Classifications

• • 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
  • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
• • 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
  • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur

Definitions

• the invention relates to novel pesticidally active compounds of the formula I
• R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, or C 1 -C 4 alkylthio;
• R 2 and R 3 independently of one another are hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1-5 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 alkanoyl-C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, C 1 -C 2 alkylthio-C 1 -C 4 alkyl, C 1 -C 2 alkanesulfinyl-C 1 -C 4 alkyl, C 1 -C 2 alkanesulfonyl-C 1 -C 4 alkyl, C 2 -C 4 alkenyl, halo-C 2 -C 4 alkenyl having 1, 2 or 3 halogen atoms, C 2 -C 4
• R 4 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms,
• R 5 and R 6 independently of one another are hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C 1 -C 2 alkyl;
• R 7 is hydrogen, halogen, C 1 -C 4 alkyl, cyclopropyl, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio;
• X is OR 10 , SR 10 or N(R 11 )R 12 ;
• R 10 is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 12 carbon atoms and which is substituted or unsubstituted, a cyclic, saturated or unsaturated hydrocarbon radical which has not more than 10 carbon atoms and which is substituted or unsubstituted, substituted or unsubstituted benzyl; or a substituted or unsubstituted heterocyclyl radical;
• R 11 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical which has not more than 8 carbon atoms and which is unsubstituted or substituted by 1-5 halogen atoms, C 1 -C 2 alkoxy. hydroxyl, nitro, cyano, C 1 -C 4 alkanoyl, halo-C 1 -C 4 alkanoyl or
• C 1 -C 4 alkoxycarbonyl a cyclic, saturated or unsaturated hydrocarbon radical which has not more than 10 carbon atoms or benzyl, in which the carbocycle is unsubstituted or mono- or disubstituted by halogen, C 1 -C 2 alkyl, halomethyl, nitro or cyano, or heterocyclyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of C 1 -C 2 alkyl, halogen, halomethyl, nitro or cyano;
• R 12 is hydrogen or C 1 -C 4 alkyl
• R 11 and R 12 together with the nitrogen atom to which they are bonded are a heterocycle which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, C 1 -C 2 alkyl, halomethyl or nitro;
• the invention furthermore relates to the preparation of these compounds, to agrochemical compositions comprising at least one of these compounds as active ingredient, and to the use of the active ingredients or the pesticides, in particular as microbicides in agriculture and horticulture.
• the compounds I and, if appropriate, their tautomers can exist in the form of salts. Since the compounds I have at least one basic centre, they can form, for example, acid addition salts. These are formed, for example, with mineral acids, for example sulfuric acid, a phosphoric acid or a hydrohalic acid, with organic carboxylic acids, for example acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with
• hydroxycarboxylic acids for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, for example methane- or p-toluenesulfonic acid.
• salts with bases are, for example, metal salts, such as alkali metal salts or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or with an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
• corresponding internal salts may be formed. Preferred within the scope of the invention are agrochemically advantageous salts.
• Alkyl groups are straight-chain or branched and are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, sec-amyl, tert-amyl, 1-hexyl or 3-hexyl.
• Alkenyl is to be understood as meaning straight-chain or branched alkenyl, for example allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkenyl radicals having a chain length of 3 to 4 carbon atoms are preferred.
• Alkynyl too can be straight-chain or branched, depending on the number of the carbon atoms, for example it can be propargyl, but-1-yn-1-yl or but-1-yn-3-yl. Propargyl is preferred.
• Unsaturated hydrocarbon radicals are alkenyl, alkynyl or alkenynyl groups having not more than 3 multiple bonds, for example butadienyl, hexatrienyl, 2-penten-4-ynyl.
• Halogen or halo are fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
• Haloalkyl can have identical or different halogen atoms, examples which may be mentioned being fluoromefhyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl.
• Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy and tert-butyloxy; preferably methoxy and ethoxy.
• Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy.
• Cycloalkyl is, depending on the size of the ring, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
• Cyclic unsaturated hydrocarbon radicals can be aromatic, for example phenyl and naphthyl, or not aromatic, for example cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctadienyl, or partially aromatic, for example tetrahydronaphthyl and indanyl.
• Alkanoyl is either straight-chain or branched, in each case taking into consideration the number of carbon atoms involved. Possible examples are formyl, acetyl, propionyl, butyryl, pivaloyl or octanoyl.
• alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyl-, nitro- or cyano-substituted carbon-containing groups and compounds such as alkoxyalkyl, alkylthioalkyl, alkanesulfinylalkyl, alkanesulfonylalkyl, nitroalkyl,cyanoalkyl and cyanoalkanesulfonyl, one of the hydrogen atoms in the unsubstituted base structure on which these groups and compounds are based is replaced by alkoxy, alkylthio, alkanesulfinyl, alkanesulfonyl, nitro or cyano.
• a heterocyclyl radical is to be understood as meaning 5- or 6-membered, aromatic and nonaromatic rings having hetero atoms N, O and/or S. Moreover, an unsubstituted or substituted benzo group may be fused to such a heterocyclyl radical bonded to the remaining moiety.
• heterocyclyl groups are pyridyl, pyrimidinyl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, triazolyl, thienyl, furanyl, pyrrolyl, morpholinyl, oxazolyl and the corresponding partially or fully hydrogenated rings.
• heterocyclyl groups having a fused benzo group examples include quinolyl, isoquinolyl, benzoxazolyl, quinoxalinyl, benzothiazolyl, benzimidazolyl, indolyl, indolinyl.
• R 10 is an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 8 carbon atoms and which is unsubstituted or substituted by 1-5 halogen atoms, C 1 -C 2 alkoxy, hydroxyl, nitro, cyano, C 1 -C 4 alkanoyl, halo-C 1 -C 4 alkanoyl or
• C 1 -C 4 alkoxycarbonyl a cyclic, saturated or unsaturated hydrocarbon radical which has not more than 10 carbon atoms, or benzyl in which the carbocycle is unsubstituted or mono- or disubstituted by halogen, C 1 -C 2 alkyl, halomethyl, nitro or cyano, or heterocyclyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, C 1 -C 2 alkyl, halomethyl, nitro or cyano, or a 5- to
• R 10 is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 12 carbon atoms and which is unsubstituted or substituted by
• U is hydrogen, C 1 -C 4 alkyl, cyano or C 1 -C 6 alkoxycarbonyl
• W is C 1 -C 6 alkoxy, C 3 -C 6 cycloalkoxy or the group -N(T 1 )T 2
• n 0, 1 or 2 and
• T 1 and T 2 independently of one another are hydrogen, C 1 -C 6 alkyl, which is unsubstituted or substituted by 1-3 halogen atoms, C 1 -C 2 alkoxy, hydroxyl, nitro, cyano, C 1 -C 4 alkanoyl, halo-C 1 -C 4 alkanoyl or C 1 -C 4 alkoxycarbonyl, or C 1 -C 6 alkenyl which is unsubstituted or substituted by 1-3 halogen atoms, C 1 -C 6 alkynyl which is unsubstituted or substituted by
• halogen atoms a cyclic, saturated or unsaturated hydrocarbon radical having not more than 10 carbon atoms or benzyl in which the carbocycle is unsubstituted or mono- or disubstituted by halogen, C 1 -C 2 alkyl, halomethyl, nitro or cyano, or heterocyclyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of C 1 -C 2 alkyl, halogen, halomethyl, nitro or cyano; or
• T 1 and T 2 together with the nitrogen atom to which they are bonded form a 5-7-membered heterocycle which can additionally have O, S and/or N as ring atoms, in which the additional nitrogen is unsubstituted or substituted by C 1 -C 4 alkyl, phenyl, C 1 -C 4 alkanoyl, benzoyl or benzyl and in which the carbon atoms of the heterocycle are unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, C 1 -C 2 alkyl, halomethyl or nitro.
• R 10 is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 6 carbon atoms and which is unsubstituted or substituted by
• W is C 1 -C 6 alkoxy, C 3 -C 6 cycloalkoxy or the group -N(T 1 )T 2 ;
• T 1 and T 2 independently of one another are hydrogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl having
• halogen atoms C 3 -C 6 cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl, naphthyl, or
• T 1 and T 2 together with the nitrogen atom to which they are bonded are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
• R 1 is hydrogen or C 1 -C 4 alkyl
• R 2 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms,
• R 3 is fluorine or chlorine
• R 4 is hydrogen or C 1 -C 4 alkyl
• R 5 is C 1 -C 4 alkyl
• R 6 is hydrogen
• R 7 is hydrogen or halogen
• X is OR 10 , SR 10 or N(R 11 )R 12 ;
• R 10 is C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, CpC ⁇ alkoxy- C 1 -C 4 alkyl, hydroxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 alkanoyl- C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, C 2 -C 4 alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C 2 -C 4 alkynyl, C 3 -C 7 cycloalkyl, C 4 -C 8 cycloalkenyl, benzyl, phenyl which is unsubstituted or mono- or disubstituted by halogen, C 1 -C 2 alky
• R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms,
• R 11 and R 12 together with the nitrogen atom to which they are bonded are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
• Preferred groups amongst the compounds mentioned under (4) are furthermore the following:
• R 1 is hydrogen or C 1 -C 4 alkyl
• R 2 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms,
• R 3 is chlorine
• R 4 is hydrogen or C 1 -C 4 alkyl
• R 5 is C 1 -C 4 alkyl
• R 6 is hydrogen
• R 7 is hydrogen
• X is OR 10 or SR 10 ;
• R 10 is the group -CH 2 -CO-W
• W is C 1 -C 6 alkoxy, C 3 -C 6 cycloalkoxy or the group -N(T 1 )T 2 ;
• T 1 and T 2 independently of one another are hydrogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl having
• halogen atoms C 3 -C 6 cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl, naphthyl, or
• T 1 and T 2 together with the nitrogen atom to which they are bonded are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
• R 2 is hydrogen, methyl or ethyl
• R 3 is fluorine or chlorine
• R 5 is methyl or ethyl
• R 7 is hydrogen or fluorine
• X is OR 10 , SR 10 or N(R 11 )R 12 ;
• R 10 is C 1 -C 4 alkyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, vinyl, allyl, 2-propynyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyanomethyl or
• R 11 is hydrogen, C 1 -C 4 alkyl, cyclohexyl, cyclopropyl or phenyl;
• R 12 is hydrogen
• R 11 and R 12 together with the nitrogen atom to which they are bonded are piperidine, morpholine or 2,6-dimethylmorpholine.
• R 2 is hydrogen, methyl or ethyl
• R 3 is fluorine or chlorine
• R 5 is methyl or ethyl
• R 7 is hydrogen or fluorine
• X is OR 10 , SR 10 or N(R 11 )R 12 ;
• R 10 is C 1 -C 4 alkyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, vinyl, allyl, 2-propynyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyanomethyl or
• R 11 is hydrogen, C 1 -C 4 alkyl, cyclohexyl, cyclopropyl or phenyl;
• R 12 is hydrogen
• Rnand R 12 together with the nitrogen atom to which they are bonded are piperidine, morpholine or 2,6-dimethylmorpholine.
• R 10 is C 1 -C 5 alkyl which is unsubstituted or mono- to trisubstituted by halogen, or
• M is hydrogen, Li + , ⁇ a + , K + , 1/2Mg 2+ or a quaternary ammonium ion;
• X is OR 10 or N(R 11 )R 12 and in which R 10 , R 11 and R 12 are as defined for formula I; if appropriate in the presence of a base; or c) to prepare a compound of the formula I in which R 4 is as defined for formula I but is other than hydrogen:
• M is hydrogen, Li + , ⁇ a + , K + , 1/2Mg 2+ or a quaternary ammonium ion;
• X' is OR 10 , SR 10 or N(R 11 )R 12 and in which R 10 , R 1 1 and R 12
• oxidant A in which the substituent A is in the 6- or 7-position and in which R 1 to R 7 and X are as defined for formula I is reacted with an oxidant.
• suitable oxidants are an iron(III) salt, SeO 2 , MnO 2 , H 2 O 2 , Br 2 , Cl 2 , I 2 , SO 3 , H 2 SO 4 , HNO 3 , N-bromosuccinimide, benzoquinones, for example 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ) or O 2 in the presence of a dehydrogenation catalyst.
• DDQ 2,3-dichloro-5,6-dicyano-l,4-benzoquinone
• reaction medium approximately -80°C to the boiling point of the reaction medium, preferably from approximately -20°C to approximately +150°C and, if required, in a sealed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
• Typical reaction conditions can be found in the examples.
• nucleofugic radicals Z or Z' are: fluorine, chlorine, bromine, iodine,
• C 1 -C 8 alkylthio such as methylthio, ethylthio or propylthio
• C 1 -C 8 alkanoyloxy such as acetoxy
• (halo-)C 1 -C 8 alkanesulfonyloxy such as methanesulfonyloxy, ethanesulfonyloxy or trifluoromethanesulfonyloxy
• substituted or unsubstituted phenylsulfonyloxy such as benzenesulfonyloxy or p-toluenesulfonyloxy, and furthermore also hydroxyl.
• Suitable bases are the hydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides or alkylsilylamides of alkali metals or alkaline earth metals, or alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
• Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium carbonate, potassium tert-butanolate, potassium carbonate, lithium
• diisopropylamide potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine,
• N,N-diethylaniline pyridine
• 4-(N,N-dimethylamino)pyridine N-methylmorpholine
• benzyltrimethylammonium hydroxide 1,8-diazabicyclo[5.4.0]undec-5-ene (DBU).
• the reactants can be reacted with each other as such, i.e. without an addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert diluent or solvent or a mixture of these is advantageous.
• solvents or diluents aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons, such as benzene, toluene, xylene, chlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane or trichloroethane; ethers, such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran or dioxane; ketones, such as acetone or methyl ethyl ketone; alcohols, such methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; esters, such as ethyl acetate or butyl acetate; amides, such as N,N-dimethylformamide, N,N-dimethylformamide, N,N-
• N-methylpyrrolidone or hexamethylphosphoric triamide N-methylpyrrolidone or hexamethylphosphoric triamide
• nitriles such as acetonitrile
• sulfoxides such as dimethyl sulfoxide.
• Bases employed in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also act as solvents or diluents.
• the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +180°C, preferably from approximately +20°C to approximately +130°C, in many cases at the reflux temperature of the solvent used.
• reaction can be carried out with phase-transfer catalysis in an organic solvent, for example methylene chloride or toluene, in the presence of an aqueous alkaline solution, for example sodium hydroxide solution, and of a phase transfer catalyst, for example tetrabutylammonium hydrogen sulfate.
• organic solvent for example methylene chloride or toluene
• a phase transfer catalyst for example tetrabutylammonium hydrogen sulfate.
• a compound I which can be obtained according to the invention or by another route or, if appropriate, a tautomer of this compound, can be converted into another compound I in a manner known per se by replacing one or more substituents of the starting compound I in the customary manner by another substituent.
• - halogen substituents can be exchanged for other substituents, such as cyano, alkylthio or alkoxy substituents;
• N-N-hydrogen can be exchanged for N-alkyl, N-benzyl, N-aryl, N-heteroaryl, N-alkanoyl, N-benzoyl or N-sulfonyl;
• - sulfides can be oxidized to give sulfoxides and sulfones
• - carbonyl groups can be sulfated to give thiocarbonyl groups.
• the invention relates to the pure isomers and to all isomer mixtures which are possible.
• the invention also relates to novel starting materials and intermediates used for the preparation of the compounds of the formula I, to their use and to processes for their preparation.
• the compounds of the formulae II, VII and IX can be prepared by known methods as shown in the equation.
• oxidants an iron(III) salt, SeO 2 , MnO 2 , H 2 O 2 , Br 2 Cl 2 , I 2 , SO 3 , H 2 SO 4 , H ⁇ O 3 , N-bromosuccinimide, benzoquinones, for example 2,3-dichloro-5,6- dicyano-1,4-benzoquinone (DDQ) or O 2 in the presence of a dehydrogenation catalyst
• DDQ 2,3-dichloro-5,6- dicyano-1,4-benzoquinone
• thionating agents are phosphorus pentasulfide or
• the compounds of the formula I can be used in the agricultural sector and in related fields as active ingredients for the control of plant pests.
• the active ingredients according to the invention are distinguished by a powerful activity at low rates of concentration and by the fact that they are well tolerated by plants and environmentally friendly. They have highly advantageous curative, preventive and systemic properties and can be used for protecting a large number of crop plants.
• the active ingredients of the formula I the pests which are found on plants or parts of plants (fruits, flowers, foliage, stalks, tubers, roots) of a range of crops of useful plants can be contained or destroyed, and parts of plants which are formed at a later point in time are also left unharmed, for example by phytopathogenic microorganisms.
• Compounds of the formula I can also be used as seed-dressing agents for the treatment of plant propagation material, in particular seed (fruits, tubers, kernels) and nursery plants (for example rice) for protecting them against fungal infection and against soil-borne phytopathogenic fungi.
• the compounds I are active for example against phytopathogenic fungi from the following classes: Fungi imperfecti (for example Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (for example Rhizoctonia, Hemileia, Puccinia). Moreover, they are active against the classes of the Ascomycetes (for example Venturia and Eiysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes (for example Phytophthora, Pythium, Plasmopara).
• Fungi imperfecti for example Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria
• Basidiomycetes for example Rhizoctonia, Hemileia, Puccinia
• Ascomycetes for example Venturia and Eiysiphe, Podos
• the compounds I according to the invention are valuable active ingredients for controlling pests of the order of the Acarina and the classes of the Insecta and Nematoda in agricultural crop plants and ornamentals, in particular in cotton, vegetable and fruit crops, in forests, in the protection of stored products and materials and in the hygiene sector, and of animal pests, in particular in domestic animals and productive livestock. They are active against a range of development stages. Their activity becomes apparent from immediate destruction of the pests or only after some time has elapsed, for example during molting, or from markedly reduced oviposition and/or hatching rates.
• the Acarina include, for example, Boophilus spp.
• the Nematoda include, for example, Heterodera glycines
• the Insecta include, for example, Nilaparvata lugens, Plutella xylostella and Musca domestica.
• target crops for the use in crop protection within the scope of the invention are the following types of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar and fodder beet); pome fruit, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and
• Active ingredients I are conventionally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients.
• These other active ingredients can be, for example, fertilizers, trace element mediators or other preparations which have an effect on the growth of plants.
• Other substances which can be used are selective herbicides and also insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of a plurality of these preparations, if appropriate together with other carriers, surfactants or other application-enhancing additives conventionally used in the art of formulation.
• Suitable carriers and additives can be solid or liquid and are those substances which are expedient in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.
• a preferred method for applying an active ingredient of the formula I or an agrochemical composition which comprises at least one of these active ingredients, is applying it to the foliage (foliar application). The frequency and rate of application will depend on the risk of infestation with the pathogen in question.
• the active ingredients I can also reach the plant via the soil through the root system (systemic action), by drenching the locus of the plant with a liquid preparation or by incorporating the substances in solid form into the soil, for example in the form of granules (soil application).
• the compounds I can also be applied to the seed kernels for seed treatment (coating) by soaking the kernels or tubers in a liquid preparation of the active ingredient or by coating them with a solid preparation.
• the compounds I are employed as pure active ingredients or, preferably, together with auxiliaries conventionally used in the art of formulation. To this end, they are expediently processed in a known manner, for example to give emulsion concentrates, spreadable pastes, ready-to-spray or ready-to-dilute solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, for example by encapsulation in, for example, polymeric substances.
• the methods of application such as spraying, atomizing, dusting, scattering, brushing on or pouring, as well as the nature of the compositions are selected to suit the intended aims and the prevailing circumstances.
• Advantageous rates of application are, in general, 5 g to 2 kg of active ingredient (A.I.) per hectare (ha), preferably 10 g to 1 kg of A.I./ha, in particular 20 g to 600 g of A.L/ha.
• A.I. active ingredient
• compositions, preparations or combinations which comprise the active ingredient of the formula I and, if desired, a solid or liquid additive are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredient with extenders, such as solvents, solid carriers and, if appropriate, surface-active compounds (surfactants).
• extenders such as solvents, solid carriers and, if appropriate, surface-active compounds (surfactants).
• solvents aromatic hydrocarbons, preferably the fractions C 8 to C 12 , for example xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and epoxidized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, and water.
• aromatic hydrocarbons preferably the fractions C 8 to C 12
• phthalic esters such as dibutyl phthalate or dioctyl phthalate
• Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite.
• ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
• highly-disperse silica or highly-disperse absorptive polymers Possible paniculate, adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, or non-sorptive carrier materials, for example calcite or sand.
• a large number of pregranulated materials of inorganic or organic nature can be used, such as dolomite or comminuted plant residues.
• Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants which have good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be formulated.
• Surfactants are also to be understood as meaning mixtures of surfactants.
• Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
• non-ionic surfactants examples include nonylphenol
• polyethoxyethanols castor oil polyglycol ether, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethylene ethanol, polyethylene glycol and
• Fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate, are also suitable.
• the cationic surfactants are, especially, quaternary ammonium salts which have at least one alkyl radical having 8 to 22 carbon atoms as N substituent and lower, free or halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents.
• the agrochemical preparations comprise 0.1 to 99 percent by weight, in particular 0.1 to 95 percent by weight, of active ingredient of the formula 1, 99.9 to 1 percent by weight, in particular 99.8 to 5 percent by weight, of a solid or liquid additive, and 0 to 25 percent by weight, in particular 0.1 to 25 percent by weight, of a surfactant.
• compositions are more preferred as commercially available goods, the end user will, as a rule, use dilute compositions.
• compositions can also comprise other additives, such as stabilizers, defoamers, viscosity regulators, binders or adhesives, and also fertilizers or other active ingredients for achieving specific effects.
• additives such as stabilizers, defoamers, viscosity regulators, binders or adhesives, and also fertilizers or other active ingredients for achieving specific effects.
• Example H- 1a 0.9 g of 7-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-3,4-dihydro-2 -methylthioquinoline and 0.86 g of 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ) are introduced into 20 ml of absolute dioxane in a sulfonation flask at room temperature and the mixture is stirred for approximately 6 hours at 85-90°C. After cooling, the mixture is diluted with 100 ml of ethyl acetate and 30 ml of water, the organic phase is separated off, and the aqueous phase is then extracted twice using ethyl acetate.
• DDQ 2,3-dichloro-5,6-dicyano-l,4-benzoquinone
• H-1.8 1.26/t/3H; 1.43/t/3H; 1.67/d/3H; 2.79/q/2H; 3.33/q/2H; 5.50/m/1H;
• H-1.16 1.07/t/3H; 1.26/t/3H; 1.67/d/3H; 1.79/m/2H; 2.79/m/2H; 3.30/t/2H;
• H-1.34 1.26/t/3H; 1.67/d/3H; 1.60-1.85/m/6H; 2.27/m/2H; 2.79/q/2H;
• H-1.60 1.05/1/3H; 1.26/t/3H; 1.44/d/3H; 1.67/d/3H; 1.66-1.81/m/2H; 2.79/q/2H;
• H-1.90 0.39/m/2H; 0.70/m/2H; 1.26/t/3H; 1.69/d/3H; 2.70/m/1H; 2.79/q/2H;
• H-1.100 1.13/t/3H; 1.23-l,35/m/6H; 1.68/d/3H; 2.79/q/2H; 3.42/q/2H; 3.55/q/2H;
• H-2.100 1.20/t/3H; 1.23-1.35/m/6H; 1.69/d/3H; 2.80/q/2H; 3.42/m/2H;
• Emulsions of any desired dilution can be prepared from these emulsion concentrates using water.
• Example F-2 Emulsion concentrate
• Emulsions of any desired dilution can be prepared from this emulsion concentrate using water.
• the solutions are suitable for use in the form of microdrops.
• wheat plants are sprayed to drip point with an aqueous spray mixture (0.2 % of active ingredient) prepared with a wettable powder of the active ingredient, and, 24 hours later, infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (environment: 95 to 100 percent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. 12 days after infection, the fungus infestation is assessed.
• aqueous spray mixture 0.2 % of active ingredient
• aqueous spray mixture (0.006 % of active ingredient relative to the soil volume) prepared with a wettable powder of the active ingredient is poured next to wheat plants 5 days after sowing. Care is taken that the spray mixture does not come into contact with aerial parts of the plants.48 hours later, the plants are infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (environment: 95 to 100 percent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°C. 12 days after infection, the fungus infestation is assessed.
• Example B-2 Activity against Phytophthora infestans in tomatoes
• Tomato plants are grown for three weeks and then sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 24 hours later, infected with a sporangia suspension of the fungus.
• the fungus infestation is assessed 5 days after the infection, during which period a relative atmospheric humidity of 90 to 100 % and a temperature of 20° are maintained.
• Tomato plants are grown for three weeks and then an aqueous spray mixture (0.006 % of active ingredient based on the soil volume) prepared with a wettable powder of the active ingredient is poured next to them. Care is taken that the spray mixture does not come into contact with the aerial parts of the plants. After 48 hours, the plants are infected with a sporangia suspension of the fungus. The fungus infestation is assessed 5 days after the infection, during which period a relative atmospheric humidity of 90 to 100 % and a temperature of 20° are maintained.
• Example B-3 Residual-protective activity against Cercospora arachidicola in groundnuts
• Groundnut plants with a height of 10 to 15 cm are sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 48 hours later, infected with a conidia suspension of the fungus.
• the plants are incubated for 72 hours at 21° and at high atmospheric humidity and then placed in a greenhouse until the typical lesions appear.
• the activity of the active ingredients is assessed 12 days after infection on the basis of number and size of the lesions.
• Example B-4 Activity against Plasmopara viticola on vines
• Vine seedlings in the 4- to 5-leaf stage are sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 24 hours later, infected with a sporangia suspension of the fungus.
• the fungus infestation is assessed 6 days after infection, during which period a relative atmospheric humidity of 95 to 100 % and a temperature of 20° are maintained.
• Example B-5 Activity against Colletotrichum lagenarium in cucumbers
• Cucumber plants are grown for 2 weeks and then sprayed with a spray mixture
• Example B-6 Residual-protective activity against Venturia inaequalis in apples
• Apple cuttings having fresh shoots of a length of 10 to 20 cm are sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 24 hours later, infected with a conidia suspension of the fungus.
• the plants are incubated for 5 days at a relative atmospheric humidity of 90 to 100 % and then placed for a further 10 days in a greenhouse at 20 to 24°.
• the fungus infestation is assessed 12 days after infection.
• Example B-7 Activity against Erysiphe graminis in barley
• Barley plants approximately 8 cm high are sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 3 to 4 hours later, dusted with conidia of the fungus.
• the infected plants are placed in a greenhouse at 22°. 12 days after infection, the fungus infestation is assessed.
• aqueous spray mixture (0.002 % of active ingredient based on the soil volume) prepared with a wettable powder of the active ingredient is poured next to barley plants approximately 8 cm in height. Care is taken that the spray mixture does not come into contact with the aerial parts of the plants. 48 hours later, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. 12 days after infection, the fungus infestation is assessed.
• Example B-8 Activity against Podosphaera leucotricha in apple shoots
• Apple cuttings having fresh shoots approximately 15 cm in length are sprayed with a spray mixture (0.06 % of active ingredient). After 24 hours, the treated plants are infected with a conidia suspension of the fungus and placed in a controlled environment cabinet at 20°C and a relative atmospheric humidity of 70 %.12 days after infection, the fungus infestation is assessed.
• Young bean plants are populated with a mixed population of Tetranychus urticae and, one day later, sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. The plants are subsequently incubated for 6 days at 25°C and then evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with those on the untreated plants.
• B-10 Activity against a mixed population of Tetranychus cinnabarinus (Acarina).
• Dwarf beans in the 2-leaf stage are populated with a mixed population (eggs,
• the products are applied to the plants in an automatic spray cabin at dosage rates of 200, 100 and 50 mg of A.I./1.
• the substances are formulated and are diluted with water to give the dosage rates in question.
• Rice plants are treated with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. After the spray coating has dried on, the rice plants are populated with plant hopper larvae of the 2nd and 3rd stage. The test is evaluated 21 days later. The percentage reduction in population (% activity) is determined by comparing the number of surviving plant hoppers on the treated plants with those on the untreated plants.
• Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. After the spray coating has dried on, the cabbage plants are populated with 10 Plutella xylostella caterpillars of the third stage and placed in a plastic container. The test is evaluated 3 days later. The percentage reduction in population and the percentage reduction of the feeding damage (% activity) are
• Example B-13 Activity against Musca domestica (Insecta)
• a lump of sugar is treated with a solution of the test substance in such a way that the concentration of test substance in the sugar is 250 ppm after drying overnight.
• This treated lump together with a wet cottonwool ball and 10 adult Musca domestica of an
• OP-resistant strain is placed onto an aluminium dish, and this is covered with a glass beaker and incubated at 25°C. After 24 hours, the mortality rate is determined.
• Sandy soil is infested with eggs of the soybean cyst nematode H. glycines, approximately 6000 eggs per pot.
• the test substances are subsequently mixed in, at the relevant concentrations, 1c pots (180 ccm) are then filled with the treated and infested soil, and three soybeans (cv. Maple Arrow) are sown per pot. Each treatment is replicated three times.
• the pots are incubated in the greenhouse for four to five weeks at approximately 27°C. The plants are then carefully removed from the pots, the roots are washed, and the number of cysts is determined.

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• 1994
  • 1994-06-27 AU AU73447/94A patent/AU7344794A/en not_active Abandoned
  • 1994-06-27 WO PCT/EP1994/002076 patent/WO1995001975A1/en not_active Application Discontinuation
  • 1994-06-27 EP EP94922239A patent/EP0707582A1/de not_active Withdrawn
  • 1994-06-27 JP JP7503793A patent/JPH09503746A/ja active Pending
  • 1994-07-07 IL IL11023694A patent/IL110236A0/xx unknown
  • 1994-07-08 ZA ZA944947A patent/ZA944947B/xx unknown
  • 1994-07-08 MX MX9405202A patent/MX9405202A/es unknown

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