Classifications

• • 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
  • A01N47/12—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, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
• • 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
  • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/32—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings
  • C07C271/34—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
  • C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C271/54—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/60—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups having oxygen atoms of carbamate groups bound to nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
  • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the present invention relates to carbamoylcarboxamides of the general formula I.
• R 1 Ci-Ce-alkyl, C 2 -C 8 alkenyl or C 2 -C 8 -Al inyl, where these radicals are partially or completely halogenated and / or can carry one to three of the following groups: cyano, -C-C 4 -alkoxyalkyl, -C-C 4 -haloalkyl, Ci - ⁇ - alkoxy, C ⁇ -C4-haloalkoxy, C ⁇ -C 4 -alkylthio, C ⁇ -C 4 -alkoxycarbonyl, C 3 -C cycloalkyl, C 3 * -C 7 -Cycloalkenyl, aryl, aryloxy and
• Heteroaryl where the cyclic radicals in turn may carry one to three of the following substituents: halogen, cyano, C4 - alkyl, C ⁇ -C4-alkoxyalkyl, C ⁇ -C4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 -haloalkoxy, -CC 4 alkylthio, -C 4 -alkoxycarbonyl, aryl, aryloxy and heteroaryl,
• C 3 -C 7 cycloalkyl or C 3 -C cycloalkenyl these radicals being partially or completely halogenated and / or carrying one to three of the following groups: cyano, C 1 -C 4 -alkyl, C -.- C 4 * Alkoxyalkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 alkoxy,
• a non-aromatic 4- to 8-membered ring which, as ring members, can contain, in addition to carbon, one or two of the heteroatoms oxygen, sulfur and nitrogen, the carbon atoms in the ring being able to carry one or two of the following groups: halogen, cyano, C * -C 4 alkyl, C ⁇ -C4-alkoxyalkyl, Ci - ⁇ - haloalkyl, C ⁇ -C 4 -alkoxy, C4-haloalkoxy, C ⁇ -C alkylthio, C ⁇ -C 4 -alkoxycarbonyl, aryl and aryloxy, and wherein the second and any further nitrogen atom as Heteroatom in the ring carries hydrogen or a C 1 -C 4 -alkyl group,
• Aryl or heteroaryl where these radicals may carry one to three of the following groups: halogen, cyano, C 4 -alkyl, C 4 alkoxyalkyl, C ⁇ - * C 4 haloalkyl, C ⁇ -C4-alkoxy, C ⁇ -C -haloalkoxy, -C-C 4 -alkylthio, -C-C 4 -alkoxycarbonyl,
• W - W 2 C N-, where W 1 denotes Ci-Cs-alkyl, which can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C 1 -C 4 -alkoxyalkyl, C ⁇ -C4-haloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy,
• C 1 -C 4 alkylthio, aryl, aryloxy and heteroaryl the cyclic groups in turn being able to carry one to three of the following substituents: halogen, cyano, C 1 -C 4 alkyl, C 4 -C 4 alkoxyalkyl, C 1 -C 4 - haloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C ⁇ -C 4 alkylthio, C ⁇ * -C 4 alkoxycarbonyl, aryl, aryloxy,
• C 2 ⁇ C 8 alkenyl or C 2 -Cs alkynyl these radicals being partially or completely halogenated and / or carrying one to three of the following groups: cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxyalkyl , C ⁇ -C4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C 4 -alkoxycarbonyl, aryl and aryloxy, wherein the cyclic groups, in turn, one to three of the following may carry substituents: halogen, cyano, C * 4 -alkyl, C 4 alkoxyalkyl, C ⁇ -C 4 halo-alkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C ⁇ -C 4 ⁇ Alkylthio, -CC 4 alkoxycarbonyl, aryl and aryloxy
• C 3 -C -cycloalkyl or C 3 -C cycloalkenyl where these radicals may carry one to three of the following groups: halogen, cyano, C 4 -alkyl, * -C 4 alkoxyalkyl, C ⁇ -C 4 - haloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C 4 -alkoxycarbonyl, aryl and aryl- (C 1 -C 4) alkyl, said groups, which aryl contain, can carry one to three of the following substituents: halogen, cyano, -CC 4 allyl, -C-C 4 alkoxyalkyl, -C-C 4 ⁇ haloalkyl, -C ⁇ C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 al
• Aryl or heteroaryl where these radicals may carry one to three of the following groups: halogen, cyano, C 4 -alkyl, C 4 alkoxyalkyl, C ⁇ -C l 4 -Halogenalk, C ⁇ -C4 ⁇ alkoxy, C ⁇ -C 4 -haloalkoxy, -C-C 4 alkylthio, -C-C 4 alkoxycarbonyl, aryl and aryloxy and
• R 2 is hydrogen or Ci-C ⁇ -alkyl or C 3 -C 7 cycloalkyl, which can be partially or completely halogenated;
• R 4 is hydrogen or one of the groups mentioned for R 3 or
• R 5 is a radical R 2 ;
• X independently of one another hydrogen, Ci-C ⁇ -alkyl and / or
• C 2 -C 8 -alkenyl where these radicals may be partially or fully logeniert ha ⁇ and / or may carry one to three of the following groups: cyano, C 4 alkoxyalkyl, C ⁇ -C4 haloalkyl, C ⁇ -C 4 -Alkoxy, -C-C 4 -haloalkoxy, -C-C 4 -alkylthio and -C-C 4 -alkoxycarbonyl, aryl and aryloxy,
• C 3 -C 7 cycloalkyl and / or C3-C 7 cycloalkenyl these radicals being partially or completely halogenated and / or carrying one to three of the following groups: cyano, C 1 -C 4 alkyl, C 1 -C 4 -Alkoxyalkyl, -C-C 4 -haloalkyl, -C-C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy, C ⁇ -C 4 -alkylthio, C ⁇ -C 4 -alkoxycarbonyl, aryl, aryloxy and aryl- (C 1 -C 4 ) alkyl, the cyclic groups in turn can carry one to three of the following substituents: halogen, cyano, C 4 -alkyl, C 4 alkoxyalkyl, C ⁇ -C4 haloalkyl, C ⁇ -C 4 alkoxy, C ⁇ -C4-haloalkoxy, C ⁇ -
• Y 1 has the following meaning: C 3 -C cycloalkyl or C 3 -C 7 cycloalkenyl, these groups being partially or completely halogenated and / or having one to three of the following substituents : Cyano, -CC 4 -alkyl, -C-C 4 -alkoxy- alkyl, -C-C4-haloalkyl, -C-C 4 ⁇ alkoxy, C ⁇ ⁇ C 4 -haloalkoxy, -C-C 4 -alkylthio, C ⁇ -C 4 alkoxycarbonyl, aryl, aryloxy and aryl- (C 1 -C 4) -alkyl, where the cyclic groups may in turn carry from one to three of the following substituents: halogen, cyano, C 4 -alkyl, C alkoxyalkyl, C ⁇ -C4 halo-alkyl, where the cyclic groups may in turn carry from one to three
• R 6 is aryl or heteroaryl, where these radicals may carry one to three of the following groups: halogen, cyano, C 4 -alkyl, C 4 alkoxyalkyl, C ⁇ -C4-haloalkyl, C ⁇ -C 4 alkoxy, C ⁇ -C4-haloalkoxy, C ⁇ -C4-alkylthio, C ⁇ ⁇ C 4 alkoxycarbonyl, aryl, and aryloxy, wherein, it can carry one to three of the following substituents in the groups, which aryl th enthal ⁇ : halogen, cyano, C ⁇ -C 4 -alkyl, C 4 alkoxyalkyl, C ⁇ ⁇ C 4 haloalkyl, C ⁇ ⁇ C 4 -alkoxy, C 4 haloalkoxy, Ci-C 4 -Alky1thio, Ci-C 4 -Alkoxycarbony1.
• the invention relates to processes for the preparation of the compounds I, compositions containing them, a process for the production of such compositions and a process for combating harmful fungi and the use of the compounds I therefor.
• Amino acid amides with a fungicidal activity are known from the literature (cf. EP-A-0 398 072, EP-A-0 425 925, EP-A-0 472 996, EP-A-0 477 639, EP A-0 485 794, EP-A-0 493 683, EP-A-0 496 239, EP-A-0 550 788, EP-A-0 554 729), which, however, cannot yet be satisfactory in terms of their fungicidal activity.
• the present invention was therefore based on new carbamoylcarboxylic acid amides with improved activity against harmful fungi.
• the compounds I can be prepared in a manner known per se starting from the corresponding carbamoylcarboxylic acids II.
• the compounds I are preferably obtained by processes A and B described below (the literature references "Houben-Weyl” refer to: Houben-Weyl, Methods of Organic Chemistry, 4th edition, Thieme Verlag, Stuttgart) .
• the Carbamoylcarbonchureamide.I is obtained by reacting the Carbamoylcarbonchuream II with the amines III.
• the carbamoyl carboxylic acids II are known or can be prepared by known methods, especially starting from the underlying amino acids (cf. "Houben-Weyl", volume 15/1, page 46 to page 305, especially page 117 to page 125 ).
• the amines III are also known or can be obtained by known methods (cf. Organikum, 15th edition, German Publishing House of Sciences, Berlin, 1977, page 610ff .; J. Am. Chem. Soc. 79, page 1455 to page 1458 (1957); Acta Pharm. Suecica. 5, Hef 5, page 429).
• Process A is preferably carried out by first converting the carbamoylcarboxylic acids II into carboxy-activated derivatives, especially acyl cyanides or anhydrides (cf. Tetrahedron Letters, Volume 18, page 1595 to page 1598 (1973), or " Houben-Weyl ", volume 15/1, page 28 to page 32). These derivatives are then reacted with the amines III in the presence of bases.
• carboxy-activated acyl cyanides e.g. the reaction of carbamoylcarboxylic acids II with cyanophosphonic acid diethyl ester, especially in an inert solvent such as tetrahydrofuran or toluene.
• carboxy-activated anhydrides To prepare the carboxy-activated anhydrides, the reaction of carbamoylcarboxylic acid II with carbonic acid chlorides such as isobutyl chloroformate in the presence of bases and, if appropriate, in an inert solvent such as toluene or tetrahydrofuran is preferred.
• carbonic acid chlorides such as isobutyl chloroformate
• an inert solvent such as toluene or tetrahydrofuran
• the reaction of the amines III with the carboxy-activated carbamoyl carboxylic acids II is preferably carried out in a solvent such as dichloromethane, tetrahydrofuran or toluene.
• the amines III themselves can serve as bases, usually being recovered from the crude product.
• the carbamoylcarboxylic acid II, the amine III, the reagent suitable for producing the caboxy-activated derivative of carbamoylcarboxylic acid II and the base are reacted in a one-pot process, if appropriate in an inert solvent, and the crude product is subsequently reacted worked up in a known manner on the carbamoylcarboxamide I.
• the carbamoylcarboxamides I are obtained by converting the carbamoylcarboxamides I, in which the R-- ⁇ 0- (CO) group is a protective group which can be split off in a manner known per se, into amino acid amides IV and convert them with them Chlorformyloximen V in the presence of bases.
• Stage Ba production of the amino acid amides IV
• the group R 1 -0- (CO) can be split off from the carbamoylcarboxylic amides I in a manner known per se (cf. "Houben-Weyl", volume 15/1, page 46 to page 305, especially page 126 to page 129).
• Suitable cleavable groups contain a tert-butyl or benzyl group as radical R 1 .
• the cleavage is usually carried out by reaction with an acid, in particular a protonic acid such as hydrochloric acid or trifluoroacetic acid (ibid., Pages 126 to 129).
• an acid in particular a protonic acid such as hydrochloric acid or trifluoroacetic acid (ibid., Pages 126 to 129).
• the carbamoylcarboxamides I suitable as starting materials can be obtained by known processes (cf. "Houben-Weyl", volume 15/1, page 28 to page 32) or in particular by process A according to the invention.
• the amino acid amides IV resulting from the synthesis stage (Ba) are reacted with the chloroformyloximes V in the presence of bases.
• the chloroformyl oximes V are known or can be prepared by known processes, e.g. by phosgenation of oximes (see e.g. Zeitschrift für Chemie, Volume 9, page 344 to page 345 (1967)).
• the reaction is preferably carried out in an organic solvent, especially toluene, methylene chloride or tetrahydrofuran, or mixtures of these solvents.
• Inorganic and organic bases are equally suitable as bases, with organic bases and in turn tertiary amines such as triethylamine, pyridine and N-methylpiperidine being preferred.
• the reaction is usually carried out at temperatures from (-40) to 50, preferably (-10) to 20 ° C.
• reaction mixtures obtained by processes A and B are worked up in the customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographically Cleaning the raw products.
• the intermediate and end products are obtained in the form of colorless or slightly brownish, viscous oils, which can be freed from volatile components under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, the purification can also be carried out, for example, by recrystallization or digesting.
• the compounds of the formula I can optionally be in the form of geometric and / or optical isomers or isomer mixtures. Both the pure isomers and the mixtures of the isomers have the fungicidal activity.
• salts especially of acid-resistant compounds I, which contain basic centers, especially basic nitrogen atoms, in particular with mineral acids such as sulfuric acid and phosphoric acid or Lewis acids such as zinc chloride.
• basic centers especially basic nitrogen atoms, in particular with mineral acids such as sulfuric acid and phosphoric acid or Lewis acids such as zinc chloride.
• mineral acids such as sulfuric acid and phosphoric acid or Lewis acids such as zinc chloride.
• the type of salt is not important.
• salts are preferred which do not damage the plants, surfaces, materials or spaces to be kept free from harmful fungi and do not impair the action of the compounds I.
• the salts of the compounds I are accessible in a manner known per se, above all by reacting the corresponding carbamoylcarboxamides I with the acids mentioned in water or an inert organic solvent at temperatures from -80 to 120 ° C., preferably 0 to 60 ° C.
• Halogen fluorine, chlorine, bromine and iodine
• Alkyl straight-chain or branched alkyl groups with 1 to 8 carbon atoms, for example Ci-C ⁇ -alkyl such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl , n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl , 2-methylpentyl, 3-methylper ⁇ tyl, 4-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbut
• Haloalkyl or partially or completely halogenated alkyl straight-chain or branched alkyl groups with 1 to 4 or 8 carbon atoms (as mentioned above), where the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms (as mentioned above), for example C ⁇ - C 2 haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chlorine -2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethy
• Alkoxy straight-chain or branched alkoxy groups with 1 to 4 carbon atoms, for example C 1 -C 3 -alkoxy such as methyloxy, ethyloxy, propyloxy and 1-methylethyloxy;
• Alkoxyalkyl straight-chain or branched alkyl groups having 1 to 8 carbon atoms (as mentioned above) which, in any position, have a straight-chain or branched alkoxy group (as mentioned above), in the case of C 1 -C 4 -alkoxyalkyl, 1 to 4 Carry carbon atoms, such as methoxymethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl and 2-butoxyethyl;
• Halogenalkoxy straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above), in which the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms (as mentioned above), for example C 1 -C 2 -haloalkoxy such as chloromethyloxy, dichloroethyloxy, Trichloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyloxy, chlorofluoromethyloxy, dichlorofluoromethyloxy, chlorodifluoromethyloxy, 1-fluoroethyloxy, 2-fluoroethyloxy, 2,2-difluoroethyloxy, 2,2,2-trifluoroethyloxy, 2-chloro-2-fluoroethyloxy, 2-chloro-2,2-di-fluoroethyloxy, 2,2-dichloro-2-fluoroethyloxy, 2,2,2-trichloroethyloxy and
• Alkylthio straight-chain or branched alkyl groups with 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a sulfur atom (-S-), for example C 1 -C 4 -alkyl thio such as methylthio, ethylthio, propylthio, 1- Methyl ethylthio, n-butylthio and tert-butylthio; Alkoxycarbonyl: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above), which are bonded to the skeleton via a carbonyl group (-C0-);
• Alkenyl straight-chain or branched alkenyl groups with 2 to 8 carbon atoms and a double bond in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2- Butenyl, 3-butenyl, 1-methyl.
• Alkynyl straight-chain or branched alkynyl groups with 2 to 8 carbon atoms and a triple bond in any position, for example C 2 -C 6 -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3- Methyl-l-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 1-hexynyl,
• Cycloalkyl monocyclic alkyl groups with 3 to 7 carbon ring members, for example C 3 -C cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl;
• Cycloalkenyl monocyclic alkyl groups with 5 to 7 carbon ring members which contain one or more double bonds, for example C 5 -C -cycloalkenyl such as cyclopentenyl, cyclohexenyl and cycloheptenyl;
• non-aromatic 4- to 8-membered rings which, as ring members, contain one or two oxygen, sulfur or nitrogen atoms in addition to carbon, such as saturated 5- or 6-membered rings with 1 or 2 nitrogen and / or oxygen members atoms such as 3-tetrahydrofuranyl, 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-morpholinyl and 3-morpholinyl;
• Aryl monocyclic or polycyclic aromatic groups with 6 to 10 carbon atoms, such as phenyl and naphthyl;
• Arylalkyl aryl groups (as mentioned above) which, in the case of aryl (C 1 -C 4 ) alkyl, are bonded to the skeleton via alkyl groups having 1 to 4 carbon atoms (as mentioned above), for example phenyl (C 1 -C 4 ) alkyl such as benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-phenylethyl, 1-phenylpropyl and 1-phenylbutyl;
• Aryloxy aryl groups (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-), such as phenoxy, 1-naphthoxy and 2-naphthoxy;
• Heteroaryl aromatic mono- or polycyclic radicals which, in addition to carbon ring members, can additionally contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, e.g. :
• 5-membered heteroaryl containing 1 to 3 nitrogen atoms 5-ring heteroaryl groups which, in addition to carbon atoms, can contain 1 to 3 nitrogen atoms as ring members, for example 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl , 2-imidazolyl, 4-imidazolyl, l, 2,4-triazol-3-yl and l, 3,4-triazol-2-yl; 5-membered heteroaryl containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur atom or oxygen atom or 1 oxygen or 1 sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 May contain sulfur or oxygen atom or 1 oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyr
• 5-ring heteroaryl groups which, in addition to carbon atoms, contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or Can contain 1 oxygen or a sulfur atom as ring members, and in which 2 adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group;
• 6-membered heteroaryl containing 1 to 3 or 1 to 4 nitrogen atoms 6-ring heteroaryl groups which, in addition to carbon atoms, may contain 1 to 3 or 1 to 4 nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 4- Pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, l, 2,4-triazin-3- yl and 1,2,4,5-tetrazin-3-yl; Benzo-condensed 6-membered heteroaryl, containing 1 to 4 nitrogen atoms: 6-ring heteroaryl groups, in which 2 adjacent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group, for example quinoline, iso-quinoline, quinazoline and quinoxaline.
• R 1 is C 1 -C 6 -alkyl, which can carry one to three of the following groups: halogen, C 1 -C 4 -alkoxyalkyl, phenyl and phenoxy.
• R 1 is C 1 -C 4 -alkyl or benzyl.
• R 1 is C 3 -C 7 cycloalkyl, which can carry one to three of the following groups: halogen, C 1 -C 4 -alkoxyalkyl, phenyl and phenoxy.
• R 1 represents cyclopropyl, cyclopentyl or cyclohexyl.
• R 1 is aryl, which can carry one to three of the following groups: halogen, C 1 -C 4 -alkyl and C 1 -C 4 -alkoxy
• R 1 represents phenyl or naphthyl, which can be unsubstituted or can carry one to three of the following groups: fluorine, chlorine, bromine, C 1 -C 4 -alkyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, particularly preferred are compounds I in which R 1 is unsubstituted phenyl, 1-naphthyl or 2-naphthyl.
• R 2 is C 1 -C 4 -alkyl. Furthermore, compounds I are preferred in which R 2 represents hydrogen.
• compounds I are preferred in which R 3 C, ⁇ -alkyl, in particular C ⁇ -C 4 alkyl.
• R 3 is C 3 -C indicated ⁇ -cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl be ⁇ .
• R 4 is C 1 -C 4 -alkyl, especially C 1 -C 4 -alkyl.
• R 4 is C 3 -C 6 cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl.
• R 3 is C 1 -C 6 -alkyl and R 4 is hydrogen.
• R 3 is C 3 -C 6 -cycloalkyl and R 4 is hydrogen.
• R 5 is C ⁇ -C 4 alkyl, methyl and ethyl being particularly preferred.
• R 5 is C 3 -C 6 -cycloalkyl, especially cyclopropyl.
• compounds I are preferred in which the radicals X un-dependent ngig Ci-C ⁇ -alkyl, in particular C ⁇ -C 4 alkyl th each other bedeu ⁇ .
• radicals X independently of one another denote hydrogen are also preferred.
• compounds I are preferred in which the radicals X independently of one another are C 3 -C 6 -cycloalkyl, in particular cyclopropyl, cyclopentyl or cyclohexyl.
• Y 1 represents cyclopropyl, cyclopentyl or cyclohexyl are particularly preferred.
• R 6 is phenyl, which can be unsubstituted or can carry one to three of the following groups: fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkyl, trifluoromethyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, trifluoromethoxy, phenyl and phenoxy.
• R 6 is naphthyl, which may be unsubstituted or carry one to three of the following groups: fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkyl, trifluoromethyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, trifluoromethoxy, phenyl and phenoxy.
• the compounds I compiled in the tables below, in particular in Tables 3 and 4 are very particularly preferred, where C ⁇ Hii stands for cyclohexyl.
• the new compounds of formula I are suitable as fungicides.
• the new compounds, or the compositions containing them can be carried out, for example, in the form of directly sprayable solutions, powders, suspensions, also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules Spraying, atomizing, dusting, scattering or pouring can be used.
• the forms of use depend on the purposes of use; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
• the plants are normally sprayed or dusted with the active compounds or the seeds of the plants are treated with the active compounds.
• the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where in the case of water as diluent other organic solvents can also be used as auxiliary solvents.
• solvents such as aromatics (eg xylene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), ketones (eg cyclohexanone), amines (eg ethanolamine) , Dimethylformamide) and water;
• Carriers such as natural stone powder (e.g.
• Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
• non-ionic and anionic emulsifiers e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates
• dispersants such as lignin sulfite liquors and methyl cellulose.
• the surface-active substances are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and from Fatty acids, alkyl and alkyl aryl sulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols, as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids Phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated iso-octyl, octyl or nonylphenol, alkylphenol
• Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
• Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
• Solid carriers are mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, boluses, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and herbal products such as
• Cereal flour tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
• IX a stable oily dispersion of 20 parts by weight of compound no. 3.9 from Table 3, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of one Phenolsulfonic acid-urea-formaldehyde condensate and 50 parts by weight of a paraffinic mineral oil.
• the new compounds are notable for excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. They are partly sy- effective as a stem and can be used as foliar and soil fungicides.
• the compounds are used by treating the fungi or the seeds, plants, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds.
• the new compounds are particularly suitable for combating the following plant diseases:
• Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and turf, Ustilago sugar species on cereals, Ustilago sugar on cereals, Ustilago varieties on cereals, Ustilago sugar varieties on cereals, Ustilago varieties on cereals, Ustilago varieties inaegualis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mushrooms) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoeula on wheat, barley, Pyr on rice, Phytophthora infestans on potatoes and
• the new connections can also be used in material protection (wood protection), e.g. against Paecilomyces variotii.
• the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
• the application rates are between 0, C25 and 2, preferably 0.1 to 1 kg of active ingredient per ha.
• amounts of active compound of 0.001 to 50, preferably 0.01 to 10 g per kg of seed are generally required.
• agents according to the invention can also be present in the use form as fungicides together with other active ingredients, e.g. with herbicides, insecticides, growth regulators, fungicides or even with fertilizers.
• fungicides with which the compounds according to the invention can be used together is intended to illustrate, but not to limit, the possible combinations: sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganethylene bisdithiocarbamate ethylenediamin-bis-dithiocarbamate, tetramethylthiuram disulfide, ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate), ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), Zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis (thiocarbamoyl) disulfide;
• sulfur, dithiocarbamates and their derivatives such as ferridimethyldithiocarbamate, zinc dimethyldi
• Nitroderivatives such as dinitro- (l-methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl-iso-propyl carbonate, 5 -Nitro-iso-phthalic acid di-iso-propyl ester;
• heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2, 4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-diethyl-phthalimidophosphonothioate, 5-amino-l- [bis - (dimethylamino) phosphinyl] - 3-phenyl-l, 2,4-triazole, 2,3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4,5-b] -quinoxaline , 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N - (1,1,2,2-tetrachloro
• fungicides such as dodecylguanidine acetate
• Strobilurins such as methyl-E-methoximino- [ ⁇ - (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- ⁇ 2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl ⁇ -3-methoxyacrylate, methyl-E-methoximino- [ ⁇ - (2-phenoxy- phenyl)] acetamide, methyl-E-methoximino- [ ⁇ - (2, 5-dimethyloxy) - o-tolyl] acetamide.
• Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl-6 -cyclopropyl-pyrimidin-2-yl) aniline.
• Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile.
• Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acrylic morpholide.
• the active ingredients were 20 wt .-% emulsion in a mixture of 70 wt .-% of cyclohexanone, 20 wt .-% Nekanil ® LN (Lutensol ® AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) and 10 wt .-% Emulphor ® EL (Emulan ® EL, emulsifier based on ethoxylated fatty alcohols) prepared and diluted with water according to the desired concentration.
• Nekanil ® LN Litensol ® AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols
• Emulphor ® EL Emulphor ® EL
• Leaves of potted vines of the "Müller-Thurgau" variety were sprayed with an aqueous spray liquor which contained 80% by weight of active ingredient and 20% by weight of emulsifier in the dry matter.
• the plants were placed in the greenhouse for 8 days after the spray coating had dried on. Only then were the leaves sponged with a zoospore of Plasmopara viticola (vine peronospora) infected.
• the vines were first placed in a chamber with water vapor-saturated air at 24 ° C. for 48 hours and then in a greenhouse at temperatures between 20 and 30 ° C. for 5 days. After this time, the plants were again placed in the moist chamber for 16 hours to accelerate the sporangium carrier outbreak. Then the extent of the fungal outbreak on the undersides of the leaves was assessed visually.
• Leaves of potted plants of the "large meat tomato” variety were sprayed with an aqueous spray mixture which contained 80% by weight of active compound and 20% by weight of emulsifier in the dry matter. After 24 hours, the leaves were infected with a zoospore suspension of the Phytophthora infestans fungus. The plants were then placed in a chamber with water vapor-saturated air at temperatures between 16 and 18 ° C. After 6 days, the infection on the untreated but infected control plants had developed to such an extent that the fungicidal activity of the substances could be assessed visually.

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• 1995
  • 1995-02-20 WO PCT/EP1995/000600 patent/WO1995023784A1/de active Application Filing
  • 1995-02-20 AU AU18103/95A patent/AU1810395A/en not_active Withdrawn

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