CN101022725A - Insecticides based on neonicotinoids and safeners - Google Patents

Insecticides based on neonicotinoids and safeners Download PDF

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CN101022725A
CN101022725A CN 200580031408 CN200580031408A CN101022725A CN 101022725 A CN101022725 A CN 101022725A CN 200580031408 CN200580031408 CN 200580031408 CN 200580031408 A CN200580031408 A CN 200580031408A CN 101022725 A CN101022725 A CN 101022725A
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alkyl
acid
compound
phenyl
representative
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CN100566563C (en
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R·菲舍尔
W·安德施
H·亨格伯格
W·蒂勒特
L·威尔姆斯
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Bayer Intellectual Property GmbH
Bayer CropScience AG
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Bayer CropScience AG
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Abstract

Disclosed are insecticides that are used for controlling arthropods and are characterized by an active moiety of an active substance combination comprising (a) at least one compound of formula (I), wherein Het, A, R, and X have the meaning indicated in the description, and (b) at least one compound which improves crop plant tolerance and is part of the group of compounds indicated in the description. Also disclosed is a method for controlling arthropods by treating plants and the seeds thereof with the inventive insecticides.

Description

Insecticide based on anabasine and safener
The insecticidal activity bond (combination) that the present invention relates to a kind of reactive compound is used for preventing and treating better the purposes of various useful crop plants insects, described bond comprises, first, one or more are selected from the compound of anabasine (neonicotinoid) class, and, the second, the compound of at least a raising crop plants compatibility.
Known following formula (I) compound has insecticidal activity:
Figure A20058003140800091
Wherein
The Het representative is optional separately to be replaced or polysubstituted heterocycle by fluorine, chlorine, methyl or ethyl list,
Described heterocycle is selected from:
Pyridin-3-yl, pyridine-5-base, 3-pyridine subbase (pyridinio), 1-oxidation (oxido)-5-pyridine subbase, 1-oxidation-5-pyridine subbase, oxolane-3-base, thiazole-5-base,
A represents C 1-C 6Alkyl ,-N (R 1) (R 2) or S (R 2),
Wherein
R 1Represent hydrogen, C 1-C 6Alkyl, phenyl-C 1-C 4Alkyl, C 3-C 6Cycloalkyl, C 2-C 6Thiazolinyl or C 2-C 6Alkynyl, and
R 2Represent C 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl ,-C (=O)-CH 3Or benzyl,
R represents hydrogen, C 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl ,-C (=O)-CH 3Or benzyl, or and R 2Represent following groups together:
-CH 2-CH 2-、-CH 2-CH 2-CH 2-、-CH 2-O-CH 2-、-CH 2-S-CH 2-、
-CH 2-NH-CH 2-,-CH 2-N (CH 3)-CH 2-, and
X represents N-NO 2, N-CN or CH-NO 2(seeing for example EP-A1-192 606, EP-A2-580533, EP-A2-376 279, EP-A2-235 725).
Yet, the compatibility of the plant of these compounds and its processing, particularly the compatibility with monocot crops is not all to be entirely satisfactory under all rate of application and all conditions.
Surprisingly, have now found that the insecticide that is selected from anabasine compound is with the following compound (safener or antipoison) of crop plants compatibility that improves when using, have unexpectedly good crop plants tolerance, and can be particularly advantageously as the wide spectrum conjugate preparations of preventing and treating insects.
Therefore, the invention provides the Pesticidal combination (composition) that is used to prevent and treat insects, described composition contains the following component of effective dose:
(a) at least a formula (I) compound
Figure A20058003140800101
Wherein Het, A, R and X as above define,
With
(b) at least a compound that improves the crop plants compatibility that is selected from following compound:
4-dichloro-acetyl-1-oxa--4-azaspiro [4.5] decane (AD-67, MON-4660),
1-dichloro-acetyl six hydrogen-3,3,8a-trimethyl pyrrolo-[1,2-a] pyrimidine-6 (2H)-ketone (dicyclonon, BAS-145138),
4-dichloro-acetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (benoxacor (benoxacor)),
5-chloroquinoline-own the ester of 8-ethoxyacetic acid 1-methyl (cloquitocet_mexyl (cloquintocet-mexyl)---referring to also related compound among EP-A-86750, EP-A-94349, EP-A-191736, the EP-A-492366),
3-(2-chlorophenylmethyl)-1-(1-methyl isophthalic acid-phenylethyl) urea (cumyluron (cumyluron)),
α-(cyano group methoxyimino) benzene acetonitrile (cyometrinil (cyometrinil)),
The 2,4 dichloro benzene ethoxyacetic acid (2,4-drip (2,4-D)),
4-(2,4 dichloro benzene oxygen base) butyric acid (2,4-Embutox (2,4-DB)),
1-(1-methyl isophthalic acid-phenylethyl)-3-(4-aminomethyl phenyl) urea (daimuron (daimuron, dymron)),
3,6-two chloro-O-Anisic Acids (dicamba (dicamba)),
Piperidines-1-bamic acid S-1-methyl isophthalic acid-phenyl chlorocarbonate (dimepiperate (dimepiperate)),
2,2-two chloro-N-(2-oxo-2-(2-acrylic amino) ethyl)-N-(2-acrylic) acetamide (DKA-24),
2,2-two chloro-N, N-two-2-acrylic acetamide (dichlormide (dichlormid)),
4,6-two chloro-2-phenyl pyrimidines (fenclorim (fenclorim)),
1-(2,4 dichloro benzene base)-5-trichloromethyl-1H-1,2,4-triazole-3-Ethyl formate (fenchlorazole (fenchlorazole-ethyl)---referring to also related compound among EP-A-174562 and the EP-A-346620),
2-chloro-4-trifluoromethyl thiazole-5-Formic acid benzylester (separating careless amine (flurazole)),
4-chloro-N-(1,3-dioxolanes-2-base-methoxyl group)-α-trifluoroacetyl benzophenone oxime (fluxofenim (fluxofenim)),
3-dichloro-acetyl-5-(2-furyl)-2,2-Er Jia Ji oxazolidine (Xie Cao oxazole (furilazole), MON-13900),
4,5-dihydro-5,5-diphenyl-3-isoxazole carboxylic acid ethyl ester (Shuan Ben oxazole acid (isoxadifen-ethyl)---referring to also related compound among the WO-A-95/07897),
3,6-two chloro-O-Anisic Acid 1-(ethoxy carbonyl) ethyl esters (lactidichlor),
(4-chloro-neighbour-toloxyl) acetate (MCPA),
2-(4-chloro-neighbour-toloxyl) propionic acid (Vi par (mecoprop)),
1-(2,4 dichloro benzene base)-4,5-dihydro-5-methyl isophthalic acid H-pyrazoles-3, the 5-dicarboxylate (mefenpyrdiethyl (mefenpyr-diethyl)---referring to also related compound among the WO-A-91/07874),
2-dichloromethyl-2-methyl isophthalic acid, 3-dioxolanes alkane (MG-191),
2-acrylic-1-oxa--4-azaspiro [4.5] decane-4-dithio formate (MG-838),
1, the 8-naphthalic anhydride,
α-(1,3-dioxolanes-2-base methoxyimino) benzene acetonitrile (oxabetrinil (oxabetrinil)),
2,2-two chloro-N-(1,3-dioxolanes-2-ylmethyl)-N-(2-acrylic) acetamide (PPG-1292),
3-dichloro-acetyl-2,2-Er Jia Ji oxazolidine (R-28725),
3-dichloro-acetyl-2,2,5-San Jia Ji oxazolidine (R-29148),
4-(4-chloro-neighbour-tolyl) butyric acid,
4-(4-chlorophenoxy) butyric acid,
The diphenylmethyl ethoxyacetic acid,
The diphenyl methoxy menthyl acetate,
Diphenylmethyl ethoxyacetic acid ethyl ester,
1-(2-chlorphenyl)-5-phenyl-1H-pyrazoles-3-methyl formate,
1-(2,4 dichloro benzene base)-5-methyl isophthalic acid H-pyrazoles-3-Ethyl formate,
1-(2,4 dichloro benzene base)-5-isopropyl-1H-pyrazoles-3-Ethyl formate,
1-(2,4 dichloro benzene base)-5-(1, the 1-dimethyl ethyl)-1H-pyrazoles-3-Ethyl formate,
1-(2,4 dichloro benzene base)-5-phenyl-1H-pyrazoles-3-Ethyl formate (referring to also related compound among EP-A-269806 and the EP-A-333131),
5-(2,4 dichloro benzene methyl)-2-isoxazoline-3-Ethyl formate,
5-phenyl-2-isoxazoline-3-Ethyl formate,
5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-Ethyl formate (referring to also related compound among the WO-A-91/08202),
5-chloroquinoline-8-ethoxyacetic acid 1,3-dimethyl butyrate-1-base ester,
5-chloroquinoline-8-ethoxyacetic acid 4-allyloxy butyl ester,
5-chloroquinoline-8-ethoxyacetic acid 1-allyloxy third-2-base ester,
5-chloro-quinoxaline-8-ethoxyacetic acid methyl esters,
5-chloroquinoline-8-ethoxyacetic acid ethyl ester,
5-chloro-quinoxaline-8-ethoxyacetic acid allyl ester,
5-chloroquinoline-8-ethoxyacetic acid 2-oxo third-1-base ester,
5-chloroquinoline-8-oxygen propylmalonic acid diethylester,
5-chloro-quinoxaline-8-oxygen propylmalonic acid diallyl,
5-chloroquinoline-8-oxygen propylmalonic acid diethylester (referring to also related compound among the EP-A-582198),
4-carboxyl benzodihydropyran-4-guanidine-acetic acid (AC-304415 is referring to EP-A-613618),
The 4-tomatotone,
3,3 '-dimethyl-4-methoxyl group benzophenone,
1-bromo-4-chloromethyl sulfonyl benzene,
1-[4-(N-2-methoxybenzoyl base sulfamoyl) phenyl]-3-methyl urea (being N-(2-methoxybenzoyl base)-4-[(methylamino carbonyl) amino] benzsulfamide),
1-[4-(N-2-methoxybenzoyl base sulfamoyl) phenyl]-3, the 3-dimethyl urea,
1-[4-(N-4,5-dimethylbenzoyl sulfamoyl) phenyl]-3-methyl urea,
1-[4-(N-naphthyl sulfamoyl) phenyl]-3, the 3-dimethyl urea,
N-(2-methoxyl group-5-methyl benzoyl)-4-(cyclopropyl amino carbonyl) benzsulfamide,
One of and/or (defining by general formula) following compound,
General formula (IIa)
Figure A20058003140800131
Or general formula (IIb)
Or general formula (IIc)
Figure A20058003140800133
Wherein
M represents the numeral between 0 to 5,
A 1Represent one of divalent heterocyclic group shown below
Figure A20058003140800134
N represents the numeral between 0 to 5,
A 2Representative is optional by C 1-C 4Alkyl, C 1-C 4Alkoxy carbonyl and/or C 1-C 4Two bases of the alkane with 1 or 2 carbon atom that allyloxycarbonyl replaces,
R 8Representation hydroxy, sulfydryl, amino, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group, C 1-C 6Alkyl amino or two-(C 1-C 4Alkyl) amino,
R 9Representation hydroxy, sulfydryl, amino, C 1-C 7Alkoxyl, C 1-C 6Alkene oxygen base, C 1-C 6Alkene oxygen base-C 1-C 6Alkoxyl, C 1-C 6Alkylthio group, C 1-C 6Alkyl amino or two-(C 1-C 4Alkyl) amino,
R 10The optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 4Alkyl,
R 11Represent hydrogen, perhaps the optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 6Alkyl, C 2-C 6Thiazolinyl or C 2-C 6Alkynyl, C 1-C 4Alkoxy-C 1-C 4Alkyl, dioxolanyl-C 1-C 4Alkyl, furyl, furyl-C 1-C 4Alkyl, thienyl, thiazolyl, piperidyl, perhaps representative is optional by fluorine, chlorine and/or bromine or C 1-C 4The phenyl that alkyl replaces,
R 12Represent hydrogen, perhaps the optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 6Alkyl, C 2-C 6Thiazolinyl or C 2-C 6Alkynyl, C 1-C 4Alkoxy-C 1-C 4Alkyl, dioxolanyl-C 1-C 4Alkyl, furyl, furyl-C 1-C 4Alkyl, thienyl, thiazolyl, piperidyl, perhaps representative is optional by fluorine, chlorine and/or bromine or C 1-C 4The phenyl that alkyl replaces, perhaps and R 11Representative is optional separately by C together 1-C 4Alkyl, phenyl, furyl, fused benzene rings or the C that is replaced by following two substituting groups 3-C 6Alkane two bases or C 2-C 5Oxa-alkane two bases, described two substituting groups form 5 or 6 yuan of carbocyclic rings with the C atom that they connected,
R 13Represent hydrogen, cyano group, halogen, perhaps the optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 4Alkyl, C 3-C 6Cycloalkyl or phenyl,
R 14Represent hydrogen, perhaps representative is optional by hydroxyl, cyano group, halogen or C 1-C 4The C that alkoxyl replaces 1-C 6Alkyl, C 3-C 6Cycloalkyl or three-(C 1-C 4Alkyl) silicyl,
R 15Represent hydrogen, cyano group, halogen, perhaps the optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 4Alkyl, C 3-C 6Cycloalkyl or phenyl,
X 1Represent nitro, cyano group, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy,
X 2Represent hydrogen, cyano group, nitro, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy,
X 3Represent hydrogen, cyano group, nitro, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy,
One of and/or (defining by general formula) following compound,
General formula (IId)
Figure A20058003140800151
Or general formula (IIe)
Figure A20058003140800152
Wherein
R and s represent the numeral between 0 and 5,
R 16Represent hydrogen or C 1-C 4Alkyl,
R 17Represent hydrogen or C 1-C 4Alkyl,
R 18Represent hydrogen, perhaps representative is optional separately by cyano group, halogen or C 1-C 4The C that alkoxyl replaces 1-C 6Alkyl, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group, C 1-C 6Alkyl amino or two-(C 1-C 4Alkyl) amino, perhaps representative is optional separately by cyano group, halogen or C 1-C 4The C that alkyl replaces 3-C 6Cycloalkyl, C 3-C 6Cycloalkyl oxy, C 3-C 6Cycloalkyl sulfenyl or C 3-C 6Cycloalkyl amino,
R 19Represent hydrogen, perhaps representative is optional by cyano group, hydroxyl, halogen or C 1-C 4The C that alkoxyl replaces 1-C 6Alkyl, perhaps representative is optional separately by the C of cyano group or halogen replacement 3-C 6Thiazolinyl or C 3-C 6Alkynyl, perhaps representative is optional by cyano group, halogen or C 1-C 4The C that alkyl replaces 3-C 6Cycloalkyl,
R 20Represent hydrogen, perhaps representative is optional by cyano group, hydroxyl, halogen or C 1-C 4The C that alkoxyl replaces 1-C 6Alkyl, perhaps representative is optional separately by the C of cyano group or halogen replacement 3-C 6Thiazolinyl or C 3-C 6Alkynyl, perhaps representative is optional by cyano group, halogen or C 1-C 4The C that alkyl replaces 3-C 6Cycloalkyl, perhaps representative is optional by nitro, cyano group, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4The phenyl that halogenated alkoxy replaces is perhaps with R 19Representative is optional separately by C together 1-C 4The C that alkyl replaces 2-C 6Alkane two bases or C 2-C 5Oxa-alkane two bases,
X 4Represent nitro, cyano group, carboxyl, carbamoyl, formoxyl, amino-sulfonyl, hydroxyl, amino, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy, and
X 5Represent nitro, cyano group, carboxyl, carbamoyl, formoxyl, amino-sulfonyl, hydroxyl, amino, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy.
The hydrocarbon chain that in the above-mentioned definition, the hydrocarbon chain in for example alkyl, thiazolinyl or alkane two bases comprises with hetero atom and making up--for example alkoxyl--all can be respectively a straight chain or have side chain.
Except as otherwise noted, randomly substituted group can be coverlet replacement or polysubstituted, and wherein for polysubstituted situation, substituting group can be identical or different.
In various character, formula (I) compound is main according to substituent character, can how much and/or the form of optical isomer exist, perhaps the form of the isomer mixture of forming with difference exists, described mixture can separate if desired by conventional methods.The invention provides pure isomer and isomer mixture, and their purposes and the composition that contains them.Yet below for only claiming formula (I) compound for simplicity, but its implication had both referred to pure compound, and if the suitable mixture of isomers that also refers to different proportion.
The preferred meaning of the group that defines in formula (I) compound is as follows.
Het preferably represents following heterocycle:
Pyridin-3-yl, 2-chloropyridine-5-base, 2-picoline-5-base, 1-oxidation-3-pyridine subbase, 2-chloro-1-oxidation-5-pyridine subbase, 2,3-two chloro-1-oxidations-5-pyridine subbase, oxolane-3-base, 5-methyltetrahydrofuran-3-base, 2-diuril azoles-5-base.
A preferably represents-N (R 1) (R 2) or S (R 2).
R 1Preferred hydrogen, methyl, ethyl, n-pro-pyl or isopropyl, benzyl, phenethyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, vinyl, 1-acrylic, 2-acrylic, acetenyl, 1-propinyl or the 2-propynyl represented.
R 2Preferred represent methylidene, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, vinyl, 1-acrylic, 2-acrylic, acetenyl, 1-propinyl, 2-propynyl ,-C (=O)-CH 3Or benzyl.
R preferably represent hydrogen, methyl, ethyl, n-pro-pyl or isopropyl, vinyl, 1-acrylic, 2-acrylic, acetenyl, 1-propinyl, 2-propynyl ,-C (=O)-CH 3Or benzyl, perhaps with R 2Preferably represent one of following groups together:
-CH 2-CH 2-、-CH 2-CH 2-CH 2-、-CH 2-O-CH 2-、-CH 2-S-CH 2-、
-CH 2-NH-CH 2-、-CH 2-N(CH 3)-CH 2-。
X preferably represents N-NO 2Or N-CN.
Het especially preferably represents following heterocycle:
2-chloropyridine-5-base, 2-picoline-5-base, 1-oxidation-3-pyridine subbase, 2-chloro-1-oxidation-5-pyridine subbase, 2,3-two chloro-1-oxidations-5-pyridine subbase, oxolane-3-base, 5-methyltetrahydrofuran-3-base, 2-diuril azoles-5-base.
A is representative-N (R especially preferably 1) (R 2).
R 1Especially preferably represent hydrogen, methyl or ethyl.
R 2Preferred especially represent methylidene, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, vinyl, 1-acrylic, 2-acrylic, acetenyl, 1-propinyl, 2-propynyl ,-C (=O)-CH 3Or benzyl.
R especially preferably represent hydrogen, methyl, ethyl or C (=O)-CH 3, perhaps with R 2Especially preferably represent one of following groups together:
-CH 2-CH 2-、-CH 2-CH 2-CH 2-、-CH 2-O-CH 2-、-CH 2-S-CH 2-。
Preferred formula (I) compound that can propose is " agricultural chemicals handbook (The PesticideManual) ", the 13rd edition, and listed anabasine among 2003 (the British Crop Protection Council).
The Imidacloprid (imidacloprid) that a kind of extremely particularly preferred compound is a following formula
Figure A20058003140800171
And it is known in for example EP A1 0,192 060.
The thiophene worm amine (clothianidin) that another kind of extremely particularly preferred compound is a following formula
Figure A20058003140800172
And it is known in for example EP A 20 376 279.
The thiophene worm piperazine (thiamethoxam) that another kind of extremely particularly preferred compound is a following formula
Figure A20058003140800181
And it is known in for example EP A2 0 580 553.
The thiophene worm quinoline (thiacloprid) that another kind of extremely particularly preferred compound is a following formula
Figure A20058003140800182
And it is known in for example EP A2 0 235 725.
The MTI-446 (dinotefuran) that another kind of extremely particularly preferred compound is a following formula
Figure A20058003140800183
And it is known in for example EP A1 0 649 845.
The Acetamiprid (acetamiprid) that another kind of extremely particularly preferred compound is a following formula
Figure A20058003140800184
And it is known in for example WO A1 91/04965.
The Nitenpyram (nitenpyram) that another kind of extremely particularly preferred compound is a following formula
Figure A20058003140800185
And it is known in for example EP A2 0 302 389.
Above-mentioned wide in range or preferred group definition or explanation be combination with one another as required, promptly comprises the combination between each scope and the preferable range.
The present invention preferably uses formula (I) compound of the combination that comprises above-mentioned preferred (preferably) implication.
The present invention especially preferably uses formula (I) compound of the combination that comprises above-mentioned special preferred meaning.
Preferred extremely especially formula (I) compound that uses the combination that comprises above-mentioned extremely special preferred meaning of the present invention.
Saturated or unsaturated alkyl, for example alkyl or alkenyl comprises and heteroatomic combination, alkoxyl for example all can be respectively straight chain within the bounds of possibility or have side chain.
Except as otherwise noted, randomly substituted group can be coverlet replacement or polysubstituted, and wherein under polysubstituted situation, substituting group can be identical or different.
In various character, formula (IV-a), (IV-b), (IV-c), (IV-d) and (IV-e) compound is main according to substituent character, can how much and/or the form of optical isomer exist, perhaps the form of the isomer mixture of forming with difference exists, and described mixture can separate if desired by conventional methods.In composition of the present invention, can use pure isomer and isomer mixture, and can use them according to the present invention.Yet,, only claim formula (IV-a), (IV-b), (IV-c), (IV-d) and (IV-e) compound, but its implication had both referred to pure compound, and if the suitable mixture that also refers to the isomeric compound of different proportion below for for simplicity.
The preferred meaning of the above-mentioned group that with the formula of improving the crop compatibility (IIa), (IIb), (IIc), (IId) and (IIe) compound (" herbicide-safener ") is relevant is defined as follows.
M preferably represents numeral 0,1,2,3 or 4.
A 1One of preferred representative divalent heterocyclic group shown below
Figure A20058003140800191
N preferably represents numeral 0,1,2,3 or 4.
A 2Optional separately methylene or the ethylidene that is replaced by methyl, ethyl, methoxycarbonyl group or carbethoxyl group of preferred representative.
R 8Preferred representation hydroxy, sulfydryl, amino, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, methyl mercapto, ethylmercapto group, positive rosickyite base or different rosickyite base, positive butylthio, isobutyl sulfenyl, secondary butylthio or uncle's butylthio, methylamino, ethylamino, n-pro-pyl amino or isopropyl amino, normal-butyl amino, isobutylamino, sec-butyl amino or tert-butyl group amino, dimethylamino or diethylamino.
R 9Preferred representation hydroxy, sulfydryl, amino, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, the own oxygen base of 1-methyl, allyloxy, 1-allyloxy methyl ethoxy, methyl mercapto, ethylmercapto group, positive rosickyite base or different rosickyite base, positive butylthio, the isobutyl sulfenyl, secondary butylthio or uncle's butylthio, methylamino, ethylamino, n-pro-pyl amino or isopropyl amino, normal-butyl amino, isobutylamino, sec-butyl amino or tert-butyl group amino, dimethylamino or diethylamino.
R 10Optional separately methyl, ethyl, n-pro-pyl or the isopropyl that is replaced by fluorine, chlorine and/or bromine of preferred representative.
R 11The preferred hydrogen of representing, optional separately by methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, acrylic, cyclobutenyl, propinyl or butynyl, methoxy, ethoxyl methyl, methoxy ethyl, ethoxyethyl group, dioxolanes ylmethyl, furyl, furyl methyl, thienyl, thiazolyl, the piperidyl of fluorine and/or chlorine replacement, or the optional phenyl that is replaced by fluorine, chlorine, methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group.
R 12The preferred hydrogen of representing, optional separately by methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, acrylic, cyclobutenyl, propinyl or butynyl, methoxy, ethoxyl methyl, methoxy ethyl, ethoxyethyl group, dioxolanes ylmethyl, furyl, furyl methyl, thienyl, thiazolyl, the piperidyl of fluorine and/or chlorine replacement, or the optional phenyl that is replaced by fluorine, chlorine, methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, perhaps with R 11Optional group-the CH that is replaced by methyl, ethyl, furyl, phenyl, fused benzene rings or replaced by following two substituting groups of representative together 2-O-CH 2-CH 2-and-CH 2-CH 2-O-CH 2-CH 2One of-, described two substituting groups form 5 or 6 yuan of carbocyclic rings with the C atom that is connected with them.
R 13Preferred hydrogen, cyano group, fluorine, chlorine, the bromine represented, perhaps optional separately methyl, ethyl, n-pro-pyl or isopropyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl or the phenyl that is replaced by fluorine, chlorine and/or bromine of representative.
R 14The preferred hydrogen of representing, perhaps optional separately methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group that is replaced by hydroxyl, cyano group, fluorine, chlorine, methoxyl group, ethyoxyl, positive propoxy or isopropoxy of representative.
R 15Preferred hydrogen, cyano group, fluorine, chlorine, the bromine represented, perhaps optional separately methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl or the phenyl that is replaced by fluorine, chlorine and/or bromine of representative.
X 1Preferred nitro, cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, a chlorodifluoramethyl-, a fluorine dichloromethyl, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, difluoro-methoxy or the trifluoromethoxy represented.
X 2Preferred hydrogen, nitro, cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, a chlorodifluoramethyl-, a fluorine dichloromethyl, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, difluoro-methoxy or the trifluoromethoxy represented.
X 3Preferred hydrogen, nitro, cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, a chlorodifluoramethyl-, a fluorine dichloromethyl, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, difluoro-methoxy or the trifluoromethoxy represented.
R preferably represents one of numeral 0,1,2,3 or 4.
S preferably represents one of numeral 0,1,2,3 or 4.
R 16Preferred hydrogen, methyl, ethyl, n-pro-pyl or the isopropyl represented.
R 17Preferred hydrogen, methyl, ethyl, n-pro-pyl or the isopropyl represented.
R 18The preferred hydrogen of representing, optional separately by cyano group, fluorine, chlorine, methoxyl group, ethyoxyl, the methyl that positive propoxy or isopropoxy replace, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, the sec-butyl or the tert-butyl group, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, methyl mercapto, ethylmercapto group, positive rosickyite base or different rosickyite base, positive butylthio, the isobutyl sulfenyl, secondary butylthio or uncle's butylthio, methylamino, ethylamino, n-pro-pyl amino or isopropyl amino, normal-butyl amino, isobutylamino, sec-butyl amino or tert-butyl group amino, dimethylamino or diethylamino, or optional separately by cyano group, fluorine, chlorine, bromine, methyl, ethyl, the cyclopropyl that n-pro-pyl or isopropyl replace, cyclobutyl, cyclopenta, cyclohexyl, cyclopropyl oxygen base, cyclobutyl oxygen base, cyclopentyloxy, cyclohexyl oxygen base, the cyclopropyl sulfenyl, the cyclobutyl sulfenyl, the cyclopenta sulfenyl, the cyclohexyl sulfenyl, cyclopropyl amino, cyclobutyl amino, cyclopenta amino or cyclohexyl amino.
R 19The preferred hydrogen of representing, optional separately methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group or the sec-butyl that is replaced by cyano group, hydroxyl, fluorine, chlorine, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, optional separately acrylic, cyclobutenyl, propinyl or the butynyl that is replaced by cyano group, fluorine, chlorine or bromine, or optional separately cyclopropyl, cyclobutyl, cyclopenta or the cyclohexyl that is replaced by cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-pro-pyl or isopropyl.
R 20The preferred hydrogen of representing, optional separately by cyano group, hydroxyl, fluorine, chlorine, methoxyl group, ethyoxyl, the methyl that positive propoxy or isopropoxy replace, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group or sec-butyl, optional separately by cyano group, fluorine, the acrylic that chlorine or bromine replaces, cyclobutenyl, propinyl or butynyl, optional separately by cyano group, fluorine, chlorine, bromine, methyl, ethyl, the cyclopropyl that n-pro-pyl or isopropyl replace, cyclobutyl, cyclopenta or cyclohexyl, or it is optional by nitro, cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, the sec-butyl or the tert-butyl group, trifluoromethyl, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, the phenyl that difluoro-methoxy or trifluoromethoxy replace is perhaps with R 19Representative is optional separately by the fourth-1 of methyl or ethyl replacement, 4-two bases (1, the 3-propylidene), penta-1,5-two bases, 1-oxa-fourth-1,4-two bases or 3-oxa-penta-1,5-two bases together.
X 4Preferred nitro, cyano group, carboxyl, carbamoyl, formoxyl, sulfamoyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, trifluoromethyl, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, difluoro-methoxy or the trifluoromethoxy represented.
X 5Preferred nitro, cyano group, carboxyl, carbamoyl, formoxyl, sulfamoyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl, ethyl, n-pro-pyl or isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, trifluoromethyl, methoxyl group, ethyoxyl, positive propoxy or isopropoxy, difluoro-methoxy or the trifluoromethoxy represented.
During preferred extremely especially formula (IIa) examples for compounds as herbicide-safener of the present invention is listed in the table below.
TableFormula (IIa) examples for compounds
Figure A20058003140800221
Table(continuing)
Figure A20058003140800231
Table(continuing)
Figure A20058003140800241
Table(continuing)
Figure A20058003140800251
During preferred extremely especially formula (IIb) examples for compounds as herbicide-safener of the present invention is listed in the table below.
Figure A20058003140800252
TableFormula (IIb) examples for compounds
Example number (position) X 2 (position) X 3 A 2 R 9
IIb-1 (5) Cl - CH 2 OH
IIb-2 (5) Cl - CH 2 OCH 3
IIb-3 (5) Cl - CH 2 OC 2H 5
IIb-4 (5) Cl - CH 2 OC 3H 7-n
IIb-5 (5) Cl - CH 2 OC 3H 7-i
IIb-6 (5) Cl - CH 2 OC 4H 9-n
IIb-7 (5) Cl - CH 2 OCH(CH 3)C 5H 11-n
IIb-8 (5) Cl (2) F CH 2 OH
IIb-9 (5) Cl (2) Cl CH 2 OH
IIb-10 (5) Cl - CH 2 OCH 2CH=CH 2
IIb-11 (5) Cl - CH 2 OC 4H 9-i
Table(continuing)
Figure A20058003140800271
During preferred extremely especially formula (IIc) examples for compounds as herbicide-safener of the present invention is listed in the table below.
TableFormula (IIc) examples for compounds
Figure A20058003140800281
During preferred extremely especially formula (IId) examples for compounds as herbicide-safener of the present invention is listed in the table below.
Figure A20058003140800291
TableFormula (IId) examples for compounds
Figure A20058003140800292
Table(continuing)
Figure A20058003140800301
Table(continuing)
During preferred extremely especially formula (IIe) examples for compounds as herbicide-safener of the present invention is listed in the table below.
Figure A20058003140800312
TableFormula (IIe) examples for compounds
Figure A20058003140800321
Each self-contained at least a formula (I) reactive compound that is selected from Imidacloprid, thiophene worm piperazine, thiophene worm amine, thiophene worm quinoline, Acetamiprid, Nitenpyram and MTI-446 (dinetofuran) of the preferred active agent combinations of the present invention, and each self-contained at least a above-mentioned safener.
The most preferred compound [component (b)] that improves the crop compatibility has: cloquitocet_mexyl, fenchlorazole, the acid of Shuan Ben oxazole, mefenpyrdiethyl, Xie Cao oxazole, fenclorim, cumyluron, daimuron, dimepiperate and Compound I Ie-5 and IIe-11, lay special stress on cloquitocet_mexyl and mefenpyrdiethyl.
List the example that the particularly preferred selectivity of the present invention is killed insect and/or killed the mite bond in the following table, contain a kind of formula (I) reactive compound of above-mentioned definition and a kind of safener of above-mentioned definition in every kind of the described bond.
TableThe example of bond of the present invention
The reactive compound of formula (I) Safener
Imidacloprid Cloquitocet_mexyl
Imidacloprid Fenchlorazole
Imidacloprid The acid of Shuan Ben oxazole
Imidacloprid Mefenpyrdiethyl
Imidacloprid Xie Cao oxazole
Imidacloprid Fenclorim
Imidacloprid Cumyluron
Imidacloprid Daimuron
Imidacloprid Dimepiperate
Imidacloprid IIe-11
Imidacloprid IIe-5
Thiophene worm amine Cloquitocet_mexyl
Thiophene worm amine Fenchlorazole
Thiophene worm amine The acid of Shuan Ben oxazole
Thiophene worm amine Mefenpyrdiethyl
Thiophene worm amine Xie Cao oxazole
Thiophene worm amine Fenclorim
Thiophene worm amine Cumyluron
Thiophene worm amine Daimuron
Thiophene worm amine Dimepiperate
The reactive compound of formula (I) Safener
Thiophene worm amine IIe-11
Thiophene worm amine IIe-5
Thiophene worm piperazine Cloquitocet_mexyl
Thiophene worm piperazine Fenchlorazole
Thiophene worm piperazine The acid of Shuan Ben oxazole
Thiophene worm piperazine Mefenpyrdiethyl
Thiophene worm piperazine Xie Cao oxazole
Thiophene worm piperazine Fenclorim
Thiophene worm piperazine Cumyluron
Thiophene worm piperazine Daimuron
Thiophene worm piperazine Dimepiperate
Thiophene worm piperazine IIe-5
Thiophene worm piperazine IIe-11
Thiophene worm quinoline Cloquitocet_mexyl
Thiophene worm quinoline Fenchlorazole
Thiophene worm quinoline The acid of Shuan Ben oxazole
Thiophene worm quinoline Mefenpyrdiethyl
Thiophene worm quinoline Xie Cao oxazole
Thiophene worm quinoline Fenclorim
Thiophene worm quinoline Cumyluron
Thiophene worm quinoline Daimuron
Thiophene worm quinoline Dimepiperate
Thiophene worm quinoline IIe-11
Thiophene worm quinoline IIe-5
MTI-446 Cloquitocet_mexyl
MTI-446 Fenchlorazole
MTI-446 The acid of Shuan Ben oxazole
MTI-446 Mefenpyrdiethyl
MTI-446 Xie Cao oxazole
The reactive compound of formula (I) Safener
MTI-446 Fenclorim
MTI-446 Cumyluron
MTI-446 Daimuron
MTI-446 Dimepiperate
MTI-446 IIe-5
MTI-446 IIe-11
Acetamiprid Cloquitocet_mexyl
Acetamiprid Fenchlorazole
Acetamiprid The acid of Shuan Ben oxazole
Acetamiprid Mefenpyrdiethyl
Acetamiprid Xie Cao oxazole
Acetamiprid Fenclorim
Acetamiprid Cumyluron
Acetamiprid Daimuron
Acetamiprid Dimepiperate
Acetamiprid IIe-5
Acetamiprid IIe-11
Nitenpyram Cloquitocet_mexyl
Nitenpyram Fenchlorazole
Nitenpyram The acid of Shuan Ben oxazole
Nitenpyram Mefenpyrdiethyl
Nitenpyram Xie Cao oxazole
Nitenpyram Fenclorim
Nitenpyram Cumyluron
Nitenpyram Daimuron
Nitenpyram Dimepiperate
Nitenpyram IIe-5
Nitenpyram IIe-11
As general formula (IIa) compound of safener is known compound, and/or can be by known method preparation (referring to WO-A-91/07874, WO-A-95/07897) itself.
As general formula (IIb) compound of safener is known compound, and/or can be by known method preparation (referring to EP-A-191736) itself.
As general formula (IIc) compound of safener is known compound, and/or can be by known method preparation (referring to DE-A-2218097, DE-A-2350547) itself.
As general formula (IId) compound of safener is known compound, and/or can be by known method preparation (referring to DE-A-19621522/US-A-6235680) itself.
As general formula (IIe) compound of safener is known compound, and/or can be by known method preparation (referring to WO-A-99/66795/US-A-6251827) itself.
Surprisingly, have now found that the compound that includes general formula (I) of above definition and the active agent combinations of the safener (antipoison) that (b) listed above organizes have excellent insecticidal activity, have good crop plants tolerance simultaneously, and find that they can be used for preventing and treating the insect of various crops.
Among the present invention, will be understood that very surprisingly that (b) listed above group compound can improve the insecticidal activity of general formula (I) compound in some cases, thereby obtains synergistic effect.
What can emphasize is, particularly preferred (b) group bond component has particularly advantageous effect especially when being applied to following plant, and described plant comprises: cereal, for example wheat, oat, barley, triticale and rye; And corn, grain, rice, sugarcane, soybean, potato, cotton, rape, tobacco, lupulus and fruit plant (comprise pomaceous fruits fruit, for example apple and pears; Stone fruit, for example peach, honey peach, cherry, Li Hexing; Citrus fruit, for example orange, grapefruit, bitter orange, lemon, cumquat, oranges and tangerines and Sa Mo tangerine; Nut fruits, for example pistachio nut, almond, English walnut and pecan nut; Tropical fruit (tree), for example mango, papaw, pineapple, nipa palm and banana, and grape vine).
Bond of the present invention also can be used for protecting vegetables.Wherein these vegetables comprise arithoke, eggplant, cauliflower, stem cabbage, mung bean, pea, fennel, salad usefulness witloof, cucumber, left-falling stroke indigo plant, leaf usefulness lettuce, pepper grass, leek, Switzerland's beet, carrot, green capsicum, rheum officinale, table beet, red cabbage, brussels sprouts, celery, beet, tomato, chestnut, scarlet runner bean, crow green onion, corn, asparagus, table beet, spinach, cabbage (whitec abbage), savoy cabbage, onion, shagreen bush pumpkin.
Active agent combinations of the present invention can be used for for example following plant usually:
Dicotyledonous crops with the subordinate:Gossypium (Gossypium), Glycine (Glycine), Beta (Beta), Daucus (Daucus), Phaseolus (Phaseolus), Pisum (Pisum), Solanum (Solanum), linum (Linum), Ipomoea (Ipomoea), Vicia (Vicia), Nicotiana (Nicotiana), tomato belongs to (Lycopersicon), Arachis (Arachis), Brassicas (Brassica), Lactuca (Lactuca), Cucumis (Cucumis), Cucurbita (Cuburbita), Helianthus (Helianthus).
Monocot crops with the subordinate:Oryza (Oryza), Zea (Zea), Triticum (Triticum), Hordeum (Hordeum), Avena (Avena), Secale (Secale), sorghum (Sorghum), Panicum (Panicum), saccharum (Saccharum), Ananas (Ananas), Asparagus (Asparagus), allium (Allium).
Yet the purposes of active agent combinations never only limits to these genus, but similarly also prolongs and other plants.
The beneficial effect of the crop plants compatibility of active agent combinations is particularly remarkable under some concentration ratio.Yet the weight ratio of reactive compound can change in the scope of relative broad in the active agent combinations.Generally speaking, reactive compound or its salt of the formula (I) of corresponding every weight portion exist 0.001 to 1000 weight portion, preferred 0.01 to 100 weight portion, preferred especially 0.05 to 10 weight portion, the compound (antipoison/safener) of the raising crop plants compatibility of a kind of above-mentioned (b) of 0.07 to 1.5 weight portion most preferably.
Mixture of the present invention is particularly suitable for handling seed.For example, most of infringement that cause by insect, that crop plants is caused as far back as seed when duration of storage is subjected to invading and harassing, seed broadcast soil after and just taken place during the plant germination and after the rudiment just.This stage is crucial especially, is stranded for just root and the bud growing plants is responsive especially, even very little injury also can cause whole strain plant death.Therefore, by using suitable composition to protect seed and just having special significant meaning the plant of rudiment.
Come pest control known already by handling plant seed, it also is the theme of updating.Yet the processing of seed need solve a series of problems that can not always solve with satisfactory way usually.Therefore, need develop and need not behind the plant planting or use the protection seed of crop protection products after emerging in addition and just in the method for the plant of rudiment.In addition, also need the dosage optimization of reactive compound for can be to seed and just providing best protection in order to avoid be subjected to the invasion and attack of insect the plant of rudiment, but simultaneously again can be owing to employed reactive compound injures plant itself.Especially, method for treating seeds also should consider genetically modified plants intrinsic insecticidal properties, with by using minimum crop protection products to obtain to seed with just in the best protection of the plant of rudiment.
Therefore, the present invention also relates to a kind of by protecting seed with compositions-treated seed of the present invention and just avoiding the method for insect invasion and attack the plant of rudiment especially.The present invention equally also relates to composition of the present invention and is used to handle seed with the protection seed with just avoiding the purposes that insect attacks the plant of rudiment.In addition, the invention still further relates to handled with the present composition, avoid the seed of insect invasion and attack to protect it.
One of advantage of the present invention is, absorption can mean with these compositions-treated seeds and not only protected seed self in the present composition special, attacks but also protected the plant that grows up to after emerging to avoid insect.In this mode, can save at seeding time or interior instant processing of short period after this crop.
Another advantage is that composition of the present invention is compared with each independent reactive compound has the collaborative insecticidal activity that increases.This feasible consumption that can optimize reactive compound.At this, be considered to particularly advantageous and be because (b) existence of group blending ingredients, can with effective and efficient manner restriction surprisingly or suppress fully by used insecticidal active compound cause to just in the injury of rudiment plant.
In addition, what also should think advantage is that mixture of the present invention also can be used in particular for transgenic seed, can express a kind of albumen at insect by the plant that above-mentioned transgenic seed grows up to.By with the above-mentioned seed of compositions-treated of the present invention; only the expression by for example insecticidal proteins can prevent and treat some insect; and surprisingly, the result also comprises the activity that has obtained with the cooperative compensating of composition of the present invention, and this has increased the drug effect of the protection of anti-insect invasion and attack again.
Composition of the present invention is suitable for protecting the seed of any plant variety that is used for agricultural, greenhouse, forestry, gardening or viticulture.The form of the seed of following plant particularly: corn, peanut, Canadian rape, rape, opium poppy, olive, coconut, cocoa, soybean, cotton, beet (for example sugar beet and fodder beet), rice, grain, wheat, barley, oat, rye, sunflower, sugarcane or tobacco.Similarly, composition of the present invention also is applicable to the seed of handling various vegetables, as the seed of stem cabbage, cauliflower, cabbage, tomato, green capsicum, muskmelon, shagreen bush pumpkin and cucumber, or the seed of various pomaceous fruits fruit, for example seed of apple and pears.Particularly importantly to the processing of corn, soybean, cotton, wheat and Canadian rape or rape seeds.
As mentioned above, with compositions-treated transgenic seed of the present invention also particular importance.This shows as the seed of the plant that comprises at least a heterologous gene usually, and described gene is being arranged the polypeptide expression that particularly has insecticidal properties.In the present invention, heterologous gene in the transgenic seed can come from microorganism, for example bacillus (Bacillus), rhizobium (Rhizobium), false unicellular bacterium (Pseudomonas), Serratieae (Serratia), wood mould (Trichoderma), rod shape bacillus (Clavibacter), sacculus mould (Glomus) or sticking broom mould (Gliocladium).The present invention is particularly suitable for processing and comprises at least a transgenic seed that comes from the heterologous gene of bacillus kind (Bacillus sp.), and its gene outcome shows the activity of anti-European corn borer (European corn borer) and/or corn rootworm (corn rootworm).The heterologous gene that especially preferably comes from bacillus thuringiensis (Bacillusthuringiensis).
Within the scope of the invention, composition of the present invention both can be applied to seed separately, also can the appropriate formulation form be applied to seed.Preferably, stable as it to be handled under the state that is enough in processing, avoid damaging at seed.Generally speaking, can gather and sow between any time point handle seed.Usually used seed is separated with plant, and do not contain cob, the pulp of shell, stem, epidermis, hair or fruit.
Handle kind of a period of the day from 11 p.m. to 1 a.m and must be noted that usually, the present composition is applied to the sprouting that the amount of the amount of seed and/or other additive should be chosen as seed not to be had adverse influence or does not injure the plant that grows up to.Particularly for the reactive compound that under some rate of application, has the poisonous plant effect, must keep this point firmly in mind.
Composition of the present invention can directly be used, and that is to say the component that need not to comprise other, also need not dilution.In general, preferably composition is administered on the seed in the mode of appropriate formulation.Suitable preparation that is used for seed treatment and method are for known to those of ordinary skills, and for example putting down in writing to some extent in the following document: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 A1, WO 2002/080675A1, WO 2002/028186 A2.
Active agent combinations of the present invention can be converted into conventional formulation, for example solution, emulsion, wetting powder, suspending agent, pulvis, powder agent, paste, soluble powder, granule, outstanding newborn concentrating agents, through the natural and synthetic material of reactive compound dipping, and the microcapsule formulations in the polymer.
These preparations are made in known manner, for example reactive compound are mixed with filler, promptly mix with liquid flux and/or solid carrier, can select to use simultaneously surfactant, i.e. emulsifier and/or dispersant and/or blowing agent.
If make water, for example also can use organic solvent as secondary solvent as filler.Suitable liquid flux is mainly: aromatic compound, for example dimethylbenzene, toluene or Fluhyzon; Chlorinated aromatic compound or chloro aliphatic hydrocarbon, for example chlorobenzene, vinyl chloride or carrene; Aliphatic hydrocarbon, for example cyclohexane or paraffin, for example mineral oil fractions, mineral oil and vegetable oil; Alcohol, for example butanols or ethylene glycol, and ether and ester; Ketone, for example acetone, MEK, methyl iso-butyl ketone (MIBK) or cyclohexanone; Intensive polar solvent, for example dimethyl formamide and dimethyl sulfoxide (DMSO); And water.
The solid carrier that is fit to has:
For example, ammonium salt; The natural minerals of pulverizing, for example kaolin, clay, talcum, chalk, quartz, attapulgite, montmorillonite or diatomite; And the synthetic material of pulverizing, for example high dispersive silica, aluminium oxide and silicate.The solid carrier that is applicable to granule is: for example pulverize the also natural rock of classification, for example calcite, marble, float stone, sepiolite and dolomite; And synthetic inorganic and organic powder particles, and organic particle, for example sawdust, coconut husk, corncob and tobacco stem.The emulsifier and/or the blowing agent that are fit to are: for example nonionic and anion emulsifier, for example for example alkylaryl polyglycol ether, alkylsulfonate, alkyl sulfate, arylsulphonate of polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether; And protein hydrolysate.The dispersant that is fit to is: for example lignin sulfite waste liquor and methylcellulose.
Can use tackifier in the preparation, the natural and synthetic polymer of for example carboxymethyl cellulose, and powder, particle or latex shape, for example gum Arabic, polyvinyl alcohol and polyvinyl acetate; And natural phospholipid, for example cephalin and lecithin, and synthetic phospholipid.Other possible additive is mineral oil and vegetable oil.
Can use colouring agent, for example inorganic pigment, for example iron oxide, titanium oxide and Prussian blue; And organic dyestuff, for example alizarin dyes, azo dyes and metal phthalocyanine dyestuff; And micronutrient, for example molysite, manganese salt, boron salt, mantoquita, cobalt salt, molybdenum salt and zinc salt.
Preparation generally contains the reactive compound of 0.1 to 95 weight %, preferred 0.5 to 90 weight %.
Active agent combinations is used with the form of promptly using (ready-to-use) preparation usually.Yet the reactive compound that contains in the active agent combinations also can be so that the independent dosage form that mixes again of time spent be used, and promptly the form of mixing (tank mix) with bucket is used.
Active agent combinations can also itself or in preparation, mix use with other known weed killer herbicides, can be promptly with preparation or bucket mix formulation form equally.Also can mix, for example mix with fungicide, insecticide, miticide, nematocide, attractant, disinfectant, bactericide, bird repellent, growth substance, plant nutrient and soil conditioner with other known reactive compounds.In addition, for some concrete application processes, postemergence application particularly, also can advantageously in preparation, add the mineral oil of plant compatibility or vegetable oil (for example commercially available prod " Rako Binol ") or ammonium salt for example ammonium sulfate or ammonium thiocyanate as further additive.
Active agent combinations can with itself, its dosage form or by the further dilution and the type of service that makes uses for example ready to use solution agent, suspending agent, emulsion, pulvis, paste and granule of described preparation.Can use by conventional method, for example water, spraying, atomizing, dust or spread fertilizer over the fields.
The rate of application of active agent combinations can change within the specific limits; In various factors, rate of application depends primarily on weather and edaphic factor.Generally speaking, rate of application is 0.005 to 5kg per hectare, preferred 0.01 to 2kg per hectare, preferred especially 0.05 to 1.0kg per hectare.
Active agent combinations can be used before plant emerges He after emerging, and promptly uses by seedling pretreatment process and seedling post treatment method.
Safener to be used can be used for the preliminary treatment (seed dressing) of crop plants seed or puts into the seed ditch dug with a plow prior to seeding according to its performance, or uses jointly with weed killer herbicide after plant emerges preceding or emerges.
Active agent combinations is applicable to the animal pest that control runs in agricultural, preferred arthropods and nematode, particularly insect and arachnid.Described active agent combinations is effective to common sensitivity and resistance species, and effective to the whole or single developmental stage.Above-mentioned insect comprises:
Isopoda (Isopoda), for example, comb beach louse (Oniscus asellus), pillworm (Armadillidium vulgare), Porcellio scaber.
Doubly sufficient order (Diplopoda), for example, Blaniulus guttulatus.
Lip foot order (Chilopoda), for example, Geophilus carpophagus, Scutigeraspp..
Comprehensive order (Symphyla), for example, Scutigerella immaculata.
Thysanoptera (Thysanura), for example, silverfish (Lepisma saccharina).
Collembola (Collembola), for example, arms Onychiurus arcticus (Onychiurus armatus).
Orthoptera (Orthoptera), for example, tame Xi (Acheta domesticus), Gryllotalpa spp kind (Gryllotalpa spp.), African migratory locust (Locusta migratoriamigratorioides), black locust belong to kind of (Melanoplus spp.), a desert locust (Schistocerca gregaria).
Blattaria (Blattaria), for example, oriental cockroach (Blatta orientalis), American cockroach (Periplaneta americana), leucophaea maderae (Leucophaeamaderae), blatta germanica (Blattella germanica).
Dermaptera (Dermaptera), for example, European earwig (Forficula auricularia).
Isoptera (Isoptera), for example, Reticulitermes kind (Reticulitermes spp.).
Anoplura (Phthiraptera), for example, body louse (Pediculus humanus corporis), Haematopinus kind (Haematopinus spp.), Linognathus kind (Linognathus spp.), Trichodectes kind (Trichodectes spp.), Damalinia kind (Damalinia spp.).
Thrips (Thysanoptera), for example, greenhouse bar hedge thrips (Hercinothripsfemoralis), onion thrips (Thrip stabaci), palm thrips (Thrips palmi), alfalfa thrips (Frankliniella occidentalis).
Heteroptera (Heteroptera), for example, Eurygasterspp belongs to kind of (Eurygaster spp.), a Dysdercus intermedius, square butt stinkbug (Piesma quadrata), bed bug (Cimex lectularius), phodnius prolixus (Rhodnius prolixus), Triatoma kind (Triatoma spp.).
With wing solid (Homoptera), for example, wild cabbage aleyrodid (Aleurodes brassicae), cassava aleyrodid (Bemisia tabaci), greenhouse whitefly (Trialeurodes vaporariorum), cotten aphid (Aphis gossypii), cabbage aphid (Brevicoryne brassicae), the tea Fischer conceals knurl aphid (Cryptomyzus ribis), aphis fabae (Aphis fabae), apple aphid (Aphispomi), wooly aphis (Eriosoma lanigerum), mealy plum aphid (Hyalopterusarundinis), grape phylloxera (Phylloxera vastatrix), the goitre woolly aphid belongs to kind of (a Pemphigus spp.), English grain aphid (Macrosiphum avenae), tumor aphid genus kind (Myzusspp.), phorodon aphid (Phorodon humuli), rhopalosiphum padi (Rhopalosiphumpadi), Empoasca flavescens kind (Empoasca spp.), Euscelis bilobatus, rice leafhopper (Nephotettix cincticeps), water wood hard a red-spotted lizard (Lecanium corni), black scale (Saissetia oleae), small brown rice planthopper (Laodel phax striatellus), brown planthopper (Nilaparvata lugens), red kidney Aspidiotus (Aonidiella aurantii), ivy Aspidiotus (Aspidiotus hederae), mealybug belongs to kind of (a Pseudococcus spp.), Psylla spp kind (Psylla spp.).
Lepidoptera (Lepidoptera), for example, Pectinophora gossypiella (Pectinophoragossypiella), loose looper (Bupalus piniarius), winter geometrid moth (Cheimatobiabrumata), the thin moth of apple (Lithocolletis blancardella), apple ermine moth (Hyponomeuta padella), diamond-back moth (Plutella xylostella), malacosoma neustria (Malacosoma neustria), pornography and drug moth (Euproctis chrysorrhoea), Euproctis kind (Lymantria spp.), cotton lyonetid (Bucculatrix thurberiella), tangerine lyonetid (Phyllocnistis citrella), Agrotis kind (Agrotis spp.), root eating insect belongs to kind of (an Euxoa spp.), the dirty Noctua kind (Feltia spp.) of cutting, earias insulana (Earias insulana), Heliothis kind (Heliothis spp.), tomato moth (Mamestra brassicae), small noctuid (Panolis flammea), Spodoptera kind (Spodoptera spp.), cabbage looper (Trichoplusia ni), codling moth (Carpocapsa pomonella), Pieris spp kind (Pieris spp.), straw borer spp kind (Chilo spp.), corn borer (Pyrausta nubilalis), Anagasta kuehniella (Ephestia kuehniella), greater wax moth (Galleria mellonella), curtain rain moth (Tineola bisselliella), bag rain moth (Tinea pellionella), brownly knit moth (Hofmannophila pseudospretella), the yellow volume of flax moth (Cacoecia podana), Capua reticulana, spruce bunworm (Choristoneura fumiferana), grape codling moth (Clysia ambiguella) (Clysia ambiguella), tea long paper moth (Homona magnanima), the green volume of oak moth (Tortrix viridana), Cnaphalocerus spp., Oulema oryzae (Oulemaoryzae).
Coleoptera (Coleoptera), for example, furniture death watch beetle (Anobium punctatum), lesser grain borer (Rhizopertha dominica), dislike bar bean weevil (Bruchidius obtectus), acanthoscelides obtectus (Acanthoscelides obtectus), North America house longhorn beetle (Hylotrupesbajulus), willow firefly chrysomelid (Agelastica alni), colorado potato beetle (Leptinotarsadecemlineata), horseradish daikon leaf beetle (Phaedon cochleariae), chrysomelid genus kind (Diabrotica spp.), rape golden head flea beetle (Psylliodes chrysocephala), the big Epilachna spp of Mexico (Epilachna varivestis), Atomaria spp., saw-toothed grain beetle (Oryzaephilus surinamensis), flower resembles and belongs to kind of (an Anthonomus spp.), grain weevil belongs to kind of (a Sitophilus spp.), black grape ear image (Otiorrhynchus sulcatus), the banana collar resembles (Cosmopolites sordidus), Chinese cabbage seed tortoise resembles (Ceuthorrhynchusassimilis), alfalfa leaf resembles (Hypera postica), khapra beetle belongs to kind of (Dermestesspp.), the spot khapra beetle belongs to kind of (a Trogoderma spp.), Anthrenus kind (Anthrenus spp.), moth-eaten belong to kind of (the Attagenus spp.) of fur, moth-eaten belong to kind of (the Lyctus spp.) of powder, pollen beetle (Meligethes aeneus), Ptinus kind (Ptinus spp.), golden spider beetle (Niptus hololeucus), globose spider beetle (Gibbium psylloides), Tribolium kind (Tribolium spp.), yellow mealworm (Tenebrio molitor), click beetle belongs to kind of (an Agriotes spp.), wide chest Agriotes spp kind (Conoderus spp.), the west melolonthid in May (Melolontha melolontha), the potato melolonthid (Amphimallonsolstitialis), the brown New Zealand rib wing melolonthid (Costelytra zealandica), rice root weevil (Lissorhoptrus oryzophilus).
Hymenoptera (Hymenoptera), for example, pine sawfoy belongs to kind of (Diprion spp.), a real tenthredinidae kind (Hoplocampa spp.), the hair ant belongs to kind of (Lasius spp.), a MonomoriumMayr (Monomorium pharaonis), Vespa kind (Vespa spp.).
Diptera (Diptera), for example, Aedes kind (Aedes spp.), Anopheles kind (Anopheles spp.), Culex kind (Culex spp.), black-tailed fruit flies (Drosophilamelanogaster), Musca kind (Musca spp.), Fannia kind (Fannia spp.), calliphora erythrocephala (Calliphora erythrocephala), Lucilia kind (Lucilia spp.), Carysomyia kind (Chrysomyia spp.), Cuterebra kind (Cuterebra spp.), Gasterophilus kind (Gastrophilus spp.), Hyppobosca spp., Genus Stomoxys kind (Stomoxysspp.), Oestrus kind (Oestrus spp.), Hypoderma kind (Hypoderma spp.), Gadfly kind (Tabanus spp.), Tannia spp., garden march fly (Bibio hortulanus), Oscinella frit (Oscinella frit), grass Hylemyia kind (Phorbia spp.), lamb's-quarters spring fly (Pegomyia hyoscyami), Mediterranean Ceratitis spp (Ceratitis capitata), the big trypetid of olive (Dacus oleae), Europe daddy-longlegs (Tipula paludosa), Hylemyia kind (Hylemyia spp.), liriomyza bryoniae belongs to kind of (a Liriomyza spp.).
Siphonaptera (Siphonaptera), for example, Xanthopsyllacheopis (Xenopsylla cheopis), Ceratophyllus kind (Ceratophyllus spp.).
Arachnids (Arachnida), for example, Middle East gold scorpion (Scorpio maurus), latrodectus mactans (Latrodectus mactans), Acarus siro (Acarussiro), Argas kind (Argas spp.), Ornithodoros kind (Ornithodoros spp.), Dermanyssus gallinae (Dermanyssus gallinae), tea Fischer goitre mite (Eriophyes ribis), the tangerine rust mite (Phyllocoptruta oleivora) that rues, Boophilus kind (Boophilus spp.), Rh kind (Rhipicephalus spp.), Amblyomma kind (Amblyomma spp.), Hyalomma kind (Hyalomma spp.), hard tick belongs to kind of (an Ixodes spp.), Psoroptes kind (Psoroptes spp.), Chorioptes kind (Chorioptes spp.), itch mite belongs to kind of (a Sarcoptes spp.), tarsonemid belongs to kind of (a Tarsonemus spp.), Bryobia praetiosa (Bryobia praetiosa), Panonychus citri belongs to kind of (a Panonychus spp.), Tetranychus kind (Tetranychus spp.), half tarsonemid belongs to kind of (a Hemitarsonemus spp.), short whisker Acarapis kind (Brevipalpus spp.).
Plant nematode comprises, for example, Pratylenchidae belongs to kind of (a Pratylenchus spp.), similar similes thorne (Radopholus similis), fuller's teasel stem eelworm (Ditylenchusdipsaci), the nematode (Tylenchulus semipenetrans) of partly puncturing, Heterodera kind (Heterodera spp.), ball Heterodera kind (Globodera spp.), Meloidogyne kind (Meloidogyne spp.), Aphelenchoides kind (Aphelenchoidesspp.), minute hand Turbatrix kind (Longidorus spp.), Xiphinema kind (Xiphinemaspp.), burr Turbatrix kind (Trichodorus spp.), umbrella Aphelenchoides kind (Bursaphelenchus spp.).
When using as insecticide, active agent combinations is in the type of service of its commercial preparation neutralization by these formulation preparation, and the form that can also mix with synergist exists.Synergist is the compound that improves the reactive compound activity, and the synergist that is added itself not necessarily has activity.
Reactive compound content by the type of service of commercial preparation preparation can change in the scope of broad.The activity compound concentration of type of service can be the reactive compound of 0.0000001 to 95 weight %, preferred 0.0001 to 1 weight %.
The usual manner of using to adapt with type of service carries out.
According to the present invention, can handle all plants and plant parts.The implication of plant is interpreted as all plants and plant population, for example needs and unwanted wild plant or crop plants (comprising the crop plants that nature exists).Crop plants can be for by conventional breeding method and method for optimizing or the plant that obtains by biotechnology and gene engineering method or the combination by said method; comprise genetically modified plants, also comprise the plant cultivars that is subjected to the protection of plant seedling power or is not subjected to its protection.The implication of plant parts is interpreted as all grounds of plant and underground position and organ, for example bud, leaf, Hua Hegen, can be used as that example mentions comprise leaf, needle, stem, do, flower, fruit body, fruit and seed and root, stem tuber and rhizome.The position of plant also comprises plant and asexual and sexual propagation thing, for example seedling, stem tuber, rhizome and the cutting of having gathered.Bond of the present invention also is specially adapted to handle the seed of above-mentioned crop plants.
Reactive compound used according to the invention is to the processing of plant and plant parts, directly carry out or act on its environment, habitat or storage area by conventional treatment method, the for example immersion liquid of described conventional treatment method, spraying, evaporation, atomizing, broadcast sowing, brush, and, also comprise one or more layers dressing for breeding particularly seed of thing.
As mentioned above, can handle all plants and its position according to the present invention.In preferred embodiments,---for example hybridization or protoplast merge---plant species and the botanical variety of acquisition, and their position of having handled wild plant kind and botanical variety or by conventional biological breeding method.---suitable combine---genetically modified plants and botanical variety (genetically modified organisms) and position thereof of acquisition in another embodiment preferred, if handled with conventional method by gene engineering method.Term " position " or " position of plant " or " plant parts " are explained as above.
Particularly preferably, according to the present invention plant variety plant commercially available or that use is separately handled.
According to plant species or botanical variety, its plantation place and growth conditions (soil, weather, vegetation period, nutrition), processing of the present invention also can produce superadditivity (superadditive) (" working in coordination with ") effect.Thus, for example, can obtain to exceed the following effect of actual desired: for spendable material of the present invention and composition, can reduce its rate of application and/or widen its activity profile and/or improve its activity, improve plant growing, improve high temperature or cold tolerance, the raising drought tolerance or to the tolerance of the salt content of water or soil, improve the quality of blooming, make simpler and easy, the hasting of maturity of gathering, raising gather output, improve the quality of the product of gathering and/or improve its nutritive value, improve bin stability and/or its processing characteristics of the product of gathering.
Preferably genetically modified plants or the botanical variety of being handled by the present invention (i.e. the plant that obtains by gene engineering) is included in all plants of accepting genetic material in the genetic modification, and described genetic material is given described plant with particularly advantageous useful characteristic.The example of described characteristic be improve plant growing, improve high temperature or cold tolerance, the raising drought tolerance or to the tolerance of the salt content of water or soil, improve the quality of blooming, make simpler and easy, the hasting of maturity of gathering, raising gather output, improve the quality of the product of gathering and/or improve its nutritive value, improve bin stability and/or its processing characteristics of the product of gathering.The example of ben described characteristic in addition is for improving the resistance of plant to animal pest and microorganism insect, for example to the resistance of insect, mite, phytopathogenic fungi, bacterium and/or virus, and improve the tolerance of plant to some weeding active compound.The example of the genetically modified plants that can enumerate is important crop plants, for example cereal (wheat, rice), corn, soybean, potato, cotton, rape and fruit plant (fruit is apple, pears, citrus fruit and grape), and ben be corn, soybean, potato, cotton and rape.Ben being characterized as by in plant corpus, forming toxin, particularly by the genetic material of bacillus thuringiensis,Bt (Bacillus thuringiensis) (for example by gene C ryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF with and in conjunction with) toxin that in plant corpus, forms, improve the resistance (hereinafter referred to as " Bt plant ") of plant to insects.Other ben feature is to improve the tolerance of plant to some weeding active compound, and described herbicidal active component is imidazolone type, sulfonylurea, glyphosate or phosphinotricin (for example " PAT " gene) for example.The described gene of giving desirable characteristics also can exist with the form that is bonded to each other in the genetically modified plants body.The example of described " Bt plant " is that commercially available brand name is corn mutation, cotton mutation, soybean mutation and the potato mutation of YIELD GARD  (for example corn, cotton, soybean), KnockOut  (for example corn), StarLink  (for example corn), Bollgard  (cotton), Nucotn  (cotton) and NewLeaf  (potato).The example of the plant with herbicide tolerant that can enumerate is that commercially available brand name is that Roundup Ready  (has glyphosate tolerant, for example corn, cotton, soybean), Liberty Link  (has the phosphinotricin tolerance, rape for example), corn mutation, cotton mutation and the soybean mutation of IMI  (having imidazolinone-tolerant) and STS  (having the sulfonylurea tolerance, for example corn).That can mention has herbicide resistant plants (plant with herbicide tolerant of Pei Yuing in a usual manner) and comprises with Clearfield  being the commercially available mutation (for example corn) of title.Certainly, more than narration also be applicable to have these hereditary capacities or have still wait to develop hereditary capacity, will be at the botanical variety of exploitation in future and/or listing.
Described plant and/or its seed can be handled by particularly advantageous mode with active compound combinations according to the present invention.The preferable range of said mixture also is applicable to the processing to these plants and its seed.Lay special stress on uses the mixture of specifically enumerating among the present invention to handle Plants and Seeds.
Following examples have demonstrated the good insecticidal of active agent combinations of the present invention.Though the activity of independent reactive compound a little less than, bond demonstrates the insecticidal activity of surprising enhancing.
The lethality computing formula of the bond of two kinds of reactive compounds
The expection activity of the bond of two kinds of given reactive compounds can followingly calculate (referring to Colby, S.R.; " Calculating Synergistic and AntagonisticResponses of Herbicide Combinations ", Weeds 15, the 20-22 pages or leaves, 1967):
If
X=when with mLethality when the rate of application of ppm uses reactive compound A is expressed as the % of untreated control group,
Y=when with nLethality when the rate of application of ppm uses reactive compound B is expressed as the % of untreated control group,
E=when with mPpm and nLethality when the rate of application of ppm uses reactive compound A and B is expressed as the % of untreated control group,
E = X + Y - X × Y 100
Then
If actual desinsection lethality is higher than calculated value, then the insecticidal activity of bond has superadditivity, promptly has synergistic effect.In this case, actual observation to lethality must be higher than the expected mortality value (E) that calculates by above-mentioned formula.
Embodiment A
The black peach aphid test
Solvent: the dimethyl formamide of 7 weight portions
Emulsifier: the alkylaryl polyglycol ether of 2 weight portions
For preparing suitable active agent preparations,, and dope is diluted to desired concn with the water that contains emulsifier with the reactive compound of 1 weight portion and the solvent and the emulsifier of described amount.
To be handled in the active agent preparations of wild cabbage (Brassica oleracea) the leaf immersion desired concn of the serious infringement of black peach aphid (Myzus persicae).
Through behind the required time, determine per cent death loss.All aphids are killed in 100% expression; The no aphid of 0% expression is killed.With determined lethality substitution Colby formula.
In this test, for example, the application's following active agent combinations shows the activity of Synergistic with respect to the reactive compound of using separately:
Table A 1
The black peach aphid test
Reactive compound Concentration (ppm) Lethality after 1 day (%)
Thiophene worm amine 0.8 40
Shuan Ben oxazole acid WG 50 100 0
Thiophene worm amine+Shuan Ben oxazoles acid WG 50 (1: 125) 0.8+100 Measured value* Calculated value**
75 40
Mefenpyrdiethyl WP 20 100 0
Thiophene worm amine+mefenpyrdiethyl WP 20 (1: 125) 0.8+100 Measured value* Calculated value**
60 40
* measured value=measured value
* calculated value=Colby formula calculated value
Table A 2
The black peach aphid test
Reactive compound Concentration (ppm) Lethality after 1 day (%)
Imidacloprid 0.8 45
Shuan Ben oxazole acid WG 50 100 0
Imidacloprid+Shuan Ben oxazoles acid WG 50 (1: 125) 0.8+100 Measured value* Calculated value**
85 45
* measured value=measured value
* calculated value=Colby formula calculated value
Table A 3
The black peach aphid test
Reactive compound Concentration (ppm) Lethality after 1 day (%)
Thiophene worm quinoline 0.8 10
Shuan Ben oxazole acid WG 50 100 0
Thiophene worm quinoline+Shuan Ben oxazoles acid WG 50 (1: 125) 0.8+100 Measured value* Calculated value**
30 10
Mefenpyrdiethyl WP 20 100 0
Thiophene worm quinoline+mefenpyrdiethyl WP 20 (1: 125) 0.8+100 Measured value* Calculated value**
55 10
* measured value=measured value
* calculated value=Colby formula calculated value
Embodiment B
The chrysomelid larva test of horseradish ape
Solvent: the dimethyl formamide of 7 weight portions
Emulsifier: the alkylaryl polyglycol ether of 2 weight portions
For preparing suitable active agent preparations,, and dope is diluted to desired concn with the water that contains emulsifier with the reactive compound of 1 weight portion and the solvent and the emulsifier of described amount.
Handle in the active agent preparations with wild cabbage (Brassica oleracea) leaf immersion desired concn, when leaf is still moistening, insert horseradish ape chrysomelid (Phaedon cochleariae) larva.
Through behind the required time, determine per cent death loss.The chrysomelid larva of all apes is killed in 100% expression; The chrysomelid larva of the 0% no ape of expression is killed.With determined lethality substitution Colby formula.
In this test, the application's following active agent combinations shows the activity of Synergistic with respect to the reactive compound of using separately:
Table B1
The chrysomelid larva test of horseradish ape
Reactive compound Concentration (ppm) Lethality after 1 day (%)
Thiophene worm amine 4 40
(IIe-5)WP 20 200 0
The WP20 (1: 50) of thiophene worm amine+(IIe-5) 4+100 Measured value* Calculated value**
15 0
* measured value=measured value
* calculated value=Colby formula calculated value
Table B2
The chrysomelid larva test of horseradish ape
Reactive compound Concentration (ppm) Lethality after 1 day (%)
Imidacloprid 20 65
(IIe-5)WP20 100 0
The WP20 (1: 5) of Imidacloprid+(IIe-5) 20+100 Measured value* Calculated value**
90 65
* measured value=measured value
* calculated value=Colby formula calculated value
Table B3
The chrysomelid larva test of horseradish ape
Reactive compound Concentration (ppm) Lethality after 1 day (%)
Imidacloprid 20 75
Shuan Ben oxazole acid WG 50 100 0
Imidacloprid+Shuan Ben oxazoles acid WG 50 (1: 5) 20+100 Measured value* Calculated value**
100 75
* measured value=measured value
* calculated value=Colby formula calculated value
Table B4
The chrysomelid larva test of horseradish ape
Reactive compound Concentration (ppm) Lethality after 1 day (%)
Thiophene worm quinoline 20 45
(IIe-5)WP20 100 0
The WP 20 (1: 5) of thiophene worm quinoline+(IIe-5) 20+100 Measured value* Calculated value**
80 45
* measured value=measured value
* calculated value=Colby formula calculated value
Embodiment C
Diamond-back moth test (sensitive strain)
Solvent: the dimethyl formamide of 7 weight portions
Emulsifier: the alkylaryl polyglycol ether of 2 weight portions
For preparing suitable active agent preparations,, and dope is diluted to desired concn with the water that contains emulsifier with the reactive compound of 1 weight portion and the solvent and the emulsifier of described amount.
Handle in the active agent preparations with wild cabbage (Brassica oleracea) leaf immersion desired concn, and when leaf is still moistening, insert diamond-back moth (Plutella xylostella, sensitive strain) larva.
Through behind the required time, determine per cent death loss.All larvas are killed in 100% expression; The no larva of 0% expression is killed.With determined lethality substitution Colby formula.
In this test, the application's following active agent combinations shows the activity of Synergistic with respect to the reactive compound of using separately:
Table C1
Diamond-back moth test (sensitive strain)
Reactive compound Concentration (ppm) Lethality after 1 day (%)
Imidacloprid 20 40
Shuan Ben oxazole acid WG 50 50 0
Imidacloprid+Shuan Ben oxazoles acid WG 50 (1: 2.5) 20+50 Measured value* Calculated value**
75 40
* measured value=measured value
* calculated value=Colby formula calculated value
Table C2
Diamond-back moth test (sensitive strain)
Reactive compound Concentration (ppm) Lethality after 1 day (%)
Thiophene worm quinoline 20 80
Shuan Ben oxazole acid WG 50 50 0
Thiophene worm quinoline+Shuan Ben oxazoles acid WG 50 (1: 2.5) 20+50 Measured value* Calculated value**
100 80
* measured value=measured value
* calculated value=Colby formula calculated value

Claims (8)

1. the composition that contains the active agent combinations of effective dose, described bond comprise (a) at least a formula (I) compound
Figure A2005800314080002C1
Wherein
The Het representative is optional separately to be replaced or polysubstituted heterocycle by fluorine, chlorine, methyl or ethyl list, and described heterocycle is selected from:
Pyridin-3-yl, pyridine-5-base, 3-pyridine subbase, 1-oxidation-5-pyridine subbase, 1-oxidation-5-pyridine subbase, oxolane-3-base, thiazole-5-base,
A represents C 1-C 6Alkyl ,-N (R 1) (R 2) or S (R 2),
Wherein
R 1Represent hydrogen, C 1-C 6Alkyl, phenyl-C 1-C 4Alkyl, C 3-C 6Cycloalkyl, C 2-C 6Thiazolinyl or C 2-C 6Alkynyl, and
R 2Represent C 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl ,-C (=O)-CH 3Or benzyl,
R represents hydrogen, C 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl ,-C (=O)-CH 3Or benzyl, or and R 2Represent following groups together:
-CH 2-CH 2-,-CH 2-CH 2-CH 2-,-CH 2-O-CH 2-,-CH 2-S-CH 2-,-CH 2-NH-CH 2-,-CH 2-N (CH 3)-CH 2-, and
X represents N-NO 2, N-CN or CH-NO 2,
---all possible tautomeric form and all possible salt of general formula (I) compound or adduct of acid or alkali of comprising general formula (I) compound---
With
(b) at least a compound that improves the crop plants compatibility that is selected from following compound:
4-dichloro-acetyl-1-oxa--4-azaspiro [4.5] decane (AD-67, MON-4660),
1-dichloro-acetyl-six hydrogen-3,3,8a-trimethyl pyrrolo-[1,2-a] pyrimidine-6 (2H)-ketone (dicyclonon, BAS-145138),
4-dichloro-acetyl-3; 4-dihydro-3-methyl-2H-1,4-benzoxazine (benoxacor), the 5-chloroquinoline-own ester of 8-ethoxyacetic acid 1-methyl (cloquitocet_mexyl---referring to also related compound among EP-A-86750, EP-A-94349, EP-A-191736, the EP-A-492366),
3-(2-chlorophenylmethyl)-1-(1-methyl isophthalic acid-phenylethyl) urea (cumyluron),
α-(cyano group methoxyimino) benzene acetonitrile (cyometrinil),
2,4 dichloro benzene ethoxyacetic acid (2,4-drips),
4-(2,4 dichloro benzene oxygen base) butyric acid (2, the 4-Embutox),
1-(1-methyl isophthalic acid-phenylethyl)-3-(4-aminomethyl phenyl) urea (daimuron),
3,6-two chloro-O-Anisic Acids (dicamba),
Piperidines-1-bamic acid S-1-methyl isophthalic acid-phenyl chlorocarbonate (dimepiperate),
2,2-two chloro-N-(2-oxo-2-(2-acrylic amino) ethyl)-N-(2-acrylic) acetamide (DKA-24),
2,2-two chloro-N, N-two-2-acrylic acetamide (dichlormide),
4,6-two chloro-2-phenyl pyrimidines (fenclorim),
1-(2,4 dichloro benzene base)-5-trichloromethyl-1H-1,2,4-triazole-3-Ethyl formate (fenchlorazole---referring to also related compound among EP-A-174562 and the EP-A-346620),
2-chloro-4-trifluoromethyl thiazole-5-Formic acid benzylester (separating careless amine),
4-chloro-N-(1,3-dioxolanes-2-base-methoxyl group)-α-trifluoroacetyl benzophenone oxime (fluxofenim),
3-dichloro-acetyl-5-(2-furyl)-2,2-Er Jia Ji oxazolidine (Xie Cao oxazole, MON-13900),
4,5-dihydro-5,5-diphenyl-3-isoxazole carboxylic acid ethyl ester (Shuan Ben oxazole acid---referring to also related compound among the WO-A-95/07897),
3,6-two chloro-O-Anisic Acid 1-(ethoxy carbonyl) ethyl esters (lactidichlor),
(4-chloro-neighbour-toloxyl) acetate (MCPA),
2-(4-chloro-neighbour-toloxyl) propionic acid (Vi par),
1-(2,4 dichloro benzene base)-4,5-dihydro-5-methyl isophthalic acid H-pyrazoles-3, the 5-dicarboxylate (mefenpyrdiethyl---referring to also related compound among the WO-A-91/07874),
2-dichloromethyl-2-methyl isophthalic acid, 3-dioxolanes alkane (MG-191),
2-acrylic-1-oxa--4-azaspiro [4.5] decane-4-dithio formate (MG-838),
1, the 8-naphthalic anhydride,
α-(1,3-dioxolanes-2-base-methoxyimino) benzene acetonitrile (oxabetrinil),
2,2-two chloro-N-(1,3-dioxolanes-2-base-methyl)-N-(2-acrylic) acetamide (PPG-1292),
3-dichloro-acetyl-2,2-Er Jia Ji oxazolidine (R-28725),
3-dichloro-acetyl-2,2,5-San Jia Ji oxazolidine (R-29148),
4-(4-chloro-neighbour-tolyl) butyric acid,
4-(4-chlorophenoxy) butyric acid,
The diphenylmethyl ethoxyacetic acid,
The diphenyl methoxy menthyl acetate,
Diphenylmethyl ethoxyacetic acid ethyl ester,
1-(2-chlorphenyl)-5-phenyl-1H-pyrazoles-3-methyl formate,
1-(2,4 dichloro benzene base)-5-methyl isophthalic acid H-pyrazoles-3-Ethyl formate,
1-(2,4 dichloro benzene base)-5-isopropyl-1H-pyrazoles-3-Ethyl formate,
1-(2,4 dichloro benzene base)-5-(1, the 1-dimethyl ethyl)-1H-pyrazoles-3-Ethyl formate,
1-(2,4 dichloro benzene base)-5-phenyl-1H-pyrazoles-3-Ethyl formate (referring to also related compound among EP-A-269806 and the EP-A-333131),
5-(2,4 dichloro benzene methyl)-2-isoxazoline-3-Ethyl formate,
5-phenyl-2-isoxazoline-3-Ethyl formate,
5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-Ethyl formate (referring to also related compound among the WO-A-91/08202),
5-chloroquinoline-8-ethoxyacetic acid 1,3-dimethyl butyrate-1-base ester,
5-chloroquinoline-8-ethoxyacetic acid 4-allyloxy butyl ester,
5-chloroquinoline-8-ethoxyacetic acid 1-allyloxy third-2-base ester,
5-chloro-quinoxaline-8-ethoxyacetic acid methyl esters,
5-chloroquinoline-8-ethoxyacetic acid ethyl ester,
5-chloro-quinoxaline-8-ethoxyacetic acid allyl ester,
5-chloroquinoline-8-ethoxyacetic acid 2-oxo third-1-base ester,
5-chloroquinoline-8-oxygen propylmalonic acid diethylester,
5-chloro-quinoxaline-8-oxygen propylmalonic acid diallyl,
5-chloroquinoline-8-oxygen propylmalonic acid diethylester (referring to also related compound among the EP-A-582198),
4-carboxyl benzodihydropyran-4-guanidine-acetic acid (AC-304415 is referring to EP-A-613618),
The 4-tomatotone,
3,3 '-dimethyl-4-methoxyl group benzophenone,
1-bromo-4-chloromethyl sulfonyl benzene,
1-[4-(N-2-methoxybenzoyl base sulfamoyl) phenyl]-3-methyl urea (being N-(2-methoxybenzoyl base)-4-[(methylamino carbonyl) amino] benzsulfamide),
1-[4-(N-2-methoxybenzoyl base sulfamoyl) phenyl]-3, the 3-dimethyl urea,
1-[4-(N-4,5-dimethylbenzoyl sulfamoyl) phenyl]-3-methyl urea,
1-[4-(N-naphthyl sulfamoyl) phenyl]-3, the 3-dimethyl urea,
One of N-(2-methoxyl group-5-methyl benzoyl)-4-(cyclopropyl amino carbonyl) benzsulfamide, and/or (defining by general formula) following compound,
General formula (IIa)
Figure A2005800314080005C1
Or general formula (IIb)
Figure A2005800314080005C2
Or general formula (IIc)
Figure A2005800314080005C3
Wherein
M represents the numeral between 0 to 5,
A 1Represent one of divalent heterocyclic group shown below
Figure A2005800314080005C4
N represents the numeral between 0 to 5,
A 2Representative is optional by C 1-C 4Alkyl, C 1-C 4Alkoxy carbonyl and/or C 1-C 4Two bases of the alkane with 1 or 2 carbon atom that allyloxycarbonyl replaces,
R 8Representation hydroxy, sulfydryl, amino, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group, C 1-C 6Alkyl amino or two-(C 1-C 4Alkyl) amino,
R 9Representation hydroxy, sulfydryl, amino, C 1-C 7Alkoxyl, C 1-C 6Alkene oxygen base, C 1-C 6Alkene oxygen base-C 1-C 6Alkoxyl, C 1-C 6Alkylthio group, C 1-C 6Alkyl amino or two-(C 1-C 4Alkyl) amino,
R 10The optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 4Alkyl,
R 11Represent hydrogen, perhaps the optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 6Alkyl, C 2-C 6Thiazolinyl or C 2-C 6Alkynyl, C 1-C 4Alkoxy-C 1-C 4Alkyl, dioxolanyl-C 1-C 4Alkyl, furyl, furyl-C 1-C 4Alkyl, thienyl, thiazolyl, piperidyl, perhaps representative is optional by fluorine, chlorine and/or bromine or C 1-C 4The phenyl that alkyl replaces,
R 12Represent hydrogen, perhaps the optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 6Alkyl, C 2-C 6Thiazolinyl or C 2-C 6Alkynyl, C 1-C 4Alkoxy-C 1-C 4Alkyl, dioxolanyl-C 1-C 4Alkyl, furyl, furyl-C 1-C 4Alkyl, thienyl, thiazolyl, piperidyl, perhaps representative is optional by fluorine, chlorine and/or bromine or C 1-C 4The phenyl that alkyl replaces, perhaps and R 11Representative is optional separately by C together 1-C 4Alkyl, phenyl, furyl, fused benzene rings or the C that is replaced by following two substituting groups 3-C 6Alkane two bases or C 2-C 5Oxa-alkane two bases, described two substituting groups form 5 or 6 yuan of carbocyclic rings with the C atom that they connected,
R 13Represent hydrogen, cyano group, halogen, perhaps the optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 4Alkyl, C 3-C 6Cycloalkyl or phenyl,
R 14Represent hydrogen, perhaps representative is optional by hydroxyl, cyano group, halogen or C 1-C 4The C that alkoxyl replaces 1-C 6Alkyl, C 3-C 6Cycloalkyl or three-(C 1-C 4Alkyl) silicyl,
R 15Represent hydrogen, cyano group, halogen, perhaps the optional separately C that is replaced by fluorine, chlorine and/or bromine of representative 1-C 4Alkyl, C 3-C 6Cycloalkyl or phenyl,
X 1Represent nitro, cyano group, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy,
X 2Represent hydrogen, cyano group, nitro, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy,
X 3Represent hydrogen, cyano group, nitro, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy,
One of and/or (defining by general formula) following compound,
General formula (IId)
Figure A2005800314080007C1
Or general formula (IIe)
Figure A2005800314080007C2
Wherein
R and s represent the numeral between 0 and 5,
R 16Represent hydrogen or C 1-C 4Alkyl,
R 17Represent hydrogen or C 1-C 4Alkyl,
R 18Represent hydrogen, perhaps representative is optional separately by cyano group, halogen or C 1-C 4The C that alkoxyl replaces 1-C 6Alkyl, C 1-C 6Alkoxyl, C 1-C 6Alkylthio group, C 1-C 6Alkyl amino or two-(C 1-C 4Alkyl) amino, perhaps representative is optional separately by cyano group, halogen or C 1-C 4The C that alkyl replaces 3-C 6Cycloalkyl, C 3-C 6Cycloalkyl oxy, C 3-C 6Cycloalkyl sulfenyl or C 3-C 6Cycloalkyl amino,
R 19Represent hydrogen, perhaps representative is optional by cyano group, hydroxyl, halogen or C 1-C 4The C that alkoxyl replaces 1-C 6Alkyl, perhaps representative is optional separately by the C of cyano group or halogen replacement 3-C 6Thiazolinyl or C 3-C 6Alkynyl, perhaps representative is optional by cyano group, halogen or C 1-C 4The C that alkyl replaces 3-C 6Cycloalkyl,
R 20Represent hydrogen, perhaps representative is optional by cyano group, hydroxyl, halogen or C 1-C 4The C that alkoxyl replaces 1-C 6Alkyl, perhaps representative is optional separately by the C of cyano group or halogen replacement 3-C 6Thiazolinyl or C 3-C 6Alkynyl, perhaps representative is optional by cyano group, halogen or C 1-C 4The C that alkyl replaces 3-C 6Cycloalkyl, perhaps representative is optional by nitro, cyano group, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4The phenyl that halogenated alkoxy replaces is perhaps with R 19Representative is optional separately by C together 1-C 4The C that alkyl replaces 2-C 6Alkane two bases or C 2-C 5Oxa-alkane two bases,
X 4Represent nitro, cyano group, carboxyl, carbamoyl, formoxyl, amino-sulfonyl, hydroxyl, amino, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy, and
X 5Represent nitro, cyano group, carboxyl, carbamoyl, formoxyl, amino-sulfonyl, hydroxyl, amino, halogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl or C 1-C 4Halogenated alkoxy.
2. the composition of claim 1 is characterized in that comprising the compound of following at least a reactive compound as formula (I): Imidacloprid, thiophene worm amine, thiophene worm piperazine, thiophene worm quinoline, MTI-446, Acetamiprid, Nitenpyram.
3. the composition of claim 1 is characterized in that comprising the compound of following at least a reactive compound as raising crop plants compatibility: cloquitocet_mexyl, fenchlorazole, the acid of Shuan Ben oxazole, mefenpyrdiethyl, Xie Cao oxazole, fenclorim, cumyluron, daimuron, dimepiperate, Compound I Ie-5, Compound I Ie-11.
4. the composition of claim 1 is used to prevent and treat arthropodan purposes.
5. prevent and treat arthropodan method, it is characterized in that the composition of claim 1 is acted on insect and/or arachnid and/or its habitat.
6. the composition of claim 1 is used to protect seed to resist arthropodan purposes.
7. the protection seed resists arthropodan method, it is characterized in that the compositions-treated seed with claim 1.
8. seed is characterized in that passing through the compositions-treated of claim 1.
CNB2005800314084A 2004-07-20 2005-07-18 Insecticide based on anabasine and safener Active CN100566563C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103200824A (en) * 2010-11-02 2013-07-10 先正达参股股份有限公司 Pesticidal combinations comprising a neonicotinoid insecticide and a herbicide safener
CN103204804A (en) * 2013-04-10 2013-07-17 山东省联合农药工业有限公司 Nicotine compound containing double benzene and preparation method and use thereof
CN101808519B (en) * 2007-09-26 2013-09-25 拜尔农作物科学股份公司 Active agent combinations having insecticidal and acaricidal properties

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101808519B (en) * 2007-09-26 2013-09-25 拜尔农作物科学股份公司 Active agent combinations having insecticidal and acaricidal properties
CN103200824A (en) * 2010-11-02 2013-07-10 先正达参股股份有限公司 Pesticidal combinations comprising a neonicotinoid insecticide and a herbicide safener
CN103204804A (en) * 2013-04-10 2013-07-17 山东省联合农药工业有限公司 Nicotine compound containing double benzene and preparation method and use thereof
CN103204804B (en) * 2013-04-10 2015-10-28 山东省联合农药工业有限公司 A kind of nicotine compound containing two benzene and its production and use

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