EP1117650A2 - Utilisation de 5-hydroxypyrazoles substitues, nouveaux 5-hydroxypyrazoles, procedes permettant de les preparer et agents les contenant - Google Patents

Utilisation de 5-hydroxypyrazoles substitues, nouveaux 5-hydroxypyrazoles, procedes permettant de les preparer et agents les contenant

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Publication number
EP1117650A2
EP1117650A2 EP99948860A EP99948860A EP1117650A2 EP 1117650 A2 EP1117650 A2 EP 1117650A2 EP 99948860 A EP99948860 A EP 99948860A EP 99948860 A EP99948860 A EP 99948860A EP 1117650 A2 EP1117650 A2 EP 1117650A2
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EP
European Patent Office
Prior art keywords
alkyl
subst
formula
methyl
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP99948860A
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German (de)
English (en)
Inventor
Andreas Gypser
Reinhard Kirstgen
Hubert Sauter
Herbert Bayer
Oliver Cullmann
Markus Gewehr
Wassilios Grammenos
Bernd Müller
Arne Ptock
Jordi Tormo I Blasco
Eberhard Ammermann
Thomas Grote
Gisela Lorenz
Siegfried Strathmann
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BASF SE
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BASF SE
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Publication of EP1117650A2 publication Critical patent/EP1117650A2/fr
Withdrawn legal-status Critical Current

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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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D231/08—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen or sulfur atoms directly attached to ring carbon atoms
    • 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
    • C07D401/06—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 carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to the use of 5-hydroxy-pyrazolines of the formula I.
  • R 1 is C 2 -C 0 -alkyl, -C-C ⁇ o-haloalkyl, C 3 -C ⁇ 0 -alkenyl, C 3 -C ⁇ 0 -haloalkenyl, C 3 -C ⁇ o-alkynyl or C 3 -C ⁇ o-haloalkynyl,
  • C 3 -C ⁇ 0 cycloalkyl optionally subst.
  • C 3 -C ⁇ 0 cycloalkenyl optionally subst.
  • C 3 -C ⁇ o-cycloalkynyl or
  • Aryl if necessary subst. Heterocyclyl or subst. Hetaryl;
  • R 2 is hydrogen
  • R 3 is hydrogen, nitro, cyano, N (R ') 2 , -CC alkyl, C ! -C 4 halo alkyl, -C -C alkoxy, -C -C haloalkoxy, C 2 -C alkenyl, C -C haloalkenyl, C -C alkynyl or C 2 -C haloalkynyl, where
  • R 'independently of one another is hydrogen or -CC alkyl
  • R 5 is hydrogen, C ⁇ -C 4 alkyl, -C-C haloalkyl,
  • R 4 is hydrogen, halogen, nitro, cyano, N (R '), C ⁇ . -C 4 alkyl, -C-C 4 haloalkyl, COOR ', hetaryl or heterocyclyl;
  • the invention also relates to new 5-hydroxypyrazoles and processes for their preparation.
  • Substituted pyrazolin-5-ones with herbicidal and fungicidal activity are known from DE-A 37 28 278, fungicidally active 3-aryl-pyrazoles are disclosed in WO-A 94/29276.
  • the invention thus relates to both forms, even if only the ring shape I is always mentioned for reasons of clarity.
  • This reaction usually takes place at temperatures from 0 ° C. to 200 ° C., preferably 20 ° C. to 100 ° C., in an inert organic solvent
  • an inert organic solvent J. Org. Chem. USSR (Engl. Transl.), Vol. 16, p. 371 (1980); ibid., vol. 21, p. 2279 (1985); ibid., vol. 22, p. 250 (1986); ibid., vol. 23, p. 1291 (1987); Indian J. Chem. Sect. B, Vol. 29, p. 887 (1990); Bull. Soc. Chem. Jp., Vol. 62, p. 3409 (1989)].
  • Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethylformamide and dirnethylacetamide, particularly preferably methanol, ethanol and tetrahydrofuran. Mixtures of the solvents mentioned can also be used.
  • the starting materials are generally reacted with one another in equimolar amounts. It can be advantageous for the yield to use III in an excess based on II.
  • hydrazides of the formula II required for the preparation of the compounds I are known in the literature [cf. J. Heterocycl. Chem. Vol. 16, p. 561 (1976); Helv. Chim. Acta, Vol. 27, p. 883 (1944); J. Chem. Soc. (1943) p. 413] or can be prepared according to the literature cited.
  • Hydrazides of the formula II are usually prepared from the corresponding carboxylic acid esters of the formula v by reaction with hydrazine hydrate.
  • R ' is C 1 -C 4 alkyl. This reaction usually takes place at temperatures from 0 ° C. to 150 ° C., preferably 20 ° C. to 100 ° C., in an inert organic solvent [cf. J. Heterocycl. Chem. Vol. 16, p. 561 (1976); Helv. Chim. Acta, Vol. 27, p. 883 (1944); J. Chem. Soc. (1943) p. 413].
  • the diketones of the formula III required for the preparation of the compounds I are also known in the literature [Organikum, VEB Verlag dermaschineen, 15th edition, pp. 584ff., Berlin 1976] or can be prepared in accordance with the literature cited .
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use III in an excess based on IV.
  • the sulfurization of IA takes place under conditions known per se, it usually takes place at temperatures from 0 ° C. to 180 ° C., preferably 20 ° C. to 140 ° C., in an inert organic solvent [cf. Liebigs Ann. Chem., P. 177 (1989)].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Di - Oxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, as well as dimethyl sulfoxide, particularly preferably toluene and tetrahydrofuran. Mixtures of the solvents mentioned can also be used.
  • sulfurizing agents examples include phosphorus pentasulfide or Lawesson's reagent.
  • reaction mixtures are worked up in a conventional manner, e.g. by mixing with water, separating the phases and, if necessary, purifying the crude products by chromatography.
  • the intermediate and end products fall partly in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or purified under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting.
  • Halogen fluorine, chlorine, bromine and iodine
  • Alkyl saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or 10 carbon atoms, for example C 1 -C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- Methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dirnethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3- Dimethylbutyl, 1-ethylbutyl, 2-eth
  • Alkoxy straight-chain or branched alkyl groups with 1 to 10 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-);
  • Haloalkoxy straight-chain or branched haloalkyl groups with 1 to 10 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-);
  • Alkylthio straight-chain or branched alkyl groups with 1 to 10 or 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a sulfur atom (-S-);
  • Alkylamino a straight-chain or branched alkyl group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the structure via an amino group (- H-);
  • Dialkylamino two independent, straight-chain or branched alkyl groups each having 1 to 10 carbon atoms (as mentioned above), which are bonded to the skeleton via a nitrogen atom;
  • Alkylcarbonyl a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-C0-);
  • Alkoxycarbonyl an alkoxy group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
  • Alkylt iocarbonyl an alkylthio group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
  • Alkylsulfonyl a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-S0-);
  • Dialkylaminosulfonyl a dialkylamino group (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-S0 2 -);
  • Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 4, 6, 8 or 10 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-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2- butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, l-dimethyl-2-propen
  • Haloalkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and a double bond in any position (as mentioned above), the hydrogen atoms in these groups being partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine can;
  • Alkenyloxy unsaturated, straight-chain or branched hydrocarbon radicals with 3 to 10 carbon atoms and a double bond in any position not adjacent to the hetero atom. sition (as mentioned above) which are bonded to the structure via an oxygen atom (-0-);
  • Alkenylcarbonyl unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 10 carbon atoms and a double bond in any position (as mentioned above) which are bonded to the skeleton via a carbonyl group (-CO-);
  • Alkynyl straight-chain or branched hydrocarbon groups with 2 to 4, 6, 8 or 10 carbon atoms and a triple bond in any position, e.g. C-Ce-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- Pentinyl, 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, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl,
  • Haloalkynyl unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 10 carbon atoms and a triple bond in any position (as mentioned above), the hydrogen atoms in these groups being partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine can;
  • Cycloalkyl monocyclic, saturated hydrocarbon groups with 3 to 6, 8, 10 or 12 carbon ring members, for example C 3 -Ca-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
  • Cycloalkoxy monocyclic, saturated hydrocarbon groups with 3 to 12 carbon ring members (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-);
  • Cycloalkylamino monocyclic, saturated hydrocarbon groups with 3 to 12 carbon ring members (as mentioned above) which are attached to the skeleton via an amino group (-NH-);
  • Heterocyclyl 5- or 6-membered heterocycles containing, in addition to carbon ring members, one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolididinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5- Pyrazolidinyl, 2-oxazo
  • Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. Phenyl, naphthyl and anthraceny1;
  • Aryloxy a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via an oxygen atom (-0-);
  • Arylthio a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a sulfur atom (-S-);
  • Arylamino a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via an amino group (-NH-);
  • Arylcarbonyl a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonyl group (-C0-);
  • Aryloxycarbonyl a mono- to trinuclear aryloxy group (as mentioned above) which is bonded to the skeleton via a carbonyl group (-C0-);
  • Arylthiocarbonyl a mono- to trinuclear arylthio group (as mentioned above) which is bonded to the skeleton via a carbonyl group (-C0-);
  • Arylaminocarbonyl a mono- to trinuclear arylamino group (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
  • Arylcarbonyloxy a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonyloxy group (-C0 2 -);
  • Arylcarbonylthio a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonylthio group (-COS-);
  • Arylcarbonylamino a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonylamino group (-CONH-);
  • Arylsulfonyl a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-S0 2 -);
  • Aryloxysulfonyl a mono- to trinuclear aryloxy group (as mentioned above) which is bonded to the structure via a sulfonyl group (-S0-);
  • Arylthiosulfonyl a mono- to trinuclear arylthio group (as mentioned above) which is bonded to the structure via a sulfonyl group (-S0-);
  • Arylaminosulfonyl a mono- to trinuclear arylamino group (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-S0 2 -);
  • Hetaryl - 5- ⁇ liedri ⁇ es hetaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-ring hetaryl groups, which in addition to carbon atoms contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom can contain as ring links, for example 2-furyl, 3-furyl, 2-thienyl,
  • 5-ring hetaryl groups which, in addition to carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group;
  • 5-membered hetaryl bonded via nitrogen containing one to four nitrogen atoms, or 5-membered hetaryl, which is bonded via nitrogen, contains one to three nitrogen atoms: 5-ring hetaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms May contain ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member by one
  • Buta-l, 3-dien-l, 4-diyl group can be bridged, these rings being bonded to the structure via one of the nitrogen ring members;
  • 6-membered hetaryl containing one to three or one to four nitrogen atoms 6-ring hetaryl groups which, in addition to carbon atoms, may contain one to three or one to four 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 and 1, 2, 4-triazin-3- yl;
  • organic rest if necessary subst. Alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl or hetaryl.
  • alkyl, alkenyl and alkynyl groups can be partially or completely halogenated [i.e. the hydrogen atoms of these groups can be partially or completely replaced by identical or different halogen atoms as mentioned above (preferably fluorine, chlorine or bromine) and / or can carry one to three (preferably one) of the following radicals:
  • alkyl groups in these radicals preferably containing 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms;
  • cycloalkyl cycloalkoxy, cycloalkylthio, cycloalkylamino, cycloalkyl-N-alkylamino, heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylamino or heterocyclyl-N-alkylamino, preferably 12 to 8, the cyclic systems 3 to 12, the cyclic systems, 3 to 12, the cyclic systems Contain ring members, in particular 3 to 6 ring members and the alkyl groups in these radicals preferably 1 to 6
  • the aryl radicals preferably containing 6 to 10 ring members, in particular 6 ring elements (phenyl), the hentaryl radicals (phenyl) Contain 5 or 6 ring members and the alkyl groups in these radicals preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms.
  • halogenated can [ie. the hydrogen atoms of these groups can be partially or completely replaced by identical or different halogen atoms as mentioned above (preferably fluorine, chlorine or bromine, in particular fluorine or chlorine)] and / or can carry one to four (in particular one to three) of the following radicals :
  • alkyl groups in these radicals preferably having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms contain and contain the alkyl groups in these radicals preferably having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms contain and contain the alkyl groups in these radicals preferably having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms contain and contain the alkyl groups in these radicals preferably having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms contain and contain the alkyl groups in these radicals preferably having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms contain and contain the alkyl groups in these radicals preferably having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms contain and contain the alkyl groups in these radicals preferably having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms contain and contain the alkyl groups in these radicals preferably having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms contain and
  • cycloalkyl cycloalkoxy, cycloalkylthio, cycloalkylamino, cycloalkyl-N-alkylamino, heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylamino or heterocyclyl-N-alkylamino
  • the cyclic systems preferably 3 to 12-membered rings, 3 to 12 ring members, contain in particular 3 to 6 ring members and the alkyl groups in these radicals preferably 1 to 6
  • the aryl radicals preferably containing 6 to 10 ring members, in particular 6 ring members (phenyl), in particular the 5 radicals or contain 6 ring members and the alkyl groups in these radicals preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms and / or can carry one or two (in particular one) of the following radicals:
  • Li NOR iv [where R 111 is hydrogen, alkyl, cycloalkyl and aryl and R iv is alkyl, alkenyl, haloalkenyl, alkynyl and arylalkyl (the alkyl groups mentioned preferably containing 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms , the cycloalkyl groups, alkenyl groups and alkynyl groups mentioned, preferably 3 to 8, in particular 3 to 6, carbon atoms.
  • R v is hydrogen, hydroxy, C ⁇ -C 6 alkyl, C 2 -C 6 -Alkenyl, C 2 -C 6 -alkynyl, C ⁇ -C 6 -alkoxy, C 2 -C 6 -alkenyloxy, C 2 -C 6 -alkynyloxy, C ⁇ -C 6 -alkoxy-C ⁇ -C 6 -alkyl, C ⁇ - C 6 -alkoxy- Ci-C ⁇ -alkoxy and -CC 6 alkoxycarbonyl
  • R vi is hydrogen, -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 - C6-Cycloalkyl, C 3 -C
  • Customary groups are in particular the following sub-substituents to be understood: halogen, cyano, nitro, C ⁇ -C 4 -alkyl, C 4 haloalkyl, Cx-Cj-alkoxy, C ⁇ -C4-haloalkoxy, C ⁇ -C 4 -Alkyl- amino, Di-C ⁇ -C 4 alkylamino and C ⁇ ⁇ C -alkylthio.
  • Phenyl is in particular to be understood as a phenyl ring which is substituted by halogen, cyano, nitro, hydroxy, amino, carboxyl, aminocarbonyl, C 1 -C 4 -alkyl or halogen-C 1 -C 4 -alkyl.
  • R 1 is C 1 -C 4 -haloalkyl.
  • R 1 is C 3 F 7 or C 2 F 5 are also particularly preferred.
  • R 1 represents optionally substituted phenyl
  • the compounds I are suitable as fungicides. They are characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.
  • Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, • Cercospora arachidicola on peanuts,
  • Erysiphe graminis (powdery mildew) on cereals, Fusarium and Verticillium species on various plants, • Helminthosporium species on cereals,
  • the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compound. Fabrics treated. The application can take place both before and after the infection of the materials, plants or seeds by the fungi.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
  • the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per hectare.
  • active ingredient 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
  • the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of treated material.
  • the compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • 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. B.
  • Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite 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 non-ionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • Suitable surfactants are alkali metal, Ammoni ⁇ come salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic sulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids such as so-their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polygly
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and herbal products such as
  • Cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • V. 80 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel well mixed and ground in a hammer mill (active ingredient content 80% by weight).
  • VIII.20 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene- ⁇ -sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel well mixed and ground in a hammer mill.
  • a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
  • the active ingredients as such in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring.
  • the application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • To prepare emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, wetting, adhesive,
  • Dispersants or emulsifiers and possibly solvents or oil existing concentrates are prepared which are suitable for dilution with water.
  • the active substance concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume process
  • Oils of various types, herbicides, fungicides, other pesticides, bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.
  • the agents according to the invention can also be present in the use form as fungicides together with other active ingredients, which e.g. with herbicides, insecticides, growth regulators, fungicides or even with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases.
  • Sulfur, dithiocarbamates and their derivatives such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylenediamine bis dithiocarbamate, tetramethylthiurondarbamethyne damidulfide, , Ammonia complex of zinc (N, N '-propylene-bis-dithiocarbamate), zinc (N, N' -propylene-bis-dithiocarbamate), N, N '-polypropylene-bis- (thiocarbamoyl) disulfide;
  • Nitroderivate such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-isopropyl carbonate, 5- Nitro-isophthalic acid-di-isopropyl 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-no) -phosphinyl] -3-phenyl-l, 2, 4-triazole, 2, 3-dicyano-l, 4-di-thioanthraquinone, 2- Thio-1,3-dithiolo [4,5-b] qui
  • Strobilurins such as methyl-E-methoxyimino- [ ⁇ - (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- ⁇ 2- [6- (2-cyanophenoxy) pyrimidin-4-yl- oxy] -phenyl ⁇ -3-methoxyacrylate, methyl-E-methoxyimino- [ ⁇ - (2-phenoxyphenyl)] acetamide, methyl-E-methoxyimino- [ ⁇ - (2, 5-dimethylphenoxy) -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-Me- thyl-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,
  • fungicides such as dodecylguanidine acetate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide,
  • Example 4 Under the conditions mentioned in Example 4, 0.8 g (6 mmol) of benzoic acid hydrazide was reacted with 1.5 g (6 mmol) of 5,5,6,6,7,7,7-heptafluoro-2,4 -heptanedione in 100 ml of ethanol 9.0 g of the title compound as colorless crystals.
  • the active ingredients were separated or together as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight .-% Wettol® EM (non-ionic emulsifier based on ethoxylated castor oil) prepared and diluted with water according to the desired concentration.
  • Nekanil® LN Litensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
  • .-% Wettol® EM non-ionic emulsifier based on ethoxylated castor oil
  • Leaves of potted plants of the "large meat tomato" variety were sprayed to runoff point with an aqueous suspension which was prepared from a stock solution of 10 3 active ingredient, 63% cyclohexanone and 27% emulsifier. The following day, the leaves were infected with an aqueous suspension of zoospores from Phytophthora infestans. The plants were then placed in a steam-saturated chamber at temperatures between 16 and 18oC. After 6 days, the blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.
  • Leaves of pot vines of the "Müller-Thurgau" variety were sprayed to the drip tray with aqueous active ingredient preparation which was prepared with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier.
  • aqueous active ingredient preparation which was prepared with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier.
  • the plants were placed in the greenhouse for 7 days after the spray coating had dried on. Only then were the leaves inoculated with an aqueous suspension of zoospores from Plasmopara viticola.
  • the vines were then placed for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a moist chamber for 16 hours in order to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually
  • Pepper seedlings of the "Neusiedler Ideal Elite" variety after 4-5 leaves had developed well, were sprayed to runoff point with an aqueous active compound preparation which was prepared from a stock solution of 10% active compound, 63% cyclohexanone and 27% emulsifier.
  • an aqueous active compound preparation which was prepared from a stock solution of 10% active compound, 63% cyclohexanone and 27% emulsifier.
  • the treated plants were inoculated with a spore suspension of Botrytis cinerea, which contained 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution.
  • the test plants were then placed in a climatic chamber at 22 to 24 ° C and high air humidity. After 5 days, the extent of the fungal attack on the leaves could be determined visually in%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne l'utilisation pour lutter contre des champignons nuisibles, de 5-hydroxypyrazoles de la formule (I) dans laquelle les substituants ont la signification suivante: B désigne aryle ou hétaryle; A désigne C=O, C=S ou SO2; R1 désigne alkyle, halogénure d'alkyle, alkényle, halogénure d'alkényle, alkinyle ou halogénure d'alkinyle, cycloalkyle, cycloalkényle C¿3?-C10, cycloalkinyle, ou aryle, hétérocyclyle ou hétaryle; R?2¿ désigne hydrogène; R3 désigne hydrogène, nitro, cyano, N(R')¿2?, alkyle, halogénure d'alkyle, alcoxy, halogénure d'alcoxy, alkényle, halogénure d'alkényle, alkinyle ou halogénure d'alkinyle, les restes R' désignent indépendamment les uns des autres hydrogène ou alkyle; ou R?2 et R3¿ désignent conjointement un groupe =O, =S ou =N-O-R5, R5 désignant hydrogène, alkyle, halogénure d'alkyle, alkényle, halogénure d'alkényle, alkinyle ou halogénure d'alkynyle; R4 désigne hydrogène halogène, nitro, cyano, N(R')¿2?, alkyle, halogénure d'alkyle, COOR', hétaryle ou hétérocyclyle. L'invention concerne également des agents contenant lesdits composés, ainsi que de nouveaux 5-hydroxypyrazoles et des procédés permettant de les préparer.
EP99948860A 1998-10-02 1999-09-24 Utilisation de 5-hydroxypyrazoles substitues, nouveaux 5-hydroxypyrazoles, procedes permettant de les preparer et agents les contenant Withdrawn EP1117650A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19845509 1998-10-02
DE19845509 1998-10-02
PCT/EP1999/007125 WO2000020399A2 (fr) 1998-10-02 1999-09-24 Utilisation de 5-hydroxypyrazoles substitues, nouveaux 5-hydroxypyrazoles, procedes permettant de les preparer et agents les contenant

Publications (1)

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EP1117650A2 true EP1117650A2 (fr) 2001-07-25

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EP99948860A Withdrawn EP1117650A2 (fr) 1998-10-02 1999-09-24 Utilisation de 5-hydroxypyrazoles substitues, nouveaux 5-hydroxypyrazoles, procedes permettant de les preparer et agents les contenant

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EP (1) EP1117650A2 (fr)
JP (1) JP2002526536A (fr)
AU (1) AU6196599A (fr)
WO (1) WO2000020399A2 (fr)

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Publication number Priority date Publication date Assignee Title
JP2008545731A (ja) * 2005-05-31 2008-12-18 ビーエーエスエフ ソシエタス・ヨーロピア 殺菌性ｎ−ベンジル−５−ヒドロキシ−５−フェニルピラゾリン類、その調製法、ならびにこれらの化合物を含む組成物
BRPI0610578A2 (pt) * 2005-05-31 2016-11-16 Basf Ag compostos, processo para preparar os mesmos, agente fungicida, semente, processo para combater fungos nocivos fitopatogênicos, e, uso de compostos
WO2006128815A1 (fr) * 2005-05-31 2006-12-07 Basf Aktiengesellschaft Utilisation de 5-hydroxypyrazolines bicycliques, procede de fabrication et agents contenant ces composes
EP1895845A1 (fr) * 2005-05-31 2008-03-12 Basf Se Utilisation de 5-hydroxypyrazolines fongicides, procede de fabrication et agents contenant ces composes

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JPH0532662A (ja) * 1990-11-09 1993-02-09 Nissan Chem Ind Ltd 置換ピラゾール誘導体および農園芸用殺菌剤

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Title
See references of WO0020399A3 *

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JP2002526536A (ja) 2002-08-20
WO2000020399A3 (fr) 2000-07-27
WO2000020399A2 (fr) 2000-04-13

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