WO1996021652A1 - 4-aryl- and 4-heteroaryl -5-oxopyrazoline derivatives having pesticidal properties - Google Patents
4-aryl- and 4-heteroaryl -5-oxopyrazoline derivatives having pesticidal properties Download PDFInfo
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- WO1996021652A1 WO1996021652A1 PCT/EP1995/005152 EP9505152W WO9621652A1 WO 1996021652 A1 WO1996021652 A1 WO 1996021652A1 EP 9505152 W EP9505152 W EP 9505152W WO 9621652 A1 WO9621652 A1 WO 9621652A1
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- 0 *C(C(N(*)N1*)=O)=C1O Chemical compound *C(C(N(*)N1*)=O)=C1O 0.000 description 5
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
-
- 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
- C07D231/28—Two oxygen or sulfur atoms
- C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
- C07D231/32—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
Definitions
- Examples of the unsubstituted or mono- to trisubstituted, nonaromatic, mono- or bicyclic heterocyclic rings which the substituents R 21 and R 22 , together with the nitrogen atom to which they are attached, are able to form are, for example, 1-pyrrolidinyl, 1-piperidyl, 2,6-dimeu ⁇ yl-1-piperidyl, 4-morpholinyl, 4-methylpiperazin-1-yl, 4-phenylpiperazin-1-yl, 4-benzylpiperazin- 1 -yl, 4-(3,4-dichlorophenyl)piperazin- 1 -yl, 4-thiomorpholinyl, 2,6-dimed ⁇ yl-4-morpholinyl, 2,6-dimethylthio-4-mo ⁇ pholinyl, 1,2,3,4-tetrahydroquinolin-1-yl orindolin-1-yl.
- ring systems can be substituted by halogen, C 1 -C 16 alkyl, C 1 -C 16 haloalkyl,
- heterocyclic amines such as, for example, pyridine, quinoline, isoquinoline, morpholine, N-methylmorpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as, for example, anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
- heterocyclic amines such as, for example, pyridine, quinoline, isoquinoline, morpholine, N-methylmorpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine
- A is C 1 -C 8 alkyl substituted by nitro, cyano, Si(C 1 -C 4 alkyl) 3 , amino, C 1 -C 4 alkylamino, di(C 1 -C 4 alkyl)amino, substituted or unsubstituted benzyloxy or a group -CH-NRr ⁇ Rr ⁇ , or A is C 3 -C 8 cycloalkyl which can if desired contain as heteroatom
- Salts of compounds of the formula I can be convened into the free compounds of the formula I in a customary manner; acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchanger reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchanger reagent.
- Salts of compounds of the formula I can be converted into other salts of compounds of the formula I in a manner known per se; acid addition salts, for example, can be converted into other acid addition salts, for example, by treating a salt of an inorganic acid, such as a hydrochloride, with an appropriate metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which the inorganic salt which forms, for example silver chloride, is insoluble and therefore separates out of the reaction mixture.
- an inorganic acid such as a hydrochloride
- an appropriate metal salt such as a sodium, barium or silver salt
- R 4 is C 1 - or C 2 alkyl in positions 2, 4 and 6 relative to the phenyl linkage site; and n is 3.
- Aedes spp. Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chiysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,
Abstract
The present invention relates to novel, pesticidally effective, 4-aryl- and 4-heteroaryl-5-oxo-pyrazoline derivatives of formula (I), in which R1, R2, R3 and G are as defined in claim 1, to compositions comprising these compounds, to their use as insecticides, acaricides or herbicides, especially in crops of useful plants, and to selective-herbicidal compositions comprising compounds of formula (I) and, as safeners, herbicide-antagonistically effective quantities of either a quinoline derivative of formula (X), in which R15 and X2 are as defined in the description, or a 1-phenylazole-3-carboxylic acid derivative of formula (XI), in which E, R16, R17, R18 and R19 are as defined in the description.
Description
4-Aryl- and 4-heteroaryl -5-oxopyrazol ine derivatives having pesticidal properties
The present invention relates to novel, pesticidally active 4-aryl- and
4-heteroaryl-5-oxo-pyrazoline derivatives, to a process for their preparation, to compositions which comprise these compounds as active substances, and to their use as pesticides, especially as insecticides, acaricides or herbicides.
4-Aryl-5-oxo-pyrazolines and 4-aryl- and 4-heteroarylpyrazolidine-3,5-diones having insecticidal, acaricidal and herbicidal action are already known and are described, for example, in EP-A-0508 126 and WO-92/16510.
Novel 4-aryl- and 4-heteroaryl-5-oxo-pyrazoline derivatives having pesticidal properties have now been found which are distinguished by good activity.
The compounds according to the invention are of the formula ,
in which
R1 is the group or
the substituents R4 independently of one another are halogen, nitro, cyano, C1-C4alkyl, C1-C4haloalkyI, C1-C10alkoxy, C1-C4haloalkoxy, C3-C6alkenyloxy,
C1-C4alkoxy-C2-C4alkoxy, C3-C6alkynyloxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4aIkylamino or di(C1-C4alkyl)amino;
R5 is the group or
n is 0, 1, 2, 3 or 4;
m is 0 or 1, and the sum of m and n is 0, 1, 2, 3 or 4;
q is 0, 1, 2 or 3;
Xj is oxygen, sulfur, -CH2- or -N(R7)-;
the substituents R6 independently of one another are C1-C4alkyl, halogen, C1-C4haloalkyl,
C1-C4alkoxy, C1-C4haloalkoxy, nitro, cyano, C1-C4alkoxycarbonyl, amino,
C1-C4alkylamino or di(C1-C4alkyl)amino;
R7 is hydrogen, C1-C4alkyl, formyl or C1-C4alkylcarbonyl;
R2 and R3 independently of one another are hydrogen, C1-C8alkyl, C3-C8alkenyl,
C3-C8alkynyl, C1-C8alkoxyalkyl, C1-C8alkylthioalkyl, C3-C8cycloalkyl or substituted or unsubstituted aryl; or
R2 and R3 together form the bivalent radical of a saturated or unsaturated, unsubstituted or substituted, mono-, bi-, tri- or polycyclic system, which system can optionally contain, in positions not adjacent to the nitrogen atoms shown in formula I, one or more ring hetero atoms;
G is the group -CO-A (a) or -SO2-B (b);
A is C1-C8alkyl substituted by nitro, cyano, Si(C1-C4alkyl)3, amino, C1-C4alkylamino, di(C1-C4alkyl)amino, substituted or unsubstituted benzyloxy or a group ~ CH_ NRos^ ,
COORojo or A is C3-C8cycloalkyl which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio,
C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is
C3-C8cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, or A is adamantyl, naphthyl, naphthyl substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy, or A is a group
-(CR8R9)p-(Y)o-CO-(Z)r-R10, -(CR8R9)p-R1 1 or -N(R10)R13;
R08, R09 and R010 independendy of one another are hydrogen or C1-C6alkyl;
R8 and R9 independently of one another are hydrogen, C1-C6alkyl or phenyl;
R10 is hydrogen, C1-C10alkyl, C1-C10alkyl substituted by halogen, C1-C4alkoxy,
C1-C4haloalkoxy, C1-C4alkylthio, C3-C12cycloalkyl, cyano, aryl or aryloxy,
C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, C3-C10alkenyl,
C3-C10alkynyl, C3-C10haloalkenyl, C3-C10haloalkynyl, aryl, aryl substituted by halogen,
C1-C4alkyl, C1-C4haloalkyl, C1-C6alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy or halo-substituted phenoxy;
o and r independently of one another are 0 or 1;
Y and Z independently of one another are oxygen or NR12;
p is 1 to 10;
R11 is C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, aryloxy, aryloxy substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy,
C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy or halo-substituted phenoxy, benzyloxy, benzyloxy substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy or halo-substituted phenoxy, norbornyl or adamantyl, where aryloxy with the exception of phenoxy can in each case be
any desired aryloxy group;
R12 is hydrogen, C1-C4alkyl, C3-C8cycloalkyl, C3-C10alkenyl or C3-C10alkynyl;
R13 is C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, or cyano-C1-C6alkyl;
B is C1-C10alkyl substituted by C1-C4alkoxy, C1-C6alkoxy-C1-C4alkoxy,
C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfinyl,
C1-C4alkylsulfonyl, C1-C4alkylsulfonyloxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylcarbonyloxy, di(C1-C4alkyl)amino, C3-C8cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or pyridyl, it being possible for the aryl and pyridyl groups if desired to be substituted by halogen, C1-C4alkyl,
C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy, halo-substituted phenoxy, phenylthio or halo-substituted phenylthio, or B is
C3-C10alkenyl, C3-C10haloalkenyl, C3-C10alkynyl, C3-C10haloalkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, benzyl, benzyl substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy, naphthyl, naphthyl substituted by halogen or nitro, or B is a group -N(R21)R22;
R21 is C1-C10alkyl substituted by C1-C4alkoxy, C1-C6alkoxy-C1-C4alkoxy,
C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfinyl,
C1-C4alkylsulfonyl, C1-C4alkylsulfonyloxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylcarbonyloxy, di(C1-C4alkyl)amino, C3-C8cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or pyridyl, it being possible for the aryl and pyridyl groups if desired to be substituted by halogen, C1-C4alkyl,
C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy, halo-substituted phenoxy, phenylthio or halo-substituted phenylthio, or R21 is
C3-C20alkenyl, C3-C20haloalkenyl, C3-C20alkynyl, C3-C2ohaloalkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, benzyl or aryl, it being possible for the benzyl and aryl groups if desired to be substituted by halogen, C1-C4alkyl,
C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, benzoyl, halo-substituted benzoyl, phenoxy or halo-substituted phenoxy;
R22 is as defined for R21 or else alternatively is C1-C10alkyl; or
R21 and R22, together with the nitrogen atom to which they are attached, form an unsubstituted or mono- to trisubstituted, nonaromatic, mono- or bicyclic heterocyclic ring in which the substituents can be C1-C4alkyl, C1-C4alkyl substituted by halogen,
C1-C4alkoxy, phenyl, benzodioxoyl or trifluoromethylphenyl, C1-C4alkoxy,
C1-C4_dkoxycarbonyl, C1-C4alkylcarbonyl, phenyl, phenyl substituted by halogen, C1-C4alkyl, C1-C4 alkoxy, nitro or trifluoromethyl, pyridyl, pyrimidinyl or formyl, and salts and diastereomers of the compounds of the formula I, with the proviso that, if R21
and R22 are alkyl, at least one of these radicals is a substituted alkyl.
In the above definitions, halogen (halo) refers to iodine and preferably to fluorine, chlorine and bromine.
Unless specifically mentioned, the alkyl, alkenyl and alkynyl groups preferably have 1 or, respectively, 2 to 8 carbon atoms and can be straight-chain or branched, specifications which also apply to the alkyl, alkenyl and alkynyl moieties of alkylsilanes, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, alkenyloxy, alkynyloxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkenylthio, alkynylthio, alkylthioalkyl, alkylsulfinyl,
alkylsulfonyl, alkylamino and dialkylamino groups.
Examples of the alkyl groups occurring in the definitions of the substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, and the isomeric
pentyls, hexyls, heptyls and octyls. The alkyl groups occurring as or in the substituents preferably have 1-8 carbon atoms.
Alkenyl refers for example to allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Preferred alkenyl radicals are those having a chain length of 2 to 8 carbon atoms. The alkenyl
radicals are preferably attached to a heteroatom via a saturated carbon atom.
Examples of alkynyl are propargyl, but-2-yn-1-yl, 2-methylbutyn-2-yl, but-3-yn-2-yl and pent-4-yn-1-yl. Preferred alkynyl radicals are those having a chain length of 2 to 8 carbon atoms. The alkynyl radicals are preferably attached to a heteroatom via a saturated carbon atom.
Haloalkyl radicals preferably have a chain length of 1 to 8 carbon atoms. Haloalkyl is for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,
1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl;
preference is given to trichloromethyl, difluorochloromethyl, difluoromethyl,
trifluoromethyl and dichlorofluoromethyl.
Suitable haloalkenyl groups are alkenyl groups substituted one or more times by halogen, in which context halogen is bromine, iodine and, in particular, fluorine and chlorine, examples being 2,2-difluoro-1-methyl vinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl,
2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-1-yl. Among
C3-C20alkenyl radicals substituted 1, 2 or 3 times by halogen, preference is given to those having a chain length of 3 to 5 carbon atoms.
Suitable haloalkynyl groups are, for example, alkynyl groups which are mono- or polysubstituted by halogen, where halogen is bromine, iodine and, in particular, fluorine and chlorine, examples being 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and
4,4,4-trifluorobut-2-yn-1-yl. Among the alkynyl radicals substituted one or more times by halogen, preference is given to those having a chain length of 3 to 5 carbon atoms.
Alkoxy radicals preferably have a chain length of 1 to 6 carbon atoms. Alkoxy is for example methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and the isomers of pentyloxy and hexyloxy; methoxy and ethoxy are preferred.
Alkylcarbonyl is especially acetyl and propionyl.
Alkoxycarbonyl is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl;
methoxycarbonyl and ethoxycarbonyl are preferred.
Haloalkoxy radicals preferably have a chain length of 1 to 8 carbon atoms. Haloalkoxy is for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy,
1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and
2,2,2-trichloroethoxy; difluoromethoxy, 2-chloroethoxy and trifluoromethoxy are preferred.
Alkylthio radicals preferably have a chain length of 1 to 8 carbon atoms. Alkyl thio is for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio,
sec-butylthio or tert-butylthio; methylthio and ethylthio are preferred.
Alkylsulfinyl is methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl,
n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; methylsulfinyl and
ethylsulfinyl are preferred.
Alkylsulfonyl is methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl,
n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl; methylsulfonyl and ethylsulfonyl are preferred.
Alkoxyalkoxy radicals preferably have a chain length of 1 to 8 carbon atoms. Examples of alkoxyalkoxy are methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy and butoxybutoxy.
Alkylamino is for example methylamino, ethylamino, n-propylamino, isopropylamino and the isomeric butylamines.
Dialkylamino is for example dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Preference is given to alkylamino radicals having a chain length of 1 to 4 carbon atoms.
Alkoxyalkyl radicals preferably have 1 to 8 carbon atoms. Alkoxyalkyl is for example methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl,
n-propoxyethyl, isopropoxymethyl and isopropoxyethyl.
Alkylthioalkyl radicals preferably have 1 to 8 carbon atoms. Alkylthioalkyl is for example methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl,
butylthioethyl or butylthiobutyl.
The cycloalkyl radicals preferably have 3 to 8 ring carbon atoms, for example
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. These cycloalkyl radicals can if desired be interrupted by heteroatoms such as, for example, oxygen atoms and/or sulfur atoms and/or nitrogen atoms. Similar comments apply to the cycloalkyloxy radicals.
Phenyl, on its own or as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl or phenoxyalkyl, can in general be unsubstituted or substituted. In the latter case the substituents can be in an ortho, meta and/or para position. Preferred substituent positions are the ortho and para positions relative to the ring linking site.
Preferred substituents are halogen, nitro, cyano, C1-C4alkoxy, C1-C4haloalkoxy,
C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkyl and C1-C4haloalkyl.
Aryl in the definition of the radicals R2, R3 and R10 is α- or β-naphthyl, especially phenyl, which aromatic ring systems can carry one or more identical or different substituents, examples being halogen, nitro, cyano, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkyl and C1-C4haloalkyl. Corresponding comments apply to
aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy and arylcarbonyl in the definition of the radicals R10, R11, R21, R22 and B.
Examples of the unsubstituted or mono- to trisubstituted, nonaromatic, mono- or bicyclic heterocyclic rings which the substituents R21 and R22, together with the nitrogen atom to which they are attached, are able to form are, for example, 1-pyrrolidinyl, 1-piperidyl, 2,6-dimeuτyl-1-piperidyl, 4-morpholinyl, 4-methylpiperazin-1-yl, 4-phenylpiperazin-1-yl, 4-benzylpiperazin- 1 -yl, 4-(3,4-dichlorophenyl)piperazin- 1 -yl, 4-thiomorpholinyl, 2,6-dimedιyl-4-morpholinyl, 2,6-dimethylthio-4-moιpholinyl, 1,2,3,4-tetrahydroquinolin-1-yl orindolin-1-yl.
Examples of saturated or unsaturated and unsubstituted or substituted mono-, bi-, tri- or polycyclic systems which the substituents R2 and R3, together with the two nitrogen atoms of the pyrazoline ring to which they are attached, are able to form are:
These ring systems can be substituted by halogen, C1-C16alkyl, C1-C16haloalkyl,
C2-C16alkenyl, C1-C16alkoxy-C2-C6alkyl, C1-C6polyalkoxy-C2-C6alkyl or by phenyl or benzyl each of which is unsubstituted or substituted by halogen, nitro, C1-C4alkyl, C1-C3alkoxy or C1-C3haloalkyl; and R14 is halogen or unsubstituted or halo-substituted C1- or C2alkoxy.
Corresponding meanings can also be assigned to the substituents in composite definitions, for example haloalkoxy, haloalkylthio, alkoxyalkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfinyl, alkylsulfonyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio and cycloalkylthio.
The invention likewise comprises the salts which the compounds of the formula I can form with acids. Suitable acids for the formation of the acid addition salts are both organic and inorganic acids. Examples of such acids are inter alia hydrochloric acid, hydrobromic acid, nitric acid, various phosphorus acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, organic sulfonic acids, lactic acid, tartaric acid, citric acid and salicylic acid.
The salts of the compounds of the formula I containing acidic hydrogen, as for example in the definition of the substituent A as C1-C8alkyl substituted by a group , in
which R010 is hydrogen, can also be alkali metal salts, for example sodium salts and potassium salts; alkaline earth metal salts, for example calcium salts and magnesium salts; ammonium salts, i.e. unsubstituted ammonium salts and mono- or polysubstituted ammonium salts, and salts with other organic nitrogen bases.
Correspondingly, suitable salt formers are alkali metal hydroxides and alkaline earth metal hydroxides, especially the hydroxides of litfiium, sodium, potassium, magnesium or calcium, with particular importance being attached to those of sodium or potassium.
Examples of amines suitable for forming ammonium salts include not only ammonia but also primary, secondary and tertiary C1-C18alkylamines, C1-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,
methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine,
ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine,
N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine,
n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine,
methoxyethylamine and ethoxyethylamine; heterocyclic amines such as, for example, pyridine, quinoline, isoquinoline, morpholine, N-methylmorpholine, thiomorpholine,
piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as, for example, anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
In addition, it is possible if desired to form corresponding inner salts, for example in the case of the radical A as C1-C8alkyl substituted by a group , in which R08,
R09 and R010 are hydrogen.
Furthermore, it is possible for certain substituents R1, R4 to R13, and R2 and R3 alone or in combination with one another or in combination with the parent structure to which they are attached to exhibit chirality. The invention comprises both the racemate and the enriched and optically pure forms of the respective stereoisomers.
In the processes described in this application, the asymmetrically substituted compounds of the formula I are generally - unless chiral precursors are used - obtained as racemates. The stereoisomers can then be separated on the basis of physicochemical properties by known methods, for instance fractional crystallization after the formation of salts with optically pure bases, acids or metal complexes, or else by chromatographic methods such as, for example, high-performance liquid chromatography (HPLC) on acetylcellulose. In the present invention, references to the active substances of the formula I include both the pure optical isomers and the racemates and/or diastereomers. Where no specific reference to the individual optical isomers is made, the formula given should be taken to refer to those racemic mixtures which are produced in the preparation process indicated. Where an aliphatic C=C double bond is present, geometric isomerization can also occur.
The formula I is intended to embrace all of these possible isomers and mixtures thereof.
With respect to the insecticidal and acaricidal actions, emphasis should be put on the following compounds of the formula I:
Preferred compounds of the formula I are those in which R1 is the group . Of these compounds, particular preference is given to those in which
R4 is fluorine, chlorine or C1-C4alkyl; n is 1, 2 or 3; and m is 0.
Of these compounds, very particular prcference is given to those in which R4 is fluorine, chlorine or methyl; and n is 2 or 3.
Preference is likewise given to compounds in which R2 and R3 are C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH^s-- -(CH2)4- or -(CH2)3-.
Compounds which are likewise preferred are those in which G is the group -CO-A (a). Among these compounds, particular preference is given to those in which A is a group -(CR8R9)p-(Y)o-CO-(Z)r-R10, -(CR8R9)p-R11 or -N(R10)R13, or substituted or unsubstituted naphthyl.
Among these compounds, very particular preference is given to those in which R8 and R9 independently of one another are hydrogen or methyl; and p is 1 or 2.
Of these compounds, very special importance attaches to those in which R8 and R9 are methyl.
Likewise particularly preferred are compounds in which R10 is C1-C8-alkyl, preferably C1-C4-alkyl, C3-C6cycloalkyl, phenyl, phenyl substituted by halogen, or is naphthyl; R11 is C3-C8cycloalkyl, benzyloxy, benzyloxy substituted by halogen, C1-C4alkyl,
C1-C4haloalkyl or phenoxy, or is naphthyloxy; and R13 is C3-C7cycloalkyl or
cyano-C1-C6alkyl.
Other particularly preferred compounds are those in which Y and Z are NR12. Among these compounds, particular preference is given to those in which R12 is hydrogen or C1-C4alkyl.
Particular preference is similarly given to compounds in which R8 and R9 independendy of one another are hydrogen or methyl; p is 1 or 2; R10 is C1-C4alkyl, C3-C6cycloalkyl, phenyl, phenyl substituted by halogen, or is naphthyl; R1 1 is C3-C6cycloalkyl, benzyloxy, benzyloxy substituted by halogen, C1-C4alkyl, C1-C4 haloalkyl or phenoxy, or is naphthyloxy; Y and Z are NR12 ; R12 is hydrogen or C1-C4alkyl; and R13 is
C3-C8cycloalkyl orcyano-C1-C6alkyl.
Preferred compounds are those in which R1 is the group ; R4 is fluorine,
chlorine or C1-C4alkyl; n is 1, 2 or 3; m is 0; R2 and R3 are C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-; G is the group -CO-A (a); A is a group -(CR8R9)p-(Y)o-CO-(Z)r-R10, -(CR8R9)p-R11 or -N(R10)R13, or is unsubstituted or substituted naphthyl; R8 and R9 independently of one another are hydrogen or methyl; p is 1 or 2; R10 is C1-C4alkyl, C3-C6cycloalkyl, phenyl, phenyl substituted by halogen, or is naphthyl; R11 is C3-C8cycloalkyl, benzyloxy, benzyloxy substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or phenoxy, or is naphthyloxy; and R13 is C3-C8cycloalkyl orcyano-C1-C6alkyl.
With regard to the herbicidal properties, preferred compounds of the formula I are those following in which R1 is the group ; and m is 0. Among these
compounds, particular preference is given to those following in which R4 is C1- or C2alkyl; and n is 1, 2 or 3.
Among these compounds of the formula I, very particular preference is given to those in which R4 is C1- or C2alkyl in positions 2, 4 and 6 relative to the phenyl linkage site; and n is 3.
Other preferred compounds are those in which R1 is the group ; m is 0;
R4 is C1- or C2alkyl; n is 1, 2 or 3; R2 and R3 are C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-.
Likewise preferred are compounds in which G is a group -CO-A (a); and A is C1-C8alkyl substituted by nitro, cyano, Si(C1-C4alkyl)3, amino, C1-C4alkylamino,
di(C1-C4alkyl)amino, substituted or unsubstituted benzyloxy or a group ,
or A is C3-C8cycloalkyl, which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio,
C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is C3-C8cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by C1-C4alkyl, or A is a group
-(CR8R9)p-(Y)o-CO-(Z)r-R10 or -(CR8R9)p-R11.
Other preferred compounds are those in which R1 is the group ; R4 is C1-
or C2alkyl; n is 1, 2 or 3; m is 0; R2 and R3 are C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-; G is the group -CO-A (a); and A is C1-C8alkyl substituted by nitro, cyano, Si(C1-C4alkyl)3, amino, C1-C4alkylamino, di(C1-C4alkyl)amino, substituted or unsubstituted benzyloxy or a group -CH-NRrøRrø , or A is C3-C8cycloalkyl which can if desired contain as heteroatom
COORøio
oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkyldιio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is C3-C8cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by C1-C4alkyl, or A is a group
-(CR8R9)p-(Y)o-CO-(Z)r-R10 or -(CR8R9)p-R11.
Especially preferred is the compound of the formula I, in which R1 is
2,4,6-trimethylphenyl, R2 and R3 together are -(CH2)4- and G is
-C(=O)-N(CH3)CH2CH2CN.
Also especially preferred is the compound of the formula I, in which R1 is
2,4,6-trimethylphenyl, R2 and R3-N together are -CH2CH2CH(CH3)CH2-N and G is -C(=O)-N(CH3)CH2CH2CN.
Also especially preferred is the compound of the formula I, in which R1 is
2,6-dichlorophenyl, R2 and R3 together are -(CΗ2)4- and G is -C(=O)-N(CH3)CH2CH2CN.
The process according to the invention for the preparation of compounds of the formula I is carried out in analogy to known processes and comprises
a) for the preparation of the 4-aryl- and 4-heteroaryl-5-oxopyrazoline derivatives of the formula
in which R1, R2 and R3 are as defined under formula I, G is the group -CO-A (a) and A is
as defined under formula I with the exception of the group -N(R10)R13, reacting a compound of the formula
in which R1, R2 and R3 are as defined, with a compound of the formula
in which A is as defined and E1 is a leaving group, preferably halogen and especially chlorine; b) for the preparation of the 4-aryl- and 4-heteroaryl-5-oxopyrazoline derivatives of the formula
in which R1, R2 and R3 are as defined under formula I, G is the group -CO-A (a), and A is -N(R10)R13, where R10 and R13 are as defined under formula I with the exception of R10 as hydrogen, reacting a compound of the formula
in which R1, R2 and R3 are as defined, with a compound of the formula
in which R10 and R13 are as defined and E1 is a leaving group, preferably halogen and especially chlorine; or c) for the preparation of the 4-aryl- and 4-heteroaryl-5-oxopyrazoline derivatives of the formula
in which R1, R2 and R3 are as defined under formula I, G is the group -CO-A (a), and A is -NHR13, where R13 is as defined under formula I, reacting a compound of the formula
in which R1, R2 and R3 are as defined, with an isocyanate of the formula
R13-N=C=O (V),
in which R13 is as defined.
The process according to the invention for the preparation of compounds of the formula o G
in which R1, R2 and R3 are as defined under formula I, G is the group -SO2-B (b), and B is as defined under formula I, is carried out in analogy to known processes as described, for example, in EP-A-0508 126, and comprises reacting a compound of the formula
in which R1, R2 and R3 are as defined under formula I, with a compound of the formula
B-SO2-E1 (VI),
in which B is as defined and E1 is a leaving group such as halogen, especially chlorine, if desired in a solvent and in the presence or absence of a base.
The reactions according to process variants (a), (b) and (c) can be carried out in analogy to known processes, advantageously in a reaction-inert, hydroxyl-free solvent in the presence of an organic base such as, for example, pyridine, 4-dimethylaminopyridine, lutidine, collidine, trialkylamines, N,N-dialkylaniline, or bicyclic nonnucleophilic bases such as,
for example, 1,4-diazabicyclo[2.2.2]octane (DABOO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The reaction is generally carried out at temperatures of from 0 to 120°C, preferably from 20 to 90°C, advantageously in the presence of a reaction-inert solvent or solvent mixture. Examples of those suitable for this purpose are aliphatic and aromatic hydrocarbons such as benzene, toluene, petroleum ether or hexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; ethers and ether-like compounds, such as dialkyl ethers, for example diethyl ether, diisopropyl ether and tert-butyl methyl ether, and also anisole, dioxane and tetrahydrofuran; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate, propyl acetate and butyl acetate; ketones such as acetone, diethyl ketone and methyl ethyl ketone; and mixtures of such solvents.
The reaction of the compound of the formula II with the reactive sulfonic acid derivative of the formula VI takes place advantageously in equimolar quantities at temperatures of from 0 to 150°C, preferably from 20 to 70°C. Suitable solvents are the customary reaction-inert, polar, organic solvents, such as ethers, amides, nitriles, alcohols, sulfones or sulfoxides, especially dimethyl sulfoxide, tetrahydrofuran or N,N-dimedιylformamide. Suitable binding agents for the acid formed are the known inorganic and organic bases such as sodium hydroxide, sodium carbonate, potassium carbonate or pyridines. The reaction can take place under elevated pressure or, in particular, at atmospheric pressure. If desired it is also possible to operate under phase transfer conditions, in which case from 0.3 to 1.5 mol of reactive sulfonic acid derivative of the formula VI are employed per mole of the compound of the formula II at from 0 to 150°C, preferably from 20 to 70°C. Phase transfer catalysts which can be used are the customary quaternary ammonium salts, such as tetraoctylammonium bromide or benzyltriethylammonium chloride. In this case suitable organic solvents are all inert apolar solvents, such as benzene or toluene.
The compounds of the formula II, in which R1, R2 and R3 are as defined under formula I, are known from EP-A-0508 126 and WO 92/16510 and can be prepared by the processes disclosed.
The compounds of the formulae III, IV, V and VI required for the preparation processes are either commercial products or can be prepared in analogy to known standard
processes.
The end products of the formula I can be isolated in a customary manner by concentration
and/or evaporation of the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, alkanes, aromatic hydrocarbons or chlorinated hydrocarbons, or by means of chromatography over a silica gel column.
Salts of compounds of the formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of the formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases by treatment with a suitable base or a suitable ion exchanger reagent
Salts of compounds of the formula I can be convened into the free compounds of the formula I in a customary manner; acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchanger reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchanger reagent.
Salts of compounds of the formula I can be converted into other salts of compounds of the formula I in a manner known per se; acid addition salts, for example, can be converted into other acid addition salts, for example, by treating a salt of an inorganic acid, such as a hydrochloride, with an appropriate metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which the inorganic salt which forms, for example silver chloride, is insoluble and therefore separates out of the reaction mixture.
Depending on the procedure and reaction conditions, the compounds of the formula I with salt-forming properties can be obtained in free form or in the form of salts.
Unless specific synthesis is carried out for the isolation of pure isomers, the product can be obtained as a mixture of two or more isomers. The isomers can be separated by methods known per se.
For the compositions comprising the compounds of the formula I, the preferences which apply are the same as those for the compounds of the formula I.
The present invention also relates to a selective-herbicidal composition for controlling grasses and weeds in crops of useful plants, especially in crops of maize and cereal, which composition comprises a herbicide and a safener (counteracting agent, antidote) and which protects the useful plants but not the weeds against the phytotoxic action of the herbicide,
and to the use of this composition for weed control in crops of useful plants.
When herbicides are used it is possible, for example, depending on the rate and mode of application of the herbicide, on the crop plant, on the nature of the soil and on the climatic conditions, such as period of exposure to light, temperature and amounts of precipitation, for the crop plants as well to be damaged to a considerable extent.
In order to counter this and similar problems, a variety of substances have already been proposed as safeners, which are capable of antagonizing the damaging effect of the herbicide on the crop plant, in other words of protecting the crop plant from said effect, while causing virtually no impairment of the herbicidal action on the weeds to be controlled. In this context it has been found that the proposed safeners often have a very specific action with respect to the crop plants and with respect to the herbicide and, in some cases, in dependence on the mode of application; in other words, a certain safener is often suitable only for one specific crop plant and one specific class of herbicide or a specific herbicide. Thus, for example, EP-A-0094 349 discloses quinoline derivatives which protect crop plants against the phytotoxic effect of herbicides of particular classes, for example chloroacetanilides, phenoxypropionates, ureas, triazines, carbamates or diphenyl ethers.
EP-A-0558 448 describes 1,5-diphenylpyrazole-3-carboxylic acid derivatives for protecting against the phytotoxic effect of sulfonylureas.
It has now been found that safener compounds selected from the classes of the quinoline, pyrazole or triazole derivatives are suitable for protecting crop plants against the phytotoxic effect of 4-aryl- and 4-heteroaryl-5-oxopyrazoline derivatives of the formula I.
In accordance with the invention, therefore, a selective-herbicidal composition is proposed which comprises, in addition to customary inert formulation auxiliaries such as carriers, solvents and wetting agents, an active substance comprising a mixture of
a) a herbicidally effective quantity of a herbicide compound of the formula I as defined hereinbefore and
b) a herbicide-antagonistically effective quantity of either a quinoline derivative of the formula
in which
R15 is hydrogen, C1-C8alkyl or C1-C8alkyl which is substituted by C1-C6alkoxy or
C3-C6alkenyloxy; and
X2 is hydrogen or chlorine; or
of a 1-phenylazole-3-carboxylic acid derivative of the formula
in which
E is nitrogen or methine;
R16 is -CCI3 or unsubstituted or halo-substituted phenyl;
R17 and R18 independently of one another are hydrogen or halogen; and
R19 is C1-C4alkyl.
Preferred compounds of the formula I in the composition according to the invention are those in which R1 is the group ; and m is 0- Among these, particular
preference is given to those compounds in which R4 is C1- or C 2alkyl; and n is 1, 2 or 3.
In particular, among these compounds, very particular preference is given to those in which R4 is C1- or C2alkyl in positions 2, 4 and 6 relative to the phenyl linkage site; and n is 3.
Likewise preferred are compositions according to the invention in which, in the
compounds of the formula I, R1 is the group ; m is 0; R4 is C1- or
C2alkyl; n is 1, 2 or 3; R2 and R3 are C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-.
Also preferred are those compositions in which G is the group -CO-A (a); and A is C1-C8alkyl substituted by nitro, cyano, Si(C1-C4alkyl)3, amino, C1-C4alkylamino, di(C1-C4alkyl)amino, unsubstituted or substituted benzyloxy or a group ,
or A is C3-C8cycloalkyl which if desired can contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio,
C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is C3-C8cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by C1-C4alkyl, or A is a group
-(CR8R9)p-(Y)o-CO-(Z)r-R10 or -(CR8R9)p-R11.
Furthermore, preference is given to those compositions in which R1 is the group ; R4 is C1- or C2alkyl; n is 1, 2 or 3; m is 0; R2 and R3 are C1-C6alkyl; or
R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-; G is the group -CO-A (a); and A is C1-C8alkyl substituted by nitro, cyano, Si(C1-C4alkyl)3, amino, C1-C4alkylamino, di(C1-C4alkyl)amino, unsubstituted or substituted benzyloxy or a group , or A is C3-C8cycloalkyl which can if
desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, C1-C4 alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is C3-C8cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by C1-C4alkyl, or A is a group -(CR8R9)p-(Y)o-CO-(Z)r-R10 or -(CR8R9)p-R11.
Furthermore, preference is given to those compositions which comprise a safener of the formula
Likewise preferred are compositions which comprise a safener of the formula
Further preferred compositions are those which comprise a safener of the formula
Further preferred compounds of the formulae X and XI are also listed in Tables 8 and 9.
The quinoline derivatives from the scope of the formula X and their preparation are known or they can be prepared by analogy with known processes, as described for example in EP-A-0094 349.
The 1-phenylazole-3-carboxylic acid derivatives from the scope of the formula XI are known and are described for example in EP-A-0268 554 and EP-A-0 174 562.
In the field of pest control the compounds of the formula I according to the invention, used even at low concentrations, are active substances having preventive and/or curative value, a very favourable biocidal spectrum and favourable tolerance by warm-blooded animals, fish and plants. The active substances according to the invention are effective against all or individual development stages of normally sensitive, but also of resistant, animal pests,
such as insects or members of the order Acarina. The insecticidal or acaricidal action of the active substances according to the invention can become apparent direcdy, i.e. in destruction of the pests which occurs immediately or only after a certain time, for example during moulting, or indirecdy, for example in reduced oviposition and/or hatching rates, the favourable action corresponding to a rate of destruction (mortality) of at least 50 to 60 %.
The animal pests mentioned include, for example:
from the order Lepidoptera, for example
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp.,
Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp.,
Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana,
Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta,
Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,
Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp.,
Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
from the order Coleoptera, for example
Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema ribialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp.,
Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp.,
Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,
Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and
Trogoderma spp.;
from the order Orthoptera, for example
Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp.,
Periplaneta spp. and Schistocerca spp.;
from the order Isoptera, for example,
Reticulitermes spp.;
from the order Psocoptera, for example
Liposcelis spp.;
π from the order Anoplura, for example
Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;
from the order Mallophaga, for example
Damalinea spp. and Trichodectes spp.;
from the order Thysanoptera, for example
Frankliniella spp., Hercinothrips spp., Taeniodirips spp., Thrips palmi, Thrips tabaci and
Scirtothrips aurantii;
from the order Heteroptera, for example
Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp.
Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,
Scotinophara spp. and Triatoma spp.;
from the order Homoptera, for example
Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp.,
Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,
Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum,
Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium comi, Lepidosaphes spp.,
Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp.,
Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp.,
Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,
Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;
from the order Hymenoptera, for example
Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma,
Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.;
from the order Diptera, for example
Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chiysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,
Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp.,
Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp.,
Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;
from the order Siphonaptera, for example
Ceratophyllus spp. and Xenopsylla cheopis;
from the order Thysanura, for example
Lepisma saccharina and
from the order Acarina, for example
Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp..
Using the active substances according to the invention it is possible to control pests of the type mentioned which occur on plants, especially on useful and ornamental plants in agriculture, gardening and forestry, or on parts of such plants, such as fruits, flowers, foliage, stems, tubers or roots, control in this context meaning restrict or destroy, while in some cases also providing protection against these pests to parts of plants which grow subsequently.
Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar and fodder beet; fruit, for example pome fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; pulses, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppy, olives, sunflowers, coconut, castor, cacao or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruits or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell pepper, the laurel family, such as avocado, cinnamon or camphor, and also tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, banana family, latex plants and ornamentals.
Further fields of use of the active substances according to the invention are the protection of stocks, warehouses and material and in the hygiene sector, especially the protection of domestic and productive animals against pests of the type mentioned.
The invention therefore also relates to pesticides which are forms, to be chosen in accordance with the intended aims and prevailing conditions, such as emulsifiable concentrates, suspension concentrates, direcdy sprayable or dilutable solutions, brushable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, dusts, granules or encapsulations in polymeric substances, and which comprise - at least - one of the active substances according to the invention.
The active substance is employed in these compositions in pure form, a solid active substance, for example, in a specific particle size, or, preferably, together with - at least - one of the auxiliaries which are customary in the art of formulation, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
Examples of suitable solvents are unmodified or partially hydrogenated aromatic hydrocarbons, preferably the C8 to C12 fractions of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphdialene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and ethers and esters thereof, such as propylene glycol, dipropylene glycol ether, ediylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unmodified or epoxidized vegetable oils, such as unmodified or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.
As solid carriers, for example for dusts and dispersible powders, use is generally made of ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties it is also possible to add highly disperse silicas or highly disperse absorbent polymers. Suitable granulated, adsorptive granule carriers are porous types, such as pumice, broken brick, sepiolite or bentonite, while suitable non-sorbent carrier materials are calcite or sand. Moreover, a large number of granulated materials of inorganic or organic type, especially dolomite or comminuted plant residues, can be used.
Suitable surface-active compounds, depending on the nature of the active substance to be formulated, are nonionic, cationic and/or anionic surfactants, or surfactant mixtures having good emulsifying, dispersing and wetting properties. The surfactants listed below should be regarded only as examples; the relevant literature describes many other surfactants which are common in the art of formulation and are suitable in accordance with the invention.
Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can have 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Also suitable are water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100
propylene glycol ether groups, of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain, per propylene glycol unit, 1 to 5 ethylene glycol units. Examples which may be mentioned are nonylphenolpolyethoxyethanols, castor polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate.
The cationic surfactants are primarily quaternary ammonium salts which have as substituents at least one alkyl radical having 8 to 22 carbon atoms and, additionally, lower, unmodified or halogenated, alkyl, benzyl or lower hydroxyalkyl radicals. These salts are preferably halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethylammonium chloride and benzyldi(2-chloroethyl)ethylammonium bromide.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds. Suitable soaps are the alkali metal, alkaline earth metal and substituted or unsubstituted ammonium salts of higher fatty acids (C10-C22). such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut oil or tall oil; the fatty acid mediyl-taurine salts should also be mentioned. More often, however, synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates and fatty sulfates are generally in the form of alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and generally have an alkyl radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. Also included are the salts of sulfuric esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having about 8 to 22 carbon atoms. Alkylarylsulfonates are, for example, the sodium, calcium or
triethanolammonium salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product Also suitable are appropriate phosphates, such as salts of the phosphoric ester of a
p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids.
The compositions generally contain from 0.1 to 99 %, in particular from 0.1 to 95 %, of
active substance and from 1 to 99.9 %, in particular from 5 to 99.9 % of - at least - one solid or liquid auxiliary, it being possible in general for from 0 to 25 %, in particular from 0.1 to 20 %, of the compositions to be surfactants (% denotes in each case percent by weight). Whereas the commercial product tends preferably to comprise concentrated compositions, the end user generally uses dilute compositions with substantially lower concentrations of active substance. Preferred compositions are composed, in particular, as follows (% = percent by weight):
The action of the compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticidal or acaricidal active substances. In this context, suitable additions of insecticidal or acaricidal active substance are, for example, representatives of the following classes of active substance: organophosphorus compounds, nitrophenols and derivatives, formamidines, acylureas, carbamates, pyrethroids, nitroenamines and derivatives, pyrroles, thioureas and
derivatives, chlorinated hydrocarbons and Bacillus thuringiensis preparations. The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unmodified or epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders and/or adhesives, and also fertilizers or other active substances for obtaining specific effects, examples being bactericides, nematicides, molluscicides or selective herbicides.
The compositions according to the invention are prepared in a known manner for example in the absence of auxiliaries, by grinding, sieving and/or compression of a solid active substance or active substance mixture, for example to a defined particle size, and, when at least one auxiliary is present, for example by intimate mixing and/or grinding of the active substance or active substance mixture with the auxiliary or auxiliaries. These processes for producing the compositions according to the invention, and the use of the compounds I for the production of these compositions, are likewise a subject of the invention.
The invention relates furthermore to the methods of application for the compositions, i.e. the methods of controlling pests of the type mentioned, these methods being chosen in accordance with the intended aims and prevailing circumstances and comprising, for instance, spraying, fogging, dusting, brushing, dressing, broadcasting or watering, and to the use of the compositions for controlling pests of the type mentioned. In tins context, typical application concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active substance. The application rates per hectare are generally from 1 to 200 g of active substance per hectare, in particular from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
A preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the frequency and rate of application depending on the extent of infestation by the respective pest. However, the active substance can also pass into the plants via the root system (systemic action), by saturating the site of the plants with a liquid composition or incorporating the active substance in solid form into the site of the plants, for example into the soil, in the form of granules, for example (soil application). In paddy rice cultures, such granules can be metered out into the flooded rice field
The compositions according to the invention are also suitable for protecting vegetative propagation stock, for example seeds, such as fruits, tubers or grains, or plant seedlings,
against animal pests. In this case the propagation stock can be treated with the
composition before being planted out; seed, for example, can be dressed before sowing. The active substances according to the invention can also be applied to seeds (coating) by either soaking the seeds in a liquid composition or coating them with a solid composition. The composition can also be applied when the propagation stock is planted out, at the planting site, for example in the seed drill in the case of sowing. These treatment methods for vegetative propagation stock, and the vegetative propagation stock dius treated, are further subjects of the invention.
The compounds of the formula I according to the invention are also herbicidally active. Suitable application methods for the herbicidal use, according to the invention, of the compounds of the formula I or of compositions comprising them are all those methods which are customary in agriculture, such as prcemergence application, postemergence application and seed dressing, and also a variety of methods and techniques such as, for example, the controlled release of active substance. For this purpose, the active substance in solution is applied to mineral granular carriers or polymerized granules
(urea/formaldehyde) which are then dried. If desired, it is additionally possible to apply a coating (coated granules) which permits the release of the active substance in regulated amounts over a defined period.
The compounds of the formula I can be employed in unaltered form, i.e. as they are obtained in the synthesis, but are preferably processed in a conventional manner, using the auxiliaries which are customary in the art of formulation, for example to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The methods of application, such as spraying, misting, dusting, wetting, scattering or pouring, are - like the nature of the compositions - chosen in accordance with the intended aims and the prevailing conditions.
The formulations, i.e. the compositions, preparations or combinations comprising the active substance of the formula I or at least one active substance of the formula I and, if desired, one or more solid or liquid additives, are produced in a known manner, for example by intimate mixing and/or grinding of the active substances with the additives, such as solvents or solid carriers, for example. It is also possible, in addition, for surface-active compounds (surfactants) to be used in the production of the formulations. Suitable solvents, solid carriers and surface-active compounds are, for example, of the type described hereinbefore.
The herbicidal formulations generally contain from 0.1 to 99 %, in particular from 0.1 to
95 %, of active substance of the formula I, from 1 to 99 % of a solid or liquid formulation auxiliary and from 0 to 25 %, in particular from 0.1 to 25 %, of a surfactant.
While the commercial product tends preferably to comprise concentrated compositions, the end user generally uses dilute compositions.
The compositions can also comprise further additives, such as stabilizers, for example unmodified or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, adhesives, and also fertilizers or other active substances for obtaining specific effects.
In particular, preferred formulations are composed as follows (% = percent by weight):
The active substances of the formula I are in general employed successfully at application
rates of from 0.001 to 2 kg/ha, in particular from 0.005 to 1 kg/ha. The rate required in order to achieve the desired effect can be determined by means of trials. It is dependent on the nature of the effect, on the stage of development of the crop plant and of the weed, and on the application (site, time, method) and can, depending on these parameters, vary within wide ranges.
The compounds of the formula I are distinguished by herbicidal properties which render them outstanding for use in crops of useful plants, especially in cereals, cotton, soya, oilseed rape, maize, rice and plantation crops. They can additionally be employed as burn-down agents, for example for potatoes, or as defoliants.
References to cultures or crops are intended to include those which have been given tolerance to herbicides or classes of herbicide by means of conventional breeding methods or methods of genetic manipulation.
The invention also relates to a process for the selective control of broad-leaved weeds and grasses in crops of useful plants, which comprises treating the useful plants, their seeds or seedlings or their cultivation area, simultaneously or independently of one another, with a herbicidally effective quantity of the herbicide of the formula I and with a
herbicide-antagonistically effective quantity of a safener of the formula X or XI.
Crop plants which can be protected by the safeners of the formulae X and XI against the damaging effect of the abovementioned herbicides are, in particular, maize and cereals.
The weeds to be controlled can be either monocotyledon or dicotyledon weeds.
The areas regarded as cultivation areas are the soil areas on which the crop plants are already growing, or soil areas sown with the seed of these crop plants, and also the areas intended for cultivation with these crop plants.
Depending on the intended use, a safener of the formula X or XI can be used for pretreating the seed of the crop plant (dressing of the seed or of the seedlings), or placed in the soil before or after sowing. It can also, however, be applied, on its own or together with the herbicide, following the emergence of the plants. The treatment of the plants or of the seed with the safener can therefore, in principle, take place independently of the point in time of the application of the herbicide. The plant treatment, however, can also be carried out by simultaneous application of herbicide and safener (for example as a tank
mix).
The application rate of safener to herbicide to be applied depends largely on the method of application. In a field treatment carried out either using a tank mix comprising a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of herbicide to safener is in general from 100:1 to 1:10, preferably from 20:1 to 1:1.
In general, in field treatment, from 0.001 to 5.0 kg of safener/ha, preferably from 0.001 to 0.5 kg of safener/ha, are applied.
The application rates of herbicide are generally between 0.001 and 2 kg/ha, but preferably between 0.005 and 1 kg/ha.
The compositions according to the invention are suitable for all application methods which are customary in agriculture, for example prcemergence application, postemergence application and seed dressing.
In the case of seed dressing, in general, from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied. If the safener is applied in liquid form shortly before sowing, accompanied by seed swelling, then it is expedient to use safener solutions which comprise the active substance in a concentration of from 1 to 10000 ppm, preferably from 100 to 1000 ppm.
For application, the safeners of the formula X or XI, or combinations of these safeners with the herbicides of the formula I, are advantageously processed together with the auxiliaries which are customary in the art of formulation to give particular formulations, for example emulsion concentrates, brushable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The formulations are prepared in a known manner, for example by intimate mixing and/or grinding of the active substances with liquid or solid formulation auxiliaries such as, for example, solvents or solid carriers. Furthermore, it is possible in addition to use surface-active compounds (surfactants) when producing the formulations. Suitable solvents, solid carriers and surface-active compounds are, for example, of the type described hereinbefore.
The agrochemical formulations generally contain from 0.1 to 99 percent by weight, in
particular from 0.1 to 95 % by weight, of safener or safener/herbicide active-substance mixture, from 1 to 99 % by weight, in particular from 5 to 99.8 % by weight, of a solid or liquid formulation auxiliary, and from 0 to 25 % by weight, in particular from 0.1 to 25 % by weight, of surfactant.
While the preferred commercial product usually comprises concentrated compositions, the end user generally uses dilute compositions.
The compositions can also comprise further additives, such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active substances.
For the use of safeners of the formulae X and XI or compositions comprising them for protecting crop plants against the damaging effects of herbicides of the formula I, a variety of methods and techniques are suitable, examples being the following: i) Seed dressing
a) The seeds are dressed by shaking them, in a vessel, together with an active substance of the formula X or XI formulated as a wettable powder until the active ingredient is distributed uniformly on the seed surface (dry seed dressing). In this case from about 1 to about 500 g of active substance of the formula X or XI (from 4 g to 2 kg of wettable powder) are used per 100 kg of seed. b) The seeds are dressed with an emulsion concentrate of the active substance of the formula X or XI in accordance with method a) (wet seed dressing). c) The seeds are dressed by immersing them into a liquor containing 100-1000 ppm of active substance of the formula X or XI for from 1 to 72 hours and then, if desired, by drying them (seed soaking).
The dressing of the seed, and the treatment of the seedling which has begun germinating, are of course the preferred methods of application, since the treatment with the active substance is directed entirely towards the target crop. As a rule, from 1 to 1000 g of antidote, preferably from 5 to 250 g of antidote, are used per 100 kg of seed, it being possible to deviate from these limit concentrations up or down repeat dressing, depending on the method, which also makes possible the addition of other active substances or micronutrients.
ii) Application as a tank mix
A liquid preparation of a mixture of antidote and herbicide (mutual quantitative ratio of between 10:1 and 1:100) is used, the application rate of herbicide being from 0.005 to 5.0 kg per hectare. Such tank mixes are applied before or after sowing. iii) Application in the seed drill
The safener is incorporated into the open seed drill, containing seed, as an emulsion concentrate, wettable powder or in the form of granules. After the seed drill has been covered over, the herbicide is applied preemergence in a customary manner. iv) Controlled release of active substance
The active substance of the formula X or XI is applied in solution to mineral granule carriers or polymerized granules (urea/formaldehyde), which are then dried. If desired, a coating can be applied (coated granules), which enables the release of the active substance in regulated amounts over a defined period.
The examples which follow illustrate the invention in more detail without limiting it. Temperatures are given in degrees Celsius. The temperatures given in the Tables, in the column "Phys. data", are the melting points of the corresponding compounds unless otherwise indicated.
Preparation Examples:
Example H1: Preparation of 3-oxo-2-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-3-H-pyrazoloo1,2-a]pyridazin-1-yl 2-cyclohexyl-2-methyIpropionate
1.09 g of 3-hydroxy-4-mesityl-5-oxo-1,2-tetramethylenepyrazoline and 1.4 ml of triethylamine are dissolved in 25 ml of tetrahydrofuran, and 0.75 g of 2-cyclohexyl-2-methylpropionic acid is added at 20°. The reaction mixture is stirred at 40° for 3 hours and then concentrated on a rotary evaporator. The residue is taken up in toluene and water. The toluene phase is dried over sodium sulfate and concentrated. The residue is stirred in
hexane and then filtered off with suction to give the desired compound as a white powder having a melting point of 172-173°.
Example H2: Preparation of 3-oxo-2-(2,4,6-trimethylphenyl)-5,6,7,8-tetrahydro-3-H-pyrazolo[1,2-a]pyridazin-1-yl (2-cyanoethyl )methylcarbamate
1.22 g of 3-hydroxy-4-mesityl-5-oxo-1,2-tetramethylenepyrazoline and 1.14 g of triethylamine are dissolved in 25 ml of tetrahydrofuran, and 0.7 g of (2-cyanoethyl)methylcarbamoyl chloride is added with stirring. The reaction mixture is stirred at 40° for 3 hours and then concentrated on a rotary evaporator. Dichloromethane and ice-water are added to the residue. The organic phase is dried with sodium sulfate and concentrated, and the residue obtained is stirred with hexane, filtered off with suction and dried to give the desired compound as a white powder with a melting point of 151-153°.
Example H3: Preparation of 3-oxo-2-(2,4,6-trimethyIphenyl)-5,6,7,8-tetrahydro-3H-pyrazolo[1,2-a]pyridazin-1-yl cyclohexylmethylsulfamate
2.7 g of 3-hydroxy-4-mesityl-5-oxo-1,2-tetramethylenepyrazoline and 3.0 g of triethylamine are dissolved in 30 ml of tetrahydrofuran, a solution of 2.1 g of cyclohexylmethylsulfamoyl chloride is added at room temperature, and the reaction mixture is then stirred at 40° for 8 hours. It is concentrated and the residue is taken up with ten-butyl methyl ether and ice-water. The organic phase is dried with sodium sulfate and
concentrated. The crude product is dissolved in ethyl acetate, the solution is filtered over silica gel, the filtrate is concentrated and the residue is stined with hexane. Suction filtration and drying give the desired compound as a white powder with a melting point of
171-173°.
The compounds of Tables 1-9 can be prepared by analogy with the above examples and with the preparation methods described.
Tables 1-7 below list, as compounds of the formulae la to Ig, compounds of the formula I which are preferred as insecticides and acaricides and also as herbicides.
Tables 8 and 9 list compounds which are preferred as safeners of the formulae X and XI.
The finely ground active substance is intimately mixed with the additives. In this way, a suspension concentrate is obtained which can be diluted with water to give suspensions of any desired concentration.
Biological examples (% = per cent by weight, unless otherwise indicated)
A. Insecticidal action
Example B1: Action against Myzus persicae
Pea seedlings are infected with Myzus persicae, subsequently sprayed with a spray
mixture comprising 400 ppm of active ingredient and then incubated at 20°. The test is evaluated after 3 and 6 days. The percentage reduction in the population (% action) is determined by comparing the number of dead aphids on the treated plants with those on untreated plants.
Compounds of Tables 1 to 7 exhibit a good action in this test
Example B2: Action against Nilaparvata lugens
Rice plants are treated with an aqueous emulsion spray liquor comprising 400 ppm of active ingredient and, after the spray coating has dried on, are populated with stage 2 and 3 cicada larvae. 21 days later, the percentage reduction in the population (% action) is determined by comparing the number of surviving cicadas on the treated plants with those on untreated plants.
Compounds of Tables 1 to 7 exhibit a good action in this test.
Example B3: Action against Nilaparvata lugens (systemic)
Pots containing rice plants are placed in an aqueous emulsion solution comprising 400 ppm of active ingredient. The plants are then populated with stage 2 and 3 larvae. 6 days later, the percentage reduction in the population (% action) is determined by comparing the number of cicadas on the treated plants with those on untreated plants.
Compounds of Tables 1 to 7 exhibit a good action in this test.
B. Acaricidal action
Example B4: Action against Boophilus microplus
Fully satiated adult female ticks are stuck onto a PVC plate and covered with a cottonwool pad, and 10 ml of aqueous test solution comprising 125 ppm of active ingredient are poured over the animals. The cottonwool pad is removed, and the ticks are incubated for 4 weeks for oviposition. The action is evident either in the female, as mortality or sterility, or in the eggs, as ovicidal action.
Compounds of Tables 1 to 7 exhibit a good action in this test.
Example B5: Action against Tetranychus urticae
Young bean plants are populated with a mixed population of Tetranychus urticae, sprayed 1 day later with an aqueous emulsion spray liquor comprising 400 ppm of active ingredient, incubated at 25° for 6 days and subsequently evaluated. The percentage reduction in the population (% action) is determined by comparing the number of dead
eggs, larvae and adults on the treated plants with those on untreated plants.
Compounds of Tables 1 to 7 exhibit a good action in this test An action of more than 80% is shown, in particular, by the compounds nos. 1.1 to 1.9, 1.11 to 1.28, 1.33 to 1.40, 1.44 to 1.49, 1.51, 1.53, 1.55 to 1.61, 2.2, 2.6 to 2.14, 2.16, 2.17, 2.20, 2.21, 3.1, 5.15, 5.47, 5.80, 5.88, 5.107, 5.110, 5.112, 5.122, 6.2 to 6.4 and 6.7.
C. Herbicidal action
Example B6: Herbicidal action before emergence of the plants (preemergence)
Monocotyledon and dicotyledon test plants are sown in standard soil in plastic pots.
Directly after sowing, the test substances are sprayed on in an aqueous suspension prepared from a 25 % wettable powder (Example F13, b)), at a rate of 2 kg of AS/ha (500 1 of water/ha). The test plants are subsequently grown in the greenhouse under optimum conditions. After a test duration of 3 weeks, the experiment is evaluated using a 9-point rating scale (1 = complete damage, 9 = no action). Ratings from 1 to 4 (especially 1 to 3) denote a good to very good herbicidal action.
In diis experiment, compounds of Tables 1-7 exhibit a strong herbicidal action, as can be seen, for example, from the results presented in Table 10.
Example B7: Post-emergence herbicidal action (contact herbicide)
Monocotyledon and dicotyledon test plants are grown in standard soil in the greenhouse in plastic pots and, at the 4- to 6-leaf stage, are sprayed with an aqueous suspension of the test substances of the formula I, prepared from a 25 % wettable powder (Example F13, b)), at a rate of 2000 g of AS/ha (5001 of water/ha). The test plants are subsequendy grown on in the greenhouse under optimum conditions. After a test period of about 18 days, the experiment is evaluated using a 9-point rating scale (1 = complete damage, 9 = no action). Ratings from 1 to 4 (especially 1 to 3) denote a good to very good herbicidal action.
In this experiment, compounds of Tables 1-7 exhibit a strong herbicidal action, as can be seen, for example, from the results presented in Table 11.
D. Safener effect
Example B8: Safener effect
Under greenhouse conditions, the test plants are grown in plastic pots to the 4-leaf stage. At this stage, both the herbicide alone and the mixtures of the herbicide with the test substances to be tested as safeners are applied to the test plants. Application takes place in the form of an aqueous suspension of the test substances, prepared from a 25 % wettable powder (Example F21, b)), with 5001 of water/ha. 3 weeks after application, the phytotoxic action of the herbicide on the crop plants, for example maize and cereal, is evaluated using a percentage scale. 100 % denotes that the test plant has died, while 0 % denotes no phytotoxic effect.
This experiment shows that, with compounds of the formula X or XI, for example with the compound no. 8.1, the damage caused to crop plants, for example maize or cereal plants, by herbicide compounds of the formula I, for example by the compound no. 1.13, can be substantially reduced.
Claims
1. A compound of the formula , 
in which
R1 is the group or
the substituents R4 independently of one another are halogen, nitro, cyano, C1-C4alkyl, C1-C4haloalkyl, C1-C10alkoxy, C1-C4haloalkoxy, C3-C6alkenyloxy,
C1-C4alkoxy-C2-C4alkoxy, C3-C6alkynyloxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4alkylamino or di(C1-C4alkyl)amino;
R5 is the group or
n is 0, 1, 2, 3 or 4;
m is 0 or 1, and the sum of m and n is 0, 1, 2, 3 or 4;
q is 0, 1, 2 or 3;
X1 is oxygen, sulfur, -CH2- or -N(R7)-;
the substituents R6 independently of one another are C1-C4alkyl, halogen, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, nitro, cyano, C1-C4alkoxycarbonyl, amino,
C1-C4alkylamino or di(C1-C4alkyl)amino;
R7 is hydrogen, C1-C4alkyl, formyl or C1-C4alkylcarbonyl;
R2 and R3 independently of one another are hydrogen, C1-C8alkyl, C3-C8alkenyl,
C3-C8alkynyl, C1-C8alkoxyalkyl, C1-C8alkylthioalkyl, C3-C8cycloalkyl or substituted or unsubstituted aryl; or
R2 and R3 together form the bivalent radical of a saturated or unsaturated, unsubstituted or substituted, mono-, bi-, tri- or polycyclic system, which system can optionally contain, in positions not adjacent to the nitrogen atoms shown in formula I, one or more ring hetero atoms;
G is the group -CO-A (a) or -SO2-B (b);
A is C1-C8alkyl substituted by nitro, cyano, Si(C1-C4alkyl)3, amino, C1-C4alkylamino, di(C1-C4alkyI)amino, substituted or unsubstituted benzyloxy or a group , 
or A is C3-C8cycloalkyl which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio,
C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is
C3-C8cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, or A is adamantyl, naphdiyl, naphthyl substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy, or A is a group
-(CR8R9)p-(Y)o-CO-(Z)r-R10, -(CR8R9)p-R11 or -N(R10)R13;
R08, R09 and R010 independently of one another are hydrogen or C1-C6alkyl;
R8 and R9 independently of one another are hydrogen, C1-C6alkyl or phenyl;
R10 is hydrogen, C1-C10alkyl, C1-C10alkyl substituted by halogen, C1-C4alkoxy,
C1-C4haloalkoxy, C1-C4alkylthio, C3-C12cycloalkyl, cyano, aryl or aryloxy,
C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, C3-C10alkenyl,
C3-C10alkynyl, C3-C10haloalkenyl, C3-C10haloalkynyl, aryl, aryl substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C6alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy or halo-substituted phenoxy;
o and r independently of one another are 0 or 1;
Y and Z independently of one another are oxygen or NR12;
p is 1 to 10;
R11 is C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, aryloxy, aryloxy substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy,
C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy or halo-substituted phenoxy, benzyloxy, benzyloxy substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy or halo-substituted phenoxy, norbomyl or adamantyl, where aryloxy with the exception of phenoxy can in each case be any desired aryloxy group;
R12 is hydrogen, C1-C4alkyl, C3-C8cycloalkyl, C3-C10alkenyl or C3-C10alkynyl;
R13 is C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, or cyano-C1-C6alkyl;
B is C1-C10alkyl substituted by C1-C4alkoxy, C1-C6alkoxy-C1-C4alkoxy,
C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfinyl,
C1-C4alkylsulfonyl, C1-C4alkylsulfonyloxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylcarbonyloxy, di(C1-C4alkyl)amino, C3-C8cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or pyridyl, it being possible for the aryl and pyridyl groups if desired to be substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy, halo-substituted phenoxy, phenylthio or halo-substituted phenylthio, or B is
C3-C10alkenyl, C3-C10haloalkenyl, C3-C10alkynyl, C3-C10haloalkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, benzyl, benzyl substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy, naphthyl, naphdiyl substituted by halogen or nitro, or B is a group -N(R21)R22;
R21 is C1-C10alkyl substituted by C1-C4alkoxy, C1-C6alkoxy-C1-C4alkoxy,
C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfinyl,
C1-C4alkylsulfonyl, C1-C4alkylsulfonyloxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylcarbonyloxy, di(C1-C4alkyl)amino, C3-C8cycloalkyl, aryl, aryloxy, aryldiio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or pyridyl, it being possible for the aryl and pyridyl groups if desired to be substituted by halogen, C1-C4alkyl,
C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy, halo-substituted phenoxy, phenylthio or halo-substituted phenylthio, or R21 is
C3-C20alkenyl, C3-C20haloalkenyl, C3-C2oalkynyl, C3-C2ohaloalkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen or C1-C4alkyl, benzyl or aryl, it being possible for the benzyl and aryl groups if desired to be substituted by halogen, C1-C4alkyl,
C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, benzoyl, halo-substituted benzoyl, phenoxy or halo-substituted phenoxy;
R22 is as defined for R21 or else alternatively is C1-C10alkyl; or
R21 and R22. together with the nitrogen atom to which they are attached, form an unsubstituted or mono- to trisubstituted, nonaromatic, mono- or bicyclic heterocyclic ring in which the substituents can be C1-C4alkyl, C1-C4alkyl substituted by halogen,
C1-C4alkoxy, phenyl, benzodioxoyl or trifluoromethylphenyl, C1-C4alkoxy,
C1-C4alkoxycarbonyl, C1-C4alkylcarbonyl, phenyl, phenyl substituted by halogen, C1-C4alkyl, C1-C4alkoxy, nitro or trifluoromethyl, pyridyl, pyrimidinyl or formyl, and salts and diastereomers of the compounds of the formula I, with the proviso that, if R21 and R22 are alkyl, at least one of these radicals is substituted alkyl.
2. A compound according to claim 1, in which R1 is the group
3. A compound according to claim 2, in which R4 is fluorine, chlorine or C1-C4alkyl; n is 1, 2 or 3; and m is 0.
4. A compound according to claim 3, in which R4 is fluorine, chlorine or methyl; and n is 2 or 3.
5. A compound according to claim 1, in which R2 and R3 are C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-.
6. A compound according to claim 1, in which G is the group -CO-A (a).
7. A compound according to claim 6, in which A is a group -(CR8R9)p-(Y)o-CO-(Z)r-R10, -(CR8R9)p-R11 or -N(R10)R13, or substituted or unsubstituted naphthyl.
8. A compound according to claim 7, in which R8 and R9 independently of one another are hydrogen or methyl; and p is 1 or 2.
9. A compound according to claim 8, in which R8 and R9 are methyl.
10. A compound according to claim 7, in which R10 is C1-C8alkyl, C3-C6cycloalkyl, phenyl, phenyl substituted by halogen, or is naphthyl; R11 is C3-C8cycloalkyl, benzyloxy, benzyloxy substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or phenoxy, or is naphthyloxy; and R13 is C3-C7cycloalkyl or cyano-C1-C4alkyl.
11. A compound according to claim 7, in which Y and Z are NR12.
12. A compound according to claim 11, in which R12 is hydrogen or C1-C4alkyl.
13. A compound according to claim 7, in which R8 and R9 independently of one another are hydrogen or methyl; p is 1 or 2; R10 is C1-C4alkyl, C3-C6cycloalkyl, phenyl, phenyl substituted by halogen, or is naphthyl; R11 is C3-C6cycloalkyl, benzyloxy, benzyloxy substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or phenoxy, or is naphthyloxy; Y and Z are NR12 ; R12 is hydrogen or C1-C4alkyl; and R13 is C1-C4cycloalkyl or
cyano-C1-C4alkyl.
14. A compound according to claim 1, in which R1 is the group ;R4 is 
fluorine, chlorine or C1-C4alkyl; n is 1, 2 or 3; m is 0; R2 and R3 are C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-; G is the group -CO-A (a); A is a group -(CR8R9)p-(Y)o-CO-(Z)r-Rj0,
-(CR8R9)p-R11 or -N(R10)R13, or is unsubstituted or substituted naphthyl; R8 and R9 independently of one another are hydrogen or methyl; p is 1 or 2; R10 is C1-C4alkyl, C3-C6cycloalkyl, phenyl, phenyl substituted by halogen, or is naphthyl; R11 is
C3-C8cycloalkyl, benzyloxy, benzyloxy substituted by halogen, C1-C4alkyl,
C1-C4haloalkyl or phenoxy, or is naphthyloxy; and R13 is C3-C8cycloalkyl or
cyano-C1-C6alkyl.
15. A compound according to claim 1, in which R1 is the group ; and m 
is 0.
16. A compound according to claim 15, in which R4 is C1- or C2alkyl; and n is 1, 2 or 3.
17. A compound according to claim 16, in which R4 is C1- or C2alkyl in positions 2, 4 and 6 relative to the phenyl linkage site; and n is 3.
18. A compound according to claim 1, in which R1 is the group ; m is 0;
R4 is C1- or C2alkyl; n is 1, 2 or 3; R2 and R3 are C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-.
19. A compound according to claim 1, in which G is a group -CO-A (a); and A is
C1-C8alkyl substituted by nitro, cyano, Si( C1-C4alkyl)3, amino, C1-C4alkylamino, di(C1-C4alkyl)amino, substituted or unsubstituted benzyloxy or a group , 
or A is C3-C8cycloalkyl, which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio,
C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is C3-C8cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by C1-C4alkyl, or A is a group
-(CR8R9)p-(Y)o-CO-(Z)r-R10 or -(CR8R9)p-R11.
20. A compound according to claim 1, in which R1 is the group ; R4 is 
C1- or C2alkyl; n is 1, 2 or 3; m is 0; R2 and R3 are C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-; G is the group -CO-A (a); and A is C1-C8alkyl substituted by nitro, cyano, Si( C1-C4alkyl)3, amino, C1-C4alkylamino, di( C1-C4alkyl)amino, substituted or unsubstituted benzyloxy or a group
, or A is C3-C8cycloalkyl which can if desired contain as heteroatom 
oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is C3-C8cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by C1-C4alkyl, or A is a group
-(CR8R9)p-(Y)o-CO-(Z)r-R10 or -(CR8R9 )p-R11.
21. A process for the preparation of a compound of the formula
in which R1, R2 and R3 are as defined in claim 1, G is the group -CO-A (a) and A is as defined in claim 1 with the exception of the group -N(R10)R13, which comprises reacting a compound of the formula , 
in which R1, R2 and R3 are as defined, with a compound of the formula 
,
in which A is as defined and E1 is a leaving group.
22. A process for the preparation of a compound of the formula
in which R1, R2 and R3 are as defined in claim 1, G is the group -CO-A (a), and A is -N(R10)R13, where R10 and R13 are as defined in claim 1 with the exception of R10 as hydrogen, which comprises reacting a compound of the formula
in which R1, R2 and R3 are as defined, with a compound of the formula 
in which R10 and R13 are as defined and E1 is a leaving group.
23. A process for the preparation of a compound of the formula
in which R1, R2 and R3 are as defined in claim 1, G is the group -CO-A (a), and A is -NHR13, where R13 is as defined in claim 1, which comprises reacting a compound of the formula
in which R1, R2 and R3 are as defined, with an isocyanate of the formula
R13-N=C=O (V),
in which R13 is as defined.
24. A process for the preparation of a compound of the formula 
in which R1, R2 and R3 are as defined in claim 1, G is the group -SO2-B (b), and B is as defined in claim 1, which comprises reacting a compound of the formula
in which R1, R2 and R3 are as defined in claim 1, with a compound of the formula
B-SO2-E1 (VI),
in which B is as defined and E1 is a leaving group, if desired in a solvent and in the presence or absence of a base.
25. A pesticidal composition comprising, in addition to customary formulation auxiliaries, at least one compound of the formula I according to claim 1 as active substance.
26. The use of a pesticidal composition according to claim 25 for controlling insects, representatives of the order Acarina or broad-leaved weeds and grasses.
27. A method of controlling broad-leaved weeds and grasses, which comprises treating the crop plants which are to be protected against broad-leaved weeds and grasses, or the broad-leaved weeds and grasses themselves, with a composition according to claim 25.
28. A pesticidal composition according to claim 25, which is used for controlling insects or representatives of the order Acarina.
29. A pesticidal composition according to claim 25, which is used for the selective control of broad-leaved weeds and grasses in crops for useful plants.
30. The use of a composition according to claim 26 for controlling insects or
representatives of the order Acarina.
31. The use of a composition according to claim 26 for the selective control of broad-leaved weeds and grasses in crops of useful plants.
32. A method of controlling insects or representatives of the order Acarina, which comprises applying a composition according to claim 28 to the pests or their habitat
33. A method according to claim 32 for protecting vegetative propagation stock against infestation by insects or representatives of the order Acarina, which comprises treating the propagation stock or the site where the propagation stock is planted out.
34. Vegetative propagation stock treated by the method described in claim 33.
35. A method for controlling unwanted plant growth, which comprises treating the crop plants which are to be protected against broad-leaved weeds, and/or the broad-leaved weeds and grasses, with a composition according to claim 25.
36. A composition according to claim 28, which contains from 0.1 to 99 percent by weight of active substance.
37. A method according to claim 32, wherein from 0.001 to 2 kg of active substance are applied per hectare.
38. A composition according to claim 29, which contains from 0.1 to 95 percent by weight of active substance of the formula I.
39. A method according to claim 35, which comprises applying a compound of the formula I in a quantity of from 0.001 to 2 kg per hectare.
40. A selective-herbicidal composition which comprises, in addition to customary inert formulation auxiliaries, a mixture of a herbicidally effective quantity of a compound of the formula I and safener, as active substance.
41. A herbicidal composition according to claim 40, wherein the safener is a quinoline derivative, pyrazole derivative or triazole derivative.
42. A composition according to claim 41, wherein the safener is either a quinoline derivative of the formula 
in which
R15 is hydrogen, C1-C8alkyl or C1-C8alkyl which is substituted by C1-C6alkoxy or C3-C6alkenyloxy; and
X2 is hydrogen or chlorine; or
a 1-phenylazole-3-carboxylic acid derivative of the formula
OOR
in which
E is nitrogen or methine;
R16 is -CCI3 or unsubstituted or halo-substituted phenyl;
R17 and R 18 independently of one another are hydrogen or halogen; and
R19 is C1-C4alkyl.
43. A composition according to claim 40, wherein, in the compounds of the formula I, the radical R1 is the group ; and m is 0.
44. A composition according to claim 43, in which R4 is C1- or C2alkyl; and n is 1, 2 or 3.
45. A composition according to claim 44, in which R4 is C1- or C2alkyl in positions 2, 4 and 6 relative to the phenyl linkage site; and n is 3.
46. A composition according to claim 40, wherein, in the compounds of the formula I, R1 is the group ; m is 0; R4 is C1- or C2alkyl; n is l, 2 or 3; R2 and R3 are 
C1-C6alkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH2)5-, -(CH2)4- or -(CH2)3-.
47. A composition according to claim 40, wherein, in the compounds of the formula I, G is the group -CO-A (a); and A is C1-C8alkyl substituted by nitro, cyano, Si( C1-C4alkyl)3, amino, C1-C4alkylamino, di(C1-C4alkyl)amino, unsubstituted or substituted benzyloxy or a group , or A is C3-C8cycloalkyl which if desired can contain as
heteroatom oxygen, sulfur or nitrogen and is substituted by C1-C4alkyl, C1-C4alkoxy,
C1-C4alkyldiio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is C1-C4cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by C1-C4alkyl, or A is a group -(CR8R9)p-(Y)0-CO-(Z)r-R10or -(CR8R9)p-R11.
48. A composition according to claim 40, wherein, in the compounds of the formula I, R1 is the group ; R4 is C1- or C2alkyl; n is 1, 2 or 3; m is 0; R2 and R3 are 
Q-Qalkyl; or R2 and R3 together form a substituted or unsubstituted alkylene chain -(CH^-, -(CH2)4- or -(CH2)3 ; G is the group -CO-A (a); and A is C1-C8alkyl substituted by nitro, cyano, Si(C1-C4alkyl)3, amino, C1-C4alkylamino, di(C1-C4alkyl)amino, unsubstituted or substituted benzyloxy or a group , or A is C3-C8cycloalkyl 
which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by
C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or substituted or unsubstituted phenyl, or A is C1-C4cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by
C1-C4alkyl, or A is a group -(CR8R9)p-(Y)o-CO-(Z)r-R10or -(CR8R9)p-R11.
49. A composition according to claim 42, which comprises as safener a compound of the formula 
50. A composition according to claim 42, which comprises as safener a compound of the formula
51. A composition according to claim 42, which comprises as safener a compound of the formula
52. A method for the selective control of broad-leaved weeds and grasses in crops of useful plants, which comprises treating the crops, their seed or their cultivation area, simultaneously or independently of one another, with an effective quantity of a herbicide of the formula I and a herbicide-antagonistically effective quantity of a safener of the formula X or XI according to claim 42.
53. A method according to claim 52, which comprises treating stocks of crop plants or cultivation areas for crop plants with from 0.001 to 2 kg/ha of a herbicide of the formula I and a quantity of from 0.001 to 0.5 kg/ha of a safener of the formula X or XI.
54. A method according to claim 52, wherein the crop plants are maize and cereals.
55. A compound according to claim 1 of the formula I, in which R1 is 2,4,6-trimethylphenyl, R2 and R3 together are -(CH2)4- and G is
-C(=O)-N(CH3)CH2CH2CN.
56. A compound according to claim 1 of the formula I, in which R1 is
2,4,6-trimethylphenyl, R2 and R3-N together are -CH2CH2CH(CH3)CH2-N and G is -C(=O)-N(CH3)CH2CH2CN.
57. A compound according to claim 1 of the formula I, in which R1 is 2,6-dichlorophenyl, R2 and R3 together are -(CH2)4- and G is -C(=O)-N(CH3)CH2CH2CN.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MX9705247A MX9705247A (en) | 1995-01-13 | 1995-12-29 | 4-aryl- and 4-heteroaryl -5-oxopyrazoline derivatives having pesticidal properties. |
| JP8521407A JPH10512248A (en) | 1995-01-13 | 1995-12-29 | 4-Aryl- and 4-heteroaryl-5-oxo-pyrazoline derivatives having pesticidal properties |
| EP95943223A EP0804422A1 (en) | 1995-01-13 | 1995-12-29 | 4-aryl- and 4-heteroaryl -5-oxopyrazoline derivatives having pesticidal properties |
| AU44353/96A AU4435396A (en) | 1995-01-13 | 1995-12-29 | 4-aryl- and 4-heteroaryl -5-oxopyrazoline derivatives having pesticidal properties |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH00108/95 | 1995-01-13 | ||
| CH10895 | 1995-01-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996021652A1 true WO1996021652A1 (en) | 1996-07-18 |
Family
ID=4179456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1995/005152 WO1996021652A1 (en) | 1995-01-13 | 1995-12-29 | 4-aryl- and 4-heteroaryl -5-oxopyrazoline derivatives having pesticidal properties |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0804422A1 (en) |
| JP (1) | JPH10512248A (en) |
| CN (1) | CN1175248A (en) |
| AR (1) | AR002020A1 (en) |
| AU (1) | AU4435396A (en) |
| BR (1) | BR9600088A (en) |
| CA (1) | CA2210286A1 (en) |
| IL (1) | IL116697A0 (en) |
| MX (1) | MX9705247A (en) |
| TR (1) | TR199600024A2 (en) |
| WO (1) | WO1996021652A1 (en) |
| ZA (1) | ZA96243B (en) |
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| WO2022041615A1 (en) * | 2020-08-29 | 2022-03-03 | 海利尔药业集团股份有限公司 | Phenylpyrazoline derivative or salt thereof, and composition and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10326386A1 (en) | 2003-06-12 | 2004-12-30 | Bayer Cropscience Ag | N-heterocyclyl-phenyl-substituted cyclic ketoenols |
| CN101580489B (en) * | 2008-05-14 | 2011-07-20 | 中国中化股份有限公司 | Nitrogenous heterocyclic ring compound and preparation method and application thereof |
| AU2011337596B2 (en) * | 2010-12-02 | 2016-07-07 | Ono Pharmaceutical Co., Ltd. | Novel compound and medical use thereof |
| JP2017214289A (en) * | 2014-09-12 | 2017-12-07 | 公益財団法人相模中央化学研究所 | Pyrazolinone derivative, method for producing the same and herbicide containing the same as an active ingredient |
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- 1995-12-29 EP EP95943223A patent/EP0804422A1/en not_active Withdrawn
- 1995-12-29 CN CN95197652A patent/CN1175248A/en active Pending
- 1995-12-29 MX MX9705247A patent/MX9705247A/en unknown
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| WO1999047525A1 (en) * | 1998-03-13 | 1999-09-23 | Novartis Ag | Herbicidally active 3-hydroxy-4-aryl-5-oxopyrazoline derivatives |
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| WO2021205448A1 (en) | 2020-04-06 | 2021-10-14 | Adama Agan Ltd. | Co-crystals of antioxidants and active ingredients and use of antioxidants as stabilizer |
| WO2022041615A1 (en) * | 2020-08-29 | 2022-03-03 | 海利尔药业集团股份有限公司 | Phenylpyrazoline derivative or salt thereof, and composition and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AR002020A1 (en) | 1998-01-07 |
| CN1175248A (en) | 1998-03-04 |
| BR9600088A (en) | 1998-01-27 |
| IL116697A0 (en) | 1996-05-14 |
| MX9705247A (en) | 1997-10-31 |
| EP0804422A1 (en) | 1997-11-05 |
| AU4435396A (en) | 1996-07-31 |
| TR199600024A2 (en) | 1996-08-21 |
| JPH10512248A (en) | 1998-11-24 |
| CA2210286A1 (en) | 1996-07-18 |
| ZA96243B (en) | 1996-08-19 |
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