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WO1995023785A1 - Amides d'acide carbamylcarboxylique, leur procede de fabrication et leur utilisation en tant que fongicides - Google Patents

Amides d'acide carbamylcarboxylique, leur procede de fabrication et leur utilisation en tant que fongicides Download PDF

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Publication number
WO1995023785A1
WO1995023785A1 PCT/EP1995/000602 EP9500602W WO9523785A1 WO 1995023785 A1 WO1995023785 A1 WO 1995023785A1 EP 9500602 W EP9500602 W EP 9500602W WO 9523785 A1 WO9523785 A1 WO 9523785A1
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Prior art keywords
alkyl
aryl
alkoxy
alkoxyalkyl
haloalkyl
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PCT/EP1995/000602
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German (de)
English (en)
Inventor
Oliver Wagner
Thomas Müller
Karl Eicken
Albrecht Harreus
Eberhard Ammermann
Gisela Lorenz
Frank Wetterich
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Basf Aktiengesellschaft
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Priority claimed from DE4407023A external-priority patent/DE4407023A1/de
Priority claimed from DE4434462A external-priority patent/DE4434462A1/de
Priority claimed from DE4446458A external-priority patent/DE4446458A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU18105/95A priority Critical patent/AU1810595A/en
Publication of WO1995023785A1 publication Critical patent/WO1995023785A1/fr

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    • 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
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • 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
    • 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
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to carbamoylcarboxamides of the general formula I.
  • R 1 is C 1 -C 8 alkyl, C 2 -C 8 alkenyl or C 2 -C 8 alkynyl, these
  • Residues can be partially or completely halogenated and / or can carry one to three of the following groups: cyano,
  • Cyano C 1 -C 4 alkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl,
  • C 3 -C 7 cycloalkyl or C 3 -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 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy,
  • Aryl or heteroaryl, where these radicals can carry one to three of the following groups: halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 - Alkoxy,
  • W 1 W 2 C N-, where W 1 is C 1 -C 8 -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,
  • Aryl or heteroaryl, where these radicals can carry one to three of the following groups: halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 - Alkoxy,
  • R 2 is hydrogen or C 1 -C 8 alkyl or C 3 -C 7 cycloalkyl, which can be partially or completely halogenated;
  • R 3 is C 1 -C 8 alkyl, C 3 -C 7 cycloalkyl, where these radicals can carry one to three of the following groups: halogen, cyano,
  • R 4 is hydrogen or one of the groups mentioned for R 3 or
  • a 4- to 8-membered ring which can contain one or two of the heteroatoms oxygen, sulfur and nitrogen in addition to carbon as ring members, wherein the carbon atoms in the ring can carry one or two of the following groups: halogen, cyano, C 1 -C 4- alkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 ⁇ haloalkoxy,
  • R 5 is a radical R 2 ;
  • X independently of one another hydrogen, C 1 -C 8 alkyl and / or
  • C 2 -C 8 alkenyl these radicals being partially or completely halogenated and / or bearing one to three of the following groups: cyano, C 1 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio and
  • halogen cyano
  • C 1 -C 4 alkyl C 1 -C 4 alkoxyalkyl
  • C 1 -C 4 haloalkyl C 1 -C 4 alkoxy
  • 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 controlling harmful fungi and the use of the compounds I therefor.
  • Amino acid amides with 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, are not yet satisfactory with regard to their fungicidal activity.
  • the present invention was therefore based on new carbamoylcarboxamides with improved activity against harmful fungi. Accordingly, the compounds I defined at the outset and agents containing them were found.
  • the compounds I can be prepared in a manner known per se starting from the corresponding carbamoylcarboxylic acids II.
  • Compounds I are preferably obtained by processes A and B (the literature citations described below)
  • the carbamoylcarboxamides I are obtained by reacting the carbamoylcarboxylic acids II with the amines III.
  • the carbamoylcarboxylic 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).
  • Process A is preferably carried out in such a way that carbamoylcarboxylic acids II are first activated in carboxy
  • carboxy-activated acyl cyanides e.g. the reaction of carbamoylcarboxylic acids II with diethyl cyanophosphonate, especially in an inert solvent such as tetrahydrofuran or toluene.
  • the reaction of the 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.
  • the reaction of the amines III with the carboxy-activated carbamoylcarboxylic 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 then reacted in a manner known per se on the
  • the carbamoylcarboxamides I are obtained by using the
  • Carbamoylcarboxamides I in which the group R 1- O- (CO) stands for a protective group which can be split off in a manner known per se, are converted into amino acid amides IV and reacted with chloroformyloximes V in the presence of bases.
  • Stage Ba preparation of the amino acid amides IV
  • the group R 1 -O- (CO) can be split off from the carbamoylcarboxamides 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 group as well as the benzyl group as radical R 1 .
  • the cleavage usually takes place by reaction with an acid, in particular a protonic acid such as, for example, hydrochloric acid or trifluoroacetic acid (ibid., Page 126 to page 129).
  • an acid in particular a protonic acid such as, for example, hydrochloric acid or trifluoroacetic acid (ibid., Page 126 to page 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 a conventional manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products by chromatography.
  • the intermediate and end products are partly 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
  • the cleaning 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.
  • preference is given to salts which do not damage the plants, surfaces, materials or spaces to be kept free from harmful fungi and which 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 C 1 -C 6 -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,
  • Haloalkyl or partially or fully halogenated alkyl straight-chain or branched alkyl groups having 1 to 4 or 8 carbon atoms (as mentioned above), in which the hydrogen atoms can be partially or completely replaced by halogen atoms (as mentioned above), e.g.
  • C 1 -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- Chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,
  • Alkoxy straight-chain or branched alkoxy groups with 1 to 4 carbon atoms, for example C 1 -C 3 -alkoxy such as methyloxy, ethyloxy, propyl ⁇ xy and 1-methylethyloxy;
  • Alkoxyalkyl straight-chain or branched alkyl groups with 1 to 8 carbon atoms (as mentioned above), which in any position carry a straight-chain or branched alkoxy group (as mentioned above) with 1 to 4 carbon atoms in the case of C 1 -C 4 -alkoxyalkyl, such as Methoxymethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl and 2-butoxyethyl;
  • Haloalkoxy 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, dichloromethyloxy, Trichloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyloxy, chlorofluoromethyloxy, dichlorofluoromethyloxy, chlorodifluoromethyloxy, 1-fluoroethyloxy, 2-fluoroethyloxy, 2,2-difluoroethyloxy, 2,2,2-trifluoroethyloxy, 2-chloro-2-fluoroethyloxy,
  • 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-methylethylthio, n-butylthio and tert-butylthio;
  • Alkoxycarbonyl straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above), which have a
  • Carbonyl group (-CO-) are attached to the skeleton
  • 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-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl2-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl- 2-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl- 2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-
  • 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, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3- Methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2- penty
  • Cycloalkyl monocyclic alkyl groups with 3 to 7 carbon ring members, for example C 3 -C 7 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 7 -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 contain, like saturated 5- or 6-membered rings with 1 or 2 nitrogen and / or oxygen 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 ) 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 structure via an oxygen atom (-O-), such as phenoxy, 1-naphthoxy and 2-naphthoxy;
  • Heteroaryl aromatic mono- or polycyclic radicals which, in addition to carbon ring members, additionally 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one oxygen or one
  • 5-ring heteroaryl groups which, in addition to carbon atoms, may contain 1 to 3 nitrogen atoms as ring members, e.g. 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl,
  • nitrogen atoms can contain 1 sulfur or oxygen atom or 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 are bridged by a buta-1,3-diene-1,4-diyl group could be;
  • nitrogen atoms 5-ring heteroaryl groups which, in addition to carbon atoms, can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring members, and in which 2 adjacent carbon ring members or one nitrogen and one adjacent carbon ring member by a butane
  • 1,3-diene-1,4-diyl group can be bridged, these rings being bonded to the skeleton via one of the nitrogen ring members; - 6-membered heteroaryl containing 1 to 3 or 1 to
  • 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, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl ; - Benzo-fused 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, isoquinoline, 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, especially in which R 1 is phenyl or naphthyl, which may be unsubstituted and / or 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.
  • R 1 is unsubstituted phenyl, 1-naphthyl or 2-naphthyl are very particularly preferred.
  • R 3 is C 1 -C 6 alkyl, particularly preferably C 1 -C 4 alkyl.
  • R 3 is C 3 -C 6 cycloalkyl, particularly preferably cyclopropyl, cyclopentyl or cyclohexyl.
  • C 1 -C 8 alkyl C 1 -C 4 alkyl being particularly preferred.
  • R 4 is C 3 -C 6 cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl.
  • R 4 represents hydrogen
  • radicals X independently of one another are C 1 -C 6 -alkyl, in particular C 1 -C 4 -alkyl.
  • 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.
  • m is 0 or 1 are also preferred.
  • C 3 -C 7 cycloalkyl which can carry one to three of the following groups: halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
  • C 5 -C 6 cycloalkenyl which can carry one to three of the following groups: halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 -Halogenalkoxy and C 1 -C 4 alkylthio.
  • R 6 is phenyl, which may be unsubstituted or may 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 new compounds of formula I are suitable as fungicides.
  • the new compounds, or the compositions containing them can be sprayed, atomized, for example in the form of directly sprayable solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules. Dusting, scattering or pouring can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the plants are sprayed or dusted with the active ingredients or the seeds of the plants are treated with the active ingredients.
  • the formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as a diluent, other organic solvents can also be used as auxiliary solvents.
  • auxiliaries solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g.
  • Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty acid alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
  • Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates)
  • Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty acid alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin-,
  • 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, bolus, 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
  • N-methyl-2-pyrrolidone 10 parts by weight of N-methyl-2-pyrrolidone, which is suitable for use in the form of tiny drops;
  • Butanol 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil;
  • silica gel Parts by weight of silica gel and 48 parts by weight of water, which can be further diluted;
  • Dodecylbenzenesulfonic acid 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 50 parts by weight of a paraffinic mineral oil.
  • the new compounds are distinguished by their outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Deuteromycetes,
  • Ascomycetes Phycomycetes and Basidiomycetes from. Some of them are systemically effective and can be used as foliar and soil fungicides.
  • the compounds are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, lawn, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers, beans and pumpkin family, as well as on the seeds of these plants.
  • 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:
  • cichoracearum and Sphaerotheca fuliginea on pumpkin plants Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helmin on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora
  • 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 0.025 and 2, preferably between 0.1 and 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.
  • the compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.
  • Sulfur, dithiocarbamates and their derivatives such as iron, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediamine bisdithiocarbamate, Tetramethylthiuramdisulfide, 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;
  • Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 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, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [bis- ( dimethylamino) -phosphinyl] - 3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo [4,5-
  • 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-phenoxyphenyl)] 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,
  • 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 fungicidal action of the compounds of general formula I was demonstrated by the following experiments:
  • the active compounds were used as 20 wt .-% emulsion in a mixture of 70 wt .-% of cyclohexanol, 20 wt .-% Nekanil ® LN (Lutensol ® AP6 , Wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight Emulphor ® EL
  • Emulan ® EL emulsifier based on ethoxylated fatty alcohols
  • Plasmopara viticola leaves of pot vines of the "Müller-Thurgau" variety were sprayed with an aqueous spray mixture containing 80% by weight of active ingredient and 20% by weight
  • Zoospores suspension of Plasmopara viticola (vine peronospora) infected.
  • the vines were first left in a cam for 48 hours mer with water vapor-saturated air at 24 ° C and then set up for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in the humid chamber for 16 hours to accelerate the sporangium carrier outbreak. The extent of the fungal outbreak on the undersides of the leaves was then 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 infestation 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des amides d'acide carbamylcarboxylique de formule générale (I) ainsi que leurs sels, où R1 représente alkyle éventuellement substitué, alcényle, alcynyle, cycloalkyle, cycloalcényle, aryle ou hétéroaryle ou un carbocycle ou un hétérocycle non aromatique éventuellement substitué, W1W2C=N-, où W1 représente alkyle éventuellement substitué, alcényle, alcynyle, cycloalkyle, cycloalcényle, aryle ou hétéroaryle et W2 représente hydrogène ou W1; R2 représente hydrogène ou alkyle éventuellement halogéné ou cycloalkyle; R3 représente alkyle éventuellement substitué, cycloalkyle ou phénylalkyle; R4 représente hydrogène ou un radical R?3, ou R3 et R4¿ représentent avec l'atome de carbone auquel ils sont liés un carbocycle ou un hétérocycle saturé éventuellement substitué; R5 représente un radical R2; X représente indépendamment l'un de l'autre hydrogène ou alkyle éventuellement substitué ou alcényle; m est égal à 0, 1, 2; A représente cycloalkyle éventuellement substitué ou cycloalcényle; R6 représente aryle éventuellement substitué ou hétéroaryle. L'invention concerne également les agents renfermant ces substances, leur procédé de fabrication et leur utilisation en tant que fongicides.
PCT/EP1995/000602 1994-03-03 1995-02-20 Amides d'acide carbamylcarboxylique, leur procede de fabrication et leur utilisation en tant que fongicides WO1995023785A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU18105/95A AU1810595A (en) 1994-03-03 1995-02-20 Carbamoyl carboxylic acid amides, process for producing them and their use as fungicides

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE4407023A DE4407023A1 (de) 1994-03-03 1994-03-03 Carbamoylcarbonsäureamide
DEP4407023.3 1994-03-03
DEP4434462.7 1994-09-27
DE4434462A DE4434462A1 (de) 1994-09-27 1994-09-27 Carbamoylcarbonsäureamide
DEP4446458.4 1994-12-27
DE4446458A DE4446458A1 (de) 1994-12-27 1994-12-27 Carbamoylcarbonsäureamide

Publications (1)

Publication Number Publication Date
WO1995023785A1 true WO1995023785A1 (fr) 1995-09-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103408465A (zh) * 2013-07-29 2013-11-27 南开大学 一种n-二取代苯基甲基缬氨酰胺氨基甲酸酯衍生物及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0398072A2 (fr) * 1989-05-13 1990-11-22 Bayer Ag Dérivés d'amides d'aminoacides
EP0485794A1 (fr) * 1990-11-10 1992-05-20 Bayer Ag Dérivés substitués d'amides d'aminoacides, leur préparation et utilisation
EP0496239A2 (fr) * 1991-01-24 1992-07-29 Bayer Ag Dérivés des amides d'aminoacides substitués, leur préparation et utilisation comme fungicide
EP0554729A1 (fr) * 1992-02-04 1993-08-11 Bayer Ag Amides substitués d'aminoacides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0398072A2 (fr) * 1989-05-13 1990-11-22 Bayer Ag Dérivés d'amides d'aminoacides
EP0485794A1 (fr) * 1990-11-10 1992-05-20 Bayer Ag Dérivés substitués d'amides d'aminoacides, leur préparation et utilisation
EP0496239A2 (fr) * 1991-01-24 1992-07-29 Bayer Ag Dérivés des amides d'aminoacides substitués, leur préparation et utilisation comme fungicide
EP0554729A1 (fr) * 1992-02-04 1993-08-11 Bayer Ag Amides substitués d'aminoacides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103408465A (zh) * 2013-07-29 2013-11-27 南开大学 一种n-二取代苯基甲基缬氨酰胺氨基甲酸酯衍生物及应用
CN103408465B (zh) * 2013-07-29 2015-08-26 南开大学 一种n-二取代苯基甲基缬氨酰胺氨基甲酸酯衍生物及应用

Also Published As

Publication number Publication date
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