆。
该材料可按常规方法使用,例如用水作载体,喷雾量为约100-1000l/ha。正如以所谓的微颗粒剂形式使用一样,该材料以所谓的低容量方法(Low-Volume-Process)和超低容量方法施用也是可能的。
这些混合物的制备可以本身巳知的方式进行,例如通过研磨或混合方法。若需要,各组分的制剂可在其使用前立即混合,正如在例如所谓的罐混方法中进行的一样。
下列实施例说明本发明化合物的制备。实施例1(方法B)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-甲酰基-4-吡唑腈(carbonitrile)
将29g(9.6mmol)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-羟甲基-4-吡唑腈加入30ml二氯甲烷中,然后加入15.2g在氧化铝上的氯铬酸吡啶鎓。继续在室温下搅拌1小时,然后通过硅藻土真空过滤反应混合物并用己烷/乙酸乙酯由柱色谱法提纯。产量:1.8g=理论值的62%nD 20=1.54066实施例2(方法E)(E/Z)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-甲氧亚氨甲基-4-腈
将0.46g(1.5mmol)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-甲酰基-4-吡唑腈于室温下加入4ml吡啶中并加入0.25g(3.0mmol)O-甲基羟胺盐酸盐。室温搅拌混合物2小时,倾入水中并用乙酸乙酯振摇。用硫酸镁干燥并浓缩。使用己烷/乙酸乙酯由柱色谱法提纯。产量:0.3g=理论值的60%冰点:95-98℃实施例3(方法F)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-(2-甲氧基乙烯基)-4-吡唑腈
将2.9g(8.4mmol)甲氧基亚甲基-三苯基氯化鏻加入10ml四氧呋喃中并在0℃缓慢滴加5.6ml(9.0mmol)丁基锂的1.6M己烷溶液。将橙色溶液再搅拌30分钟,然后缓慢滴加1.0g(3.3mmol)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-甲酰基-4-吡唑腈。在室温下继续搅拌2小时。然后将反应混合物加入水中,用乙酸乙酯振摇,用硫酸镁干燥并浓缩。使用己烷/乙酸乙酯由柱色谱法提纯。实施例4(方法H)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-(1,3-二氧戊环-2-基)-4-吡唑腈
将0.6g(2.0mmol)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-甲酰基-4-吡唑腈溶于30ml甲苯中并加入0.14g(2.2mmol)乙二醇和催化量的对甲苯磺酸。在分水器上加热混合物2小时,用氯化钠溶液洗涤冷却的溶液,然后干燥并浓缩。产量:0.68g=理论值的98%冰点:70-72℃实施例5(方法H)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-(1,1-二乙酰氧基甲基)吡唑-4-腈
将5m1乙酐冷却至0-5℃并加入2滴三氟化硼-***。然后缓慢滴加2.3g(7.6mmol)1-(4-氯-5-二氟甲氧基-1-甲基-3-吡唑基)-5-甲酰基-4-吡唑腈并继续在室温下再搅拌1.5小时。加入9ml10%乙酸钠溶液,继续在室温下再搅拌20分钟,然后用乙酸乙酯振摇混合物。合并的乙酸乙酯相用碳酸氢钠和氯化钠溶液洗涤,干燥并浓缩。使用己烷/乙酸乙酯混合物由柱色谱法提纯。产量:2.5g=理论值的80%冰点:84-85℃实施例6(方法J)2-氯-3-[1-(3-氯-4,5,6,7-四氢吡唑并[1,5-a]吡啶-2-基)-4-氰基-5-吡唑基]-2-甲基丙酸乙酯
将1.6g(15.5mmol)亚硝酸叔丁酯,20ml甲基丙烯酸乙酯和1.52g氯化铜-Ⅱ加入20ml乙腈中和分3次加入2.62g(10mmol)5-氨基-1-(3-氯-4,5,6,7-四氢吡唑并[1,5-a]吡啶-2-基)-4-吡唑腈。混合物于室温搅拌20小时,加入50ml2N盐酸中,用二氯甲烷萃取3次,用硫酸镁干燥并浓缩。使用己烷/乙酸乙酯混合物由柱色谱法纯化。产量:1.6g=理论值的40%nD 20=1.54164实施例7(方法K)1-(3-氯-4,5,6,7-四氢吡唑并[1,5-a]吡啶-2-基)-4-氰基-5-吡唑羧酸异丙酯
将757mg(2.7mmol)偶氮二羧酸二乙酯滴加入800mg(2.7mmol)1-(3-氯-4,5,6,7-四氢吡唑并[1,5-a]吡啶-2-基)-4-氰基-5-吡唑羧酸中。于该温度下搅拌混合物2小时,然后浓缩并使用SiO2/己烷/乙酸乙酯由柱色谱法提纯。残余物用二异丙醚重结晶。产量:570mg=理论值的62%nD 20=1.53942
下列实施例说明本发明:BAYER-编码ALOMY 看麦娘(Alopecurus myosuroides)AGRRE 匍匐冰草(Elymus repens)AVEFA 野燕麦BROTE 雀麦(Bromus tectorum)SETVI 狗尾草PANSS 黍属SORHA ***高梁CYPES 油莎草ABUTH 苘麻IPOSS 圆叶牵牛GALAP 猪殃殃MATCH 母菊POLSS 蓼属SEBEX 田菁(Sesbania exaltata)SOLSS 茄属VERPE 大婆婆纳VIOSS 堇菜属0=无损伤 1=1-24%损伤2=25-74%损伤 3=75-89%损伤4=90-100%损伤应用实施例
在温室中的所示植物品种在出芽后用所示化合物以0.1kg活性剂/ha的施用量处理。为此,将化合物以500l水/ha的乳液使用并均匀喷于植株上。处理2周后,本发明化合物对下表所示杂草表现出显著作用。
A A A B S P S C A G I M P S S V V化合物 L G V R E A O Y B A P A O E O E I实施例号 O R E O T N R P U L O T L B L R O
M R F T V S H E T A S C S E S P S
Y E A E I S A S H P S H S X S E S
- - - - 3 3 - - 4 - 4 4 4 4 4 3 33 4 3 3 - 3 3 3 3 4 3 4 4 4 4 4 4 34 4 3 4 4 4 4 3 3 4 4 4 4 4 4 4 4 47 - - - - 3 3 - - 4 - 3 3 4 4 4 3 38 4 4 4 4 4 4 3 4 4 4 4 4 4 4 4 4 412 4 3 4 4 4 3 3 4 4 4 4 4 4 4 4 4 414 3 - - 3 4 3 - 3 4 4 4 4 4 4 4 4 431 4 3 3 3 3 - - 3 4 - 4 4 4 4 4 4 434 4 - 4 3 4 4 4 - 4 4 4 4 4 4 4 4 443 - 3 - - 3 3 3 - 4 - 4 3 4 4 4 4 344 3 - - - 3 3 3 - 4 - 4 3 4 4 4 4 352 4 - 3 3 4 4 3 3 4 4 4 4 4 4 4 4 462 4 - 4 4 4 4 3 3 4 4 4 4 4 4 4 4 465 4 - 4 3 4 4 3 4 4 4 4 4 4 4 4 4 491 4 - 4 4 4 4 4 - 4 4 4 4 4 4 4 4 492 4 - 4 3 4 4 3 - 4 4 4 4 4 4 4 4 493 4 - 4 3 4 4 4 - 4 4 4 4 4 4 4 4 495 - - - 3 4 4 3 - 3 4 4 4 4 4 4 4 496 - - 3 3 4 4 3 - 4 4 4 4 4 4 3 4 4未处理 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Claims (6)
1.通式(Ⅰ)的取代的吡唑衍生物:(Ⅰ)式中:R1=C1-C4烷基,R2=C1-C4烷基,C1-C4烷硫基,C1-C4烷氧基;或被卤素取代一次或多次的C1-C4烷基,C1-C4烷硫基,C1-C4烷氧基,R1和R2一起形成基团-(CH2)m-,R2=氢或卤素,R4=氢或C1-C4烷基,R5=氢,硝基,氰基或基团-COOR7,或
或下列基团之一:R7,R8和R9相互独立地为氢或C1-C4烷基,R8和R9与相邻氮原子一起形成5或6员饱和杂环,R10=氢,C1-C4烷基,或被卤素取代一次或多次的C1-C4烷基,R11=氢,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;或被卤素、羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;或被氧间断一次或多次的C2-C8烷基,C3-C6环烷基,C3-C8链烯基,C3-C6炔基;或基团OR12,R12=氢,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被卤素,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,Y=氧,硫,-N-OR13和
R13=氢,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被卤素,氰基,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被氧间断一次或多次的C2-C8烷基,C3-C8环烷基,C3-C8链烯基,C3-C8炔基;可任选地被卤原子取代的C1-C4烷氧羰基-C1-C4烷基;可任选地被卤原子取代的C1-C4烷氧羰基-C2-C4链烯基;C1-C4烷氧羰基,R14和R15相互独立地为氢,卤素,氰基,羧基,甲酰基,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C2-C6炔基;被卤素,氰基,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,C2-C6环烷基,C2-C6链烯基;C3-C6炔基;被氧间断一次或多次的C2-C8烷基,C3-C8环烷基,C3-C8链烯基,C3-C8炔基;可任选地被卤原子取代的C1-C4烷氧羰基-C1-C4烷基;可任选地被卤原子取代的C1-C4烷氧羰基-C2-C4链烯基;C1-C4烷氧羰基,C1-C4烷氧基或C1-C4烷硫基,R14和R15与碳原子一起形成可被氧或硫间断一次或多次的饱和碳环C3-C6环,R16=氢或C1-C4烷基,R17=氢,C1-C4烷基或卤素-C1-C4烷基,R18,R19,R20,R21,R22和R23各自独立地为氢,卤素,C1-C4烷基,C2-C4链烯基或C3-C4炔基;被卤素,氰基,硝基,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C4烷基,C2-C4链烯基,C3-C4炔基、羧基或C1-C4烷氧羰基,R24=C1-C4烷基或被卤素取代一次或多次的C1-C4烷基,m=3或4,n=0,1,2或3,p=0或1,X=氧或硫,Z=氧,硫或N-R25,R25=氢或C1-C4烷基,W=氧,硫或碳,条件是当R3为氯时,R6不为-COOH基团。
2.通式(Ⅰ)的取代的吡唑衍生物,其中R1=甲基,R2=甲硫基或二氟甲氧基,R1和R2一起形成基团-(CH2)4-,R3=氢,氯或溴,R4=氢,R5=氢,硝基,氰基或基团-COOR7或-CXR10,或下列基团之一: R7=氢或C1-C4烷基,R10=氢,C1-C4烷基,被卤素取代一次或多次的C1-C4烷基,R1l=氢,Cl-C6烷基或基团-OR12,R12=氢,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被卤素,羟基,C1-C4烷氧羰基-C1-C4烷基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C6烷基,Y=氧,硫,-N-OR13和
R13=氢,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;被氧间断一次或多次的C2-C8烷基,C3-C8环烷基,C3-C8链烯基,C3-C8炔基;可任选地被卤原子取代的C1-C4烷氧羰基-C1-C4烷基;可任选地用卤原子取代的C1-C4烷氧羰基-C2-C4链烯基;C1-C4烷氧羰基,R14和R15各自独立地为氢,卤素,氰基,羧基,甲酰基,C1-C6烷基,C3-C6环烷基,C2-C6链烯基,C3-C6炔基;可任选被卤原子取代的C1-C4烷氧羰基-C1-C4烷基;C1-C4烷氧羰基,C1-C4烷氧基或C1-C4烷硫基,R16=氢或C1-C4烷基,R17=氢,C1-C4烷基或卤素-C1-C4烷基,R18,R19,R20,R21,R22和R23各自独立地为氢,卤素,C1-C4烷基,C2-C4链烯基或C3-C4炔基;被卤素,氰基,硝基,羟基或C1-C4烷氧基相同或不同地取代一次或多次的C1-C4烷基,C2-C4链烯基,C3-C4炔基、羧基或C1-C4烷氧羰基,R24=C1-C4烷基或被卤素取代一次或多次的C1-C4烷基,m=3或4,n=0,1,2或3,p=0或l,X=氧或硫,Z=氧,硫或N-R25,R25=氢或C1-C4烷基,W=氧,硫或碳。
4.具有除草作用的试剂,其特征在于含有至少一种根据任一权利要求1-3的化合物。
5.根据权利要求4的具有除草作用的试剂,与载体和/或辅助材料混合。
6.根据任一权利要求1-3的化合物在主要农用作物中抵抗单子叶和双子叶杂草的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE4435373A DE4435373A1 (de) | 1994-09-22 | 1994-09-22 | Substituierte Pyrazolyl-pyrazolderivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Mittel mit herbizider Wirkung |
DEP4435373.1 | 1994-09-22 |
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CN1158616A CN1158616A (zh) | 1997-09-03 |
CN1046513C true CN1046513C (zh) | 1999-11-17 |
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CN95195220A Expired - Fee Related CN1046513C (zh) | 1994-09-22 | 1995-09-21 | 取代的吡唑基吡唑衍生物,其制备方法及其作除草剂的用途 |
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US (3) | US5840912A (zh) |
EP (1) | EP0782575B1 (zh) |
JP (1) | JPH10505847A (zh) |
KR (1) | KR970706281A (zh) |
CN (1) | CN1046513C (zh) |
AU (1) | AU690342B2 (zh) |
BR (1) | BR9509509A (zh) |
CA (1) | CA2200756A1 (zh) |
DE (2) | DE4435373A1 (zh) |
DK (1) | DK0782575T3 (zh) |
ES (1) | ES2191062T3 (zh) |
HU (1) | HU215096B (zh) |
IL (1) | IL115398A0 (zh) |
MX (1) | MX9702203A (zh) |
RU (1) | RU2154644C2 (zh) |
UA (1) | UA54378C2 (zh) |
WO (1) | WO1996009303A1 (zh) |
ZA (1) | ZA958050B (zh) |
Families Citing this family (13)
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DE19623892A1 (de) * | 1996-06-06 | 1997-12-11 | Hoechst Schering Agrevo Gmbh | Substituierte Pyrazolyl-pyrazolderivate |
DE19630555A1 (de) * | 1996-07-18 | 1998-01-22 | Hoechst Schering Agrevo Gmbh | Substituierte Pyrazolyl-pyrazolderivate |
DE19631865A1 (de) * | 1996-08-08 | 1998-02-12 | Bayer Ag | Substituierte 1-(3-Pyrazolyl) -pyrazole |
DE19751943A1 (de) * | 1997-11-24 | 1999-05-27 | Hoechst Schering Agrevo Gmbh | 1-Methyl-5-alkylsulfonyl-, 1-Methyl-5-alkylsulfinyl- und 1-Methyl-5-alkylthio-substituierte Pyrazolylpyrazole, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide |
ES2216559T3 (es) * | 1998-08-13 | 2004-10-16 | Bayer Cropscience Gmbh | Agentes herbicidas con aminofenilsulfonil-ureas aciladas. |
EA200100602A1 (ru) | 1998-12-04 | 2001-10-22 | Басф Акциенгезельшафт | 3-(гетероциклил)-замещенные бензоилпиразолы |
US6492529B1 (en) * | 2000-01-18 | 2002-12-10 | Boehringer Ingelheim Pharmaceuticals, Inc. | Bis pyrazole-1H-pyrazole intermediates and their synthesis |
US7244070B2 (en) * | 2005-10-19 | 2007-07-17 | Xtend Products, Llc | Camera holder and methods |
AR097245A1 (es) * | 2013-08-09 | 2016-03-02 | Kyoyu Agri Co Ltd | Derivado de pirazolilpirazol sustituido y su empleo como herbicida |
JP6128555B2 (ja) * | 2013-08-13 | 2017-05-17 | 協友アグリ株式会社 | 置換ピラゾリルピラゾール誘導体とその除草剤としての使用 |
JP6097655B2 (ja) * | 2013-08-13 | 2017-03-15 | 協友アグリ株式会社 | 置換ピラゾリルピラゾール誘導体とその除草剤としての使用 |
JP6128556B2 (ja) * | 2013-08-13 | 2017-05-17 | 協友アグリ株式会社 | 置換ピラゾリルピラゾール誘導体とその除草剤としての使用 |
CN108203431A (zh) * | 2016-12-20 | 2018-06-26 | 海利尔药业集团股份有限公司 | 一种含双吡唑类化合物的除草组合物及其应用 |
Citations (1)
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WO1994008999A1 (en) * | 1992-10-12 | 1994-04-28 | Schering Aktiengesellschaft | New substituted pyrazole derivatives, processes for their preparation and their use as herbicides |
-
1994
- 1994-09-22 DE DE4435373A patent/DE4435373A1/de not_active Withdrawn
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1995
- 1995-09-21 US US08/809,391 patent/US5840912A/en not_active Expired - Fee Related
- 1995-09-21 MX MX9702203A patent/MX9702203A/es not_active IP Right Cessation
- 1995-09-21 EP EP95934093A patent/EP0782575B1/en not_active Expired - Lifetime
- 1995-09-21 DK DK95934093T patent/DK0782575T3/da active
- 1995-09-21 CA CA002200756A patent/CA2200756A1/en not_active Abandoned
- 1995-09-21 RU RU97106779/04A patent/RU2154644C2/ru not_active IP Right Cessation
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- 1995-09-21 AU AU36517/95A patent/AU690342B2/en not_active Ceased
- 1995-09-21 ES ES95934093T patent/ES2191062T3/es not_active Expired - Lifetime
- 1995-09-21 JP JP8510607A patent/JPH10505847A/ja active Pending
- 1995-09-21 WO PCT/EP1995/003732 patent/WO1996009303A1/en active IP Right Grant
- 1995-09-21 DE DE69529467T patent/DE69529467T2/de not_active Expired - Fee Related
- 1995-09-21 CN CN95195220A patent/CN1046513C/zh not_active Expired - Fee Related
- 1995-09-21 KR KR1019970701859A patent/KR970706281A/ko not_active Application Discontinuation
- 1995-09-21 BR BR9509509A patent/BR9509509A/pt not_active IP Right Cessation
- 1995-09-22 IL IL11539895A patent/IL115398A0/xx unknown
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1998
- 1998-09-04 US US09/148,383 patent/US6028034A/en not_active Expired - Fee Related
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1999
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Publication number | Priority date | Publication date | Assignee | Title |
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WO1994008999A1 (en) * | 1992-10-12 | 1994-04-28 | Schering Aktiengesellschaft | New substituted pyrazole derivatives, processes for their preparation and their use as herbicides |
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EP0782575A1 (en) | 1997-07-09 |
ES2191062T3 (es) | 2003-09-01 |
DE4435373A1 (de) | 1996-03-28 |
AU690342B2 (en) | 1998-04-23 |
DK0782575T3 (da) | 2003-05-12 |
DE69529467T2 (de) | 2003-10-02 |
US5840912A (en) | 1998-11-24 |
ZA958050B (en) | 1996-07-17 |
MX9702203A (es) | 1997-06-28 |
JPH10505847A (ja) | 1998-06-09 |
BR9509509A (pt) | 1997-09-30 |
US6028034A (en) | 2000-02-22 |
UA54378C2 (uk) | 2003-03-17 |
AU3651795A (en) | 1996-04-09 |
RU2154644C2 (ru) | 2000-08-20 |
HUT77184A (hu) | 1998-03-02 |
KR970706281A (ko) | 1997-11-03 |
DE69529467D1 (de) | 2003-02-27 |
CA2200756A1 (en) | 1996-03-28 |
WO1996009303A1 (en) | 1996-03-28 |
HU215096B (hu) | 1998-09-28 |
IL115398A0 (en) | 1995-12-31 |
US6057270A (en) | 2000-05-02 |
CN1158616A (zh) | 1997-09-03 |
EP0782575B1 (en) | 2003-01-22 |
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