EP1244635A2 - 4-aryl-1-difluoromethoxyimidazole - Google Patents

4-aryl-1-difluoromethoxyimidazole

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Publication number
EP1244635A2
EP1244635A2 EP01939981A EP01939981A EP1244635A2 EP 1244635 A2 EP1244635 A2 EP 1244635A2 EP 01939981 A EP01939981 A EP 01939981A EP 01939981 A EP01939981 A EP 01939981A EP 1244635 A2 EP1244635 A2 EP 1244635A2
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European Patent Office
Prior art keywords
alkyl
phenyl
compounds
formula
haloalkyl
Prior art date
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EP01939981A
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German (de)
English (en)
Inventor
Cyrill Zagar
Olaf Menke
Gerhard Hamprecht
Michael Puhl
Robert Reinhard
Ingo Sagasser
Peter Plath
Thorsten Volk
Karl-Otto Westphalen
Matthias Witschel
Helmut Walter
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/68—Halogen atoms

Definitions

  • the present invention relates to 4-aryl-l-difluoromethoxyimidazoles of the formula I.
  • R 1 is hydrogen, Cx-Cj-alkyl or C 1 -C 4 haloalkyl
  • R 2 is hydrogen, halogen, cyano, C 1 -C 4 -alkyl or C 1 -C 6 -haloalyl;
  • R 3 is a 5- or 6-membered aromatic radical which optionally has one, two or three heteroatoms selected from oxygen, nitrogen and sulfur, which is optionally substituted and / or a further fused, 5- or 6-membered group carbocyclic or heterocyclic ring having 1 to 3 heteroatoms, selected from nitrogen, oxygen and sulfur atoms, wherein the fused ring is partially or completely unsaturated, unsubstituted or in turn can carry one, two or three substituents, and / or can contain one or two non-adjacent carbonyl, thiocarbonyl or sulfonyl ring members,
  • WO 94/17059 and WO 99/05125 herbicidally active compounds which have a phenyl-substituted heterocycle.
  • Substituted imidazoles can be used as heterocycles.
  • EP 590 843 describes 4-phenylimidazoles, the 6 haloalkyl, a C -Cs-alkenyl nyl- or at the imidazole nitrogen, a Ci-Cio-alkyl, C ⁇ -C is a C 3 -C 5 alkynyl group may have, and their use as herbicides.
  • the object of the present invention was to provide new arylimidazoles with which undesired plants can be controlled more effectively than before.
  • the task also extended to the provision of new desiccant / defliantly effective connections.
  • the object is surprisingly achieved by 4-aryl- (1H) -imidazoles which carry a difluoromethoxy group in the 1-position of the imidazole ring.
  • the present invention therefore relates to the 4-aryl-l-difluoromethoxyimidazoles of the general formula I defined at the outset and their agriculturally acceptable salts.
  • the invention also relates to the use of compounds I and their salts as herbicides and / or for the desiccation and / or defoliation of plants, herbicidal compositions and agents for the desiccation and / or defoliation of plants which the compounds I and / or their salts are effective Contain substances, process for the preparation of the compounds I and herbicidal agents and agents for desiccation and / or
  • the compounds of the formula I can have one or more centers of chirality in the substituents and are then present as enantiomer or diastereomer mixtures.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • Agriculturally useful salts include, in particular, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate / hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably Formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • All carbon chains ie all alkyl, haloalkyl, phenylalkyl, cycloalkylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenyl -, Haloalkenyl, alkynyl and haloalkynyl groups and corresponding parts of groups in larger groups such as alkoxycarbonyl, phenylalkyl, cycloalkylalkyl, alkoxycarbonylalkyl etc.
  • Halogenated substituents preferably carry one, two, three, four or five identical or different halogen atoms.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • C 1 -C 4 alkyl for: CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, CH (CH 3 ) -C 2 H 5 , CH 2 -CH (CH 3 ) 2 and C (CH 3 ) 3 ;
  • -C -C haloalkyl for: a C 1 -C 4 -alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CH 2 F, CHF 2 , CF 3 , CH 2 C1, dichloromethyl, trichloromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl,
  • 2-chloroethyl 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro 2-fluoroethyl, 2,2,2-trichloroethyl, C 2 F 5 , 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl,
  • -CC 6 alkyl for: C] .- C 4 alkyl as mentioned above, and for example n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1- ⁇ thylpropyl, n- hexyl,
  • Cj-Cs-Haloalkyl for: a Ci-C ⁇ -alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example one of the radicals mentioned under C 1 -C 4 -haloalkyl and for 5 -Fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl,
  • Phenyl-C ⁇ -C 4 alkyl for: benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-l-yl, 1-phenylbut-l -yl, 2-phenylbut-l-yl, 3-phenylbut-l-yl, 4-phenylbut-l-yl, l-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl , 3-phenylbut-2-yl, 4-phenylbut-2-yl, l- (phenylmethyl) -eth-l-yl,
  • Heterocyclyl -CC 4 -alkyl for: heterocyclylmethyl, 1-heterocyclyl-ethyl, 2-heterocyclyl-ethyl,
  • C ⁇ -C4-haloalkylthio for: a C ⁇ -C4-alkylthio as mentioned above which is partially or fully substituted by, iodine of fluorine, chlorine, bromine and / or substituted, eg SCH 2 F, SCHF 2, SCH 2 C1, SCH (C1) 2 , SC (Cl) 3 , SCF 3 , chlorofluoromethylthio, dichlorofluoromethylthio, Chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio,
  • -C-C 4 -alkoxy-C ⁇ -C alkyl for: by C ! -C 4 -alkoxy - as mentioned above - substituted -CC 4 alkyl, for example for CH 2 -0CH 3 , CH 2 -OC 2 H 5 , n-propoxymethyl, CH 2 -OCH (CH 3 ) 2 , n -Butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, CH 2 -OC (CH 3 ) 3 , 2- (methoxy) ethyl,
  • C ⁇ -C 4 alkylthio-C 1 -C 4 alkyl by C ⁇ -C 4 alkylthio - as mentioned above - substituted C ⁇ -C4 alkyl, eg CH -SCH 3, CH 2 -SC 2 H 5 , n-propylthiomethyl, CH 2 -SCH (CH 3 ) 2 , n-butylthiomethyl, (1-methylpropylthio) methyl, (2-methylpropyl hio) methyl, CH 2 -SC (CH 3 ) 2 , 2- (methylthio) ethyl, (ethylthio) ethyl, 2- (n-propylthio) ethyl, 1-methylethylthio) ethyl, 2- (n-butylthio) ethyl,
  • (-C-C 4 alkyl) carbonyl for : c ⁇ -CH 3 , CO-CH 5 , CO-CH 2 -C 2 H 5 , CO-CH (CH 3 ) 2 , n-butylcarbonyl, CO-CH (CH 3 ) -C 2 H 5 , CO-CH 2 -CH (CH 3 ) 2 or CO-C (CH 3 ) 3 , preferably for CO-CH 3 or CO-C 2 H 5 ;
  • Nonafluorobutylcarbonyl preferably for C0-CF 3 , C0-CH 2 C1, or 2,2, 2-trifluoroethylcarbonyl;
  • 0-CO-CH (CH 3 ) -C 2 H 5 0-C0-CH 2 -CH (CH 3 ) 2 or 0-C0-C (CH 3 ) 3 , preferably for 0-C0-CH 3 or 0 -CO-C 2 H 5 ?
  • (C 1 -C -Halogenalkyl) carbonyloxy for: a (-CC 4 -alkyl) carbonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 0-CO-CH 2 F, 0-C0-CHF 2 , 0-C0-CF 3 , 0-C0-CH 2 Cl, 0-C0-CH (Cl) 2 , 0-C0-C (Cl) 3 , chlorofluoromethylcarbonyloxy, dichlorofluoromethylcarbonyloxy, chlorodifluoromethylcarbonyloxy , 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethylcarbonyloxy, 2-iodoethylcarbonyloxy, 2, 2-difluoroethylcarbonyloxy, 2, 2, 2-trifluoroethylcarbonyloxy, 2-chlor
  • C 1 -C 4 alkylsulfinyl for: S0-CH 3 , SO-C 2 H 5 , SO-CH 2 -C 2 H 5 , SO-CH (CH 3 ) 2 , n-butylsulfinyl, SO-CH (CH 3 ) -C 2 H 5 , SO-CH 2 -CH (CH 3 ) 2 or SO-C (CH 3 ) 3 , preferably for S0-CH 3 or SO-C 2 H 5 ;
  • - C ⁇ -C4-haloalkylsulfonyl of: a C 1 -C 4 -alkylsulfonyl radical - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine is substituted, eg S0 2 -CH 2 F, S0 2 -CHF 2 , S0 2 -CF 3 , S0 2 -CH 2 C1, S0 2 -CH (C1) 2 , S0 2 -C (C1) 3 , chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2 -Bromethylsulfonyl, 2-iodoethylsulfonyl, 2, 2-difluoroethylsul
  • 2,2,2-trichloroethylsulfonyl S0 2 -C 2 F 5 , 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl, 2, 3-difluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2,3-dichlorosulfonyl, 2,3-dichlorosulfonyl 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 3, 3, 3-trifluoropropylsulfonyl, 3,3, 3-trichloropropylsulfonyl, S0 2 -CH 2 -C 2 F 5 , S0 2 -CF 2 -C 2 F 5 , 1- (fluoromethyl ) -2-fluoroethy
  • N- (1, 1-dimethylethyl) -N- (2-methylpropyl) amino preferably for N (CH 3 ) 2 or N (C 2 H 5 );
  • N-butyl-N- (2-methylpropyl) aminocarbonyl N-butyl-N- (1, 1-dimethylethyl) aminocarbonyl, N- (1-methylpropyl) -N- (2-methylpropyl) aminocarbonyl, N- (1, 1-dimethylethyl) -N- (1-methylpropyl ) —Aminocarbonyl or N- (1, 1-dimethylethyl) -N- (2-methylpropyl) aminocarbonyl;
  • Di- (C ⁇ -C alkyl) aminocarbonyl-C ⁇ -C 4 alkoxy By di- (C ⁇ -C alkyl) aminocarbonyl monosubstituted C ⁇ -C 4 alkoxy, for example, di- (C 1 -C 4 - alkyl) —aminocarbonylmethoxy, 1- or 2-di- (-C-C 4 alkyl) —aminocarbonylethoxy, 1-, 2- or 3-di- (C ⁇ -C 4 -alkyl) —aminocarbonylpropoxy;
  • C 2 -C 6 haloalkenyl for: C 2 -C 6 alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example 2-chlorovinyl, 2-chloroallyl, 3-chloroallyl, 2 , 3-dichlorallyl, 3,3-dichlorallyl, 2, 3, 3-trichlorallyl, 2, 3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2, 3-dibromoallyl, 3,3-dibromoallyl, 2 , 3, 3-tribromoallyl and 2, 3-dibromobut-2-enyl, preferably for C 3 - or C -haloalkenyl;
  • C -C 6 alkynyl for: ethynyl and CC 5 ⁇ alkynyl such as prop-1-in-1-yl, prop-2-in-1-yl, n-but-1-in-1-yl, n-but -l-in-3-yl, n-but-l-in-4-yl, n-but-2-in-l-yl, n-pent-1-in-l-yl, n-pent-l -in-3-yl, n-pent-1-in-4-yl, n-pent-1-in-5-yl, n-pent-2-in-1-yl, n-pent-2-in -4-yl, n-pent-2-yn-5-yl, 3-methyl-but-l-yn-3-yl, 3-methyl-but-l-yn-4-yl, n-hex-1 -in-l-yl, n-hex-l-in-3-yl
  • C 2 -C 6 haloalkynyl for: C 2 -C 6 alkynyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example l, l-difluoroprop-2-yn-l-yl , 1, 1-difluorobut-2-in-l-yl,
  • 5-fluoropent-3-yl or 6-fluorohex-4-yl preferably C 3 or C 4 haloalkynyl;
  • C 3 -Ca cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyi or cyclooctyl;
  • C 3 -C 6 -cycloalkyl which contains a carbonyl or thiocarbonyl ring member, for example for cyclobutanon-2-yl, cyclobutanon-3-yl, cyclopentanon-2-yl, cyclopentanon-3-yl, cyclohexanon-2-yl, cyclohexanone -4-yl, cycloheptanon-2-yl, cyclooctanon-2-yl, cyclobutanthion-2-yl, cyclobutanthion-3-yl, cyclopentanthion-2-yl, cyclopentanthion-3-yl, cyclohexanthion-2-yl,
  • C 3 -C 8 cycloalkyl-C 4 -C 4 alkyl for: cyclopropylmethyl, 1-cyclopropyl-ethyl, 2-cyclopropyl-ethyl, 1-cy ⁇ lopropyl-prop-l-yl, 2-cyclopropyl-prop-l-yl, 3-cyclopropy1-prop-1-yl, 1-cyclopropy1-but-1-yl, 2-cyclopropyl-but-l-yl, 3-cyclopropyl-but-l-yl, 4-cyclopropyl-but-l-yl, l-cyclopropyl-but-2-yl, 2-cyclopropyl-but-2-yl, 3-cyclopropyl-but-2-yl, 4-cyclopopy1-but-2-y1, 1- (cyclopropyl ethy1) -eth- l-yl, l- (cyclopropylmethyl) -l- (methyl) -eth-l
  • CC 8 cycloalkyl -CC 4 -alkyl which contains a carbonyl or thiocarbonyl ring member, for example for cyclobutanon-2-ylmethyl, cyclobutanon-3-ylmethyl, cyclopentanon-2-ylmethyl, cyclopentanon-3-ylmethyl, cyclohexanone 2-ylmethyl, cyclohexanon-4-ylmethyl, cycloheptanon-2-ylmethyl, cyclooctanon-2-ylmethyl, cyclobutanthion-2-ylmethyl, cyclobutanthion-3-ylmethyl, cyclopentanthion-2-ylmethyl, cyclopentanthion-3-ylmethyl, cyclopentanthion-3-ylmethyl ylmethyl, cyclohexanthion-4-ylmethyl, cycloheptanthion-2-ylmethyl, cyclooctanthion-2-ylmethyl, 1- (cycl
  • 3- to 7-membered heterocy ⁇ lyl are to be understood as meaning both saturated, partially or completely unsaturated and aromatic heterocycles having one, two or three heteroatoms, the heteroatoms being selected from nitrogen atoms, oxygen and sulfur atoms.
  • saturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are:
  • unsaturated heterocycles which may contain a carbonyl or thiocarbonyl ring member are: dihydrofuran-2-yl, 1,2-oxazolin-3-yl, 1,2-oxazolin-5-yl, 1,3-oxazolin 2-yl.
  • aromatic heterocyclyl examples are 5- and
  • 6-membered aromatic, heterocyclic radicals for example furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 5 -Isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-0xazolyl, 4-oxazolyl and 5-0xazolyl, thiazolyl such as 2- , 4-thiazolyl and 5-thiazolyl, imidazolyl such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl such as l, 2,4-oxadiazol-3-yl,
  • 5- or 6-membered aromatic radicals for the purposes of this invention are phenyl and the aforementioned 5- or 6-membered aromatic heterocyclyl radicals, in particular phenyl or pyridyl, for example 2-pyridyl. According to the invention, these can be substituted and / or have a fused, 5- or 6-membered carbocyclic or heterocyclic ring with 1 to 3 heteroatoms, selected from nitrogen, oxygen and sulfur atoms, the fused ring being partially or completely unsaturated, un - Can be substituted or in turn carry one, two or three substituents and can also contain one or two non-adjacent carbonyl, thiocarbonyl or sulfonyl ring members. Examples of suitable substituents on the aromatic radical are the meanings given below for R 4 , R 5 and R 6 .
  • fused rings in addition to phenyl are the aforementioned heteroaromatic groups, in particular pyridine, pyrazine, pyridazine, pyrimidine, furan, dihydrofuran, thiophene, dihydrothiophene, pyrrole, dihydropyrrole, 1,3-dioxolane, 1,3-dioxolan-2-one, isoxazole , Oxazole, oxazolinone, isothiazole, thiazole, pyrazole, pyrazoline, idazole, imidazolinone, dihydroimidazole, 1,2,3-triazole, 1, 1-dioxodihydroisothiazole, dihydro-l, 4-dioxin, pyridone, dihydro-1,4- oxazin, dihydro-l, 4-oxazin-2-one, dihydro-1, 4-oxazin-3-one, dihydro
  • R 1 is hydrogen, methyl, ethyl or C ! -C 2 haloalkyl
  • R 2 is hydrogen, halogen, preferably chlorine or bromine, cyano
  • R 3 is a radical of the general formula II
  • R 4 is hydrogen or halogen
  • R5 hydrogen, cyano, nitro, halogen, -CC 4 alkyl, OH, SH, NH 2 , C ! -C 4 -haloalkyl, -C-C 4 alkoxy or -C-C 4 haloalkoxy;
  • X is a chemical bond or a methylene, ethylene,
  • Q is nitrogen or a group CR 7 , where R 7 is hydrogen NH 2 , OH or SH;
  • R 6 is hydrogen, nitro, cyano, halogen, halosulfonyl, -OYR 8 , -0-CO-YR 8 , -N (YR 8 ) (ZR 9 ), -N (YR 8 ) -S0 2 -ZR 9 ,
  • Y, Z independently of one another: a chemical bond, a methylene or ethylene group, which may be unsubstituted or carry one or two substituents, each selected from the group consisting of carboxy, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, (C 1 -C 4 alkoxy) carbonyl and phenyl;
  • R 8 , R 9 independently of one another: hydrogen, -CC 6 -haloalkyl, C 2 -C 6 -alkenyl,
  • Phenyl or 3- to 7-membered heterocyclyl which may contain a carbonyl or thiocarbonyl ring member, each cycloalkyl, the phenyl and each
  • Hetero ⁇ yclyl ring can be unsubstituted or carry one to four substituents, each selected from the group consisting of cyano, nitro, amino, hydroxy, carboxy, halogen, C 1 -C 4 alkyl, C !
  • -C 4 haloalkyl C ⁇ -C alkoxy, C 1 -C 4 haloalkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C4-haloalkylthio, C ⁇ -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, ( C ⁇ -C4 alkyl) carbonyl, (C ⁇ -C 4 haloalkyl) carbonyl, (C ⁇ -C4 alkyl) carbonyloxy, (C ⁇ -C haloalkyl) carbonyloxy, (C ⁇ -C 4 alkoxy) carbonyl, and di- (C 1 -C alkyl) amino;
  • R 10 is hydrogen, C 1 -C 5 -alkyl, C 1 -C 6 -haloalkyl,
  • Phenyl-C 1 -C 4 -alkyl where the phenyl ring can be unsubstituted or can carry one to three substituents, each selected from the group consisting of cyano, nitro, Carboxy, halogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl and (C ⁇ -C 4 alkoxy) carbonyl;
  • R 14 independently of one another are hydrogen, C 6 -alkyl, C 6 haloalkyl,
  • each cycloalkyl and each Heterocyclyl ring can contain a carbonyl or thiocarbonyl ring member, and wherein each cycloalkyl, phenyl and heterocyclyl ring can be unsubstituted or can carry one to four substituents, each selected from the group consisting of cyano, nitro, amino, Hydroxy, carboxy, halogen, C ⁇ -C 4 -alkyl, C ⁇ -C 4 -haloalkyl, C ⁇ -C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C ⁇ -C 4 -haloalkylthio, C ⁇ -C 4 -haloalkylthio, C ⁇
  • R 15 is hydrogen, Ci-C ⁇ -alkyl, -C-C 5 haloalkyl,
  • variable combinations XR 6 are given in Table 1.
  • the variables Q, R 4 , R 5 , X and R 6 preferably have the following meanings, individually or in combination:
  • R 4 is hydrogen, fluorine or chlorine
  • R 5 halogen, especially chlorine
  • X is a chemical bond, methylene or ethane-1,2-diyl, ethene-1,2-diyl, 2-chloroethane-1,2-diyl and 2-chloro-ethene-1,2-diyl;
  • variables R 8 , R 9 , R 10 , Y, Z mentioned in the definition of the variables R 6 preferably have the following meanings:
  • Y, Z independently of one another are a chemical bond or methylene
  • thiocarbonyl ring member May contain thiocarbonyl ring member, phenyl or 3- to 7-membered heterocyclyl with one or two nitrogen atoms and / or an oxygen or sulfur atom as the hetero atom and, if desired, a carbonyl or thiocarbonyl ring member, each cycloalkyl, the phenyl and each Heterocyclyl ring can be unsubstituted or carry one or two substituents, each selected from the group consisting of cyano, nitro, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfonyl, (C 1 -C 4- alkyl) carbonyl, (C 1 -C 4 -alkyl) carbonyloxy and (-C-C 4 -alkoxy) carbonyl;
  • Ci-Ce-haloalkyl C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CH (R n ) (R 12 ), -C (RH) (R 2 ) -CO-OR 13 , -CfR 11 ) (R 12 ) -CO-N (R i ) R i4 or C 3 -C 8 cycloalkyl, particularly preferably hydrogen, -C-C 6 alkyl, C 2 -C 6 alkenyl, C 2 - C 6 alkynyl, -C (R 1: L ) (R 12 ) -CO-OR "or C 3 -C 8 cycloalkyl.
  • R 11 is hydrogen or C 1 -C 4 -alkyl
  • R 12 is hydrogen
  • R i , R 14 independently of one another hydrogen or -CC 6 alkyl; R 15 Ci-C ⁇ -alkyl.
  • Rio -C 6 alkyl especially methyl or ethyl.
  • R 5 and XR 6 or XR 6 and R 7 in formula II can also form a 3- or 4-membered chain which, in addition to carbon, can have 1, 2 or 3 heteroatoms, selected from nitrogen, oxygen and sulfur atoms, which may be unsubstituted or in turn bear one, two or three substituents, and the members of which may also comprise one or two non-adjacent carbonyl, thiocarbonyl or sulfonyl groups.
  • Such connections are referred to below as connections IC or ID.
  • R 18 is hydrogen, hydroxy, Cx-C ⁇ -alkyl, Cx-C ⁇ -haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 5 alkynyl, C ⁇ -C 4 alkoxy, C ⁇ -C 4 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C ⁇ -C 4 alkylsulfonyl,
  • C ⁇ -C haloalkylsulfonyl C ⁇ -C 4 alkylcarbonyl, C ⁇ -C 4 haloalkylcarbonyl, C ⁇ -C 4 alkoxycarbonyl, C ⁇ -C alkoxycarbonyl-C 1 -C 4 -alkyl, C 4 alkoxycarbonyl-C ⁇ - C 4 alkoxy, di- (-C 4 alkyl) aminocarbonyl,
  • R 19 is hydrogen, halogen, cyano, amino, -CC 6 alkyl,
  • C 1 -C 6 haloalkyl C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C ⁇ -C 4 alkylamino,
  • the variables R 16 to R 19 preferably have the following meanings:
  • R 16 , R 17 independently of one another are hydrogen or methyl
  • R 19 is hydrogen, halogen, amino, Ci-C ⁇ -alkyl, Ci-C ⁇ -haloalkyl, -C-C 4 alkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, C ⁇ -C 4 -alkylamino, Di- (-C 4 -alkyl) amino, C ⁇ -C-alkylthio, -C-C 4 -alkoxycarbonyl-C ⁇ -C 4 -alkyl, C ⁇ -C 4 -alkoxycarbonyl-C ⁇ -C 4 -alkoxy, C ⁇ -C 4 -Alkoxycarbonyl -CC 4 -alkylthio, phenyl or phenyl-C 1 -C 4 -alkyl.
  • Q and R 4 have the meanings mentioned above, Q being in particular CH and R 4 in particular having the meanings indicated as preferred.
  • R 16 and R 18 have in particular the meanings given as preferred.
  • the compounds IC are particularly preferred in which the nitrogen atom of the chain -O-CH (R l ⁇ ) -C0-N (R 18 ) -,
  • R 4 and R 5 have the meanings mentioned above, in particular the meanings given as preferred.
  • the compounds of the formula are also particularly preferred.
  • the compounds of the formula are also particularly preferred.
  • the 4-aryl-l-difluoromethoxyimidazoles of the formula I according to the invention can be prepared by the synthetic routes described below:
  • the 4-aryl-l-hydroxyimidazole of the formula III is reacted with chlorodifluoromethane, preferably in an organic solvent.
  • This reaction is preferably carried out in the presence of a base.
  • suitable bases are alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonate and hydrogen carbonate such as potassium or sodium carbonate or hydrogen carbonate or an organic base, e.g. Alcoholates such as sodium or potassium methylate or ethylate, especially tertiary amines such as triethylamine or pyridine.
  • the gaseous chlorodifluoromethane is preferably slowly added to the reaction batch, which is the compound III, which is preferably dissolved or. is suspended in a solvent, optionally containing a base and / or further catalysts.
  • a solvent optionally containing a base and / or further catalysts.
  • excess chlorodifluoromethane gas is preferably retained by a low-temperature cooler.
  • the reaction can also be carried out under elevated chlorodifluoromethane pressure in a closed apparatus (autoclave) at pressures between approximately 0.1 and 100 bar.
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably at temperatures in the range from 50 to 150.degree.
  • chlorodifluoromethane based on III.
  • the excess can be up to five times, for example molar amount of the 1-hydroxyimidazole III used.
  • Suitable solvents are inert organic solvents, for example hydrocarbons such as toluene or hexane,
  • Ethers such as diethyl ether, diethoxyethane, methyl t-butyl ether, dioxane or tetrahydrofuran (THF), amides such as dimethylformamide (DMF), N, N-dimethylacetamide (DMA) or N-methylpyrrolidone (NMP), Cx-C ⁇ -alkanols such as Methanol or ethanol, or mixtures of such solvents with each other or with water.
  • amides such as dimethylformamide (DMF), N, N-dimethylacetamide (DMA) or N-methylpyrrolidone (NMP), Cx-C ⁇ -alkanols such as Methanol or ethanol, or mixtures of such solvents with each other or with water.
  • phase transfer catalyst e.g. to add a tetraalkylammonium salt such as tetrabutylammonium chloride or a crown ether such as 18-crown-6 or 15-crown-5 in catalytic amounts (0.01-20 mol%, based on III).
  • a tetraalkylammonium salt such as tetrabutylammonium chloride or a crown ether such as 18-crown-6 or 15-crown-5 in catalytic amounts (0.01-20 mol%, based on III).
  • the l-hydroxyimidazoles of the formula III are known in principle from the literature (for example A. Katritzky, C. Rees, ed., Comprehensive Heterocyclic Chemistry, Vol. 5, p. 474 f.) Or can be known analogously to the literature Make connections. In particular, they can be produced by the two processes mentioned below:
  • NOX a is a conventional nitrating agent, where X a is , for example, an inorganic anion, for example halogen, in particular chlorine, hydrogen sulfate or tetrafluoroborate, or an alcoholate residue, such as tert-butanolate.
  • X a is , for example, an inorganic anion, for example halogen, in particular chlorine, hydrogen sulfate or tetrafluoroborate, or an alcoholate residue, such as tert-butanolate.
  • Such reactions are known in principle from the literature (e.g. M. Scheinbaum, M. Dines, Tetrahedron Lett. 24, 1971, 2205; B. Lipshutz, B. Huff, W. Vaccaro, Tetrahedron Lett. 27, 1986, 4241; J Beger, J. Prakt. Che. 311, 1969, 746).
  • nitrosating reagents such as, for example, nitrosyl chloride, nitrosylsulfuric acid, alkyl nitrites, such as, for example, t-butyl nitrite, or salts of nitrous acid, such as, for example, sodium nitrite, are also suitable as nitroso compounds.
  • R 1 and R 3 have the meanings given above.
  • R 2 ' represents hydrogen, CN, C 1 -C 4 alkyl or C 1 -C haloalkyl.
  • 4-aryl-l-difluoromethoxyimidazoles I can be prepared by functionalization, for example by halogenation of 4-aryl-l-difluoromethoxyimidazoles I in which R 2 is hydrogen:
  • Suitable halogenating agents are, for example, fluorine, DAST (diethylaminosulfur trifluoride), chlorine, N-chlorosuccinimide, sulfuryl chloride, thionyl chloride, phosgene, phosphorus trichloride, phosphorus oxychloride, bromine, N-bromosuccinimide, phosphorus tribromide and phosphorus oxybromide.
  • an inert solvent / diluent for example in a hydrocarbon such as n-hexane and toluene, a halogenated hydrocarbon such as Dichloromethane, carbon tetrachloride and chloroform, an ether such as methyl tert-butyl ether, an alcohol such as methanol and ethanol, a carboxylic acid such as acetic acid or in a polar aprotic solvent such as acetonitrile.
  • a hydrocarbon such as n-hexane and toluene
  • a halogenated hydrocarbon such as Dichloromethane, carbon tetrachloride and chloroform
  • an ether such as methyl tert-butyl ether
  • an alcohol such as methanol and ethanol
  • a carboxylic acid such as acetic acid or in a polar aprotic solvent such as acetonitrile.
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably from 0 to 100 ° C.
  • the halogenating agent is used in an approximately equimolar amount or in excess, up to about five times the molar amount, based on the amount of starting compound.
  • Nitration reagents that can be used are, for example, nitric acid in different concentrations, also concentrated and fuming nitric acid, mixtures of sulfuric acid and nitric acid, and also acetyl nitrates and alkyl nitrates.
  • the reaction can be carried out either in a solvent-free manner in an excess of the nitrating reagent or in an inert solvent or diluent, water, mineral acids, organic acids, halogenated hydrocarbons such as methylene chloride, anhydrides such as acetic anhydride and mixtures of these solvents being suitable, for example.
  • the 'reaction temperature is usually from -100 ° C to 10 200 ° C, preferably at -30 to 50 ° C.
  • the reduction is usually carried out by reacting the nitro compound with a metal such as iron, zinc or tin under acidic reaction conditions or with a complex hydride
  • the reduction being carried out in bulk or in a solvent or diluent.
  • the solvents used are e.g. Water, alcohols such as methanol, ethanol and isopropanol or
  • ethers such as diethyl ether, methyl tert. -butyl ether, dioxane,
  • the acid can also be treated with an inert solvent, e.g. dilute one of the above.
  • the reduction with complex hydrides is preferably carried out in a
  • 35 nem solvent for example an ether or an alcohol.
  • the nitro compound IA ⁇ XR 6 N0 2 ⁇ and the reducing agent are frequently used in approximately equimolar amounts; In order to optimize the course of the reaction, it can be advantageous to use one of the two components in excess, up to about a 10-fold molar amount.
  • the amount of acid is not critical. In order to reduce the starting compound as completely as possible, it is expedient to use at least an equivalent amount of acid.
  • the reaction temperature is generally in the range from -30 ° C. to 200 ° C., preferably in the range from 0 ° C. to 80 ° C.
  • the reaction mixture is usually diluted with water and the product by filtration, crystallization or extraction with a solvent which is largely immiscible with water, e.g. isolated with ethyl acetate, diethyl ether or methylene chloride. If desired, the product can then be cleaned as usual.
  • Suitable catalysts for this purpose are, for example, Raney nickel, palladium-on-carbon, palladium oxide, platinum and platinum oxide, a quantity of catalyst of 0.05 to 10.0 mol%, based on the compound to be reduced, generally being sufficient.
  • reaction solution can be worked up to the product in the customary manner.
  • the hydrogenation can be carried out under normal hydrogen pressure or under elevated hydrogen pressure.
  • XR 6 cyano or halogen ⁇ eg by Sandmeyer reaction: cf. for example Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. 5/4, 4th edition 1960, p. 438ff. ⁇ ,
  • a nitrite such as sodium nitrite and potassium nitrite
  • a nitrous acid ester such as tert-butyl nitrite and isopentyl nitrite under anhydrous reaction conditions, for example in glacial acetic acid containing hydrogen chloride, in absolute Alcohol, in dioxane or tetrahydrofuran, in acetonitrile or in acetone.
  • a copper (I) salt such as copper (I) cyanide, chloride, bromide and iodide, or with an alkali metal salt solution.
  • an aqueous acid preferably sulfuric acid.
  • a copper (II) salt such as copper (II) sulfate can have an advantageous effect on the course of the reaction. In general, this reaction is carried out at 0 to 100 ° C., preferably at the boiling point of the reaction mixture.
  • reaction temperatures are usually at -30 ⁇ C to 50 ° C.
  • All reactants are preferably used in approximately stoichiometric amounts, but an excess of one or the other component, up to approximately 3000 mol%, can also be advantageous.
  • Usable reducing agents are, for example, transition metals such as iron, zinc and tin (see, for example, "The Chemistry of the Thiol Group", John Wiley, 1974, p. 216).
  • Halosulfonation can be carried out without solvent in an excess of sulfonation reagent or in an inert
  • Solvents / diluents e.g. in a halogenated hydrocarbon, an ether, an alkyl nitrile or a mineral acid.
  • Chlorosulfonic acid is both the preferred reagent and solvent.
  • the reaction temperature is usually between 0 ° C and the boiling point of the reaction mixture.
  • reaction mixture is e.g. mixed with water, after which the product can be isolated as usual.
  • Suitable solvents are organic acids, inorganic acids, aliphatic or aromatic hydrocarbons, which can be halogenated, and ethers, sulfides, sulfoxides and sulfones.
  • halogenating agents are chlorine, bromine, N-bromosuccinimide, N-chlorosuccinimide or sulfuryl chloride.
  • a radical initiator for example an organic peroxide such as dibenzoyl peroxide or an azo compound such as azobisisobutyronitrile, or irradiation with light can have an advantageous effect on the course of the reaction.
  • a catalytic amount is usually sufficient.
  • the reaction temperature is normally from -100 ° C to 200 ° C, especially at 10 to 100 ° C or the boiling point of the reaction mixture.
  • Either the corresponding alcohols, thiols, carboxylic acids or amines are used as the nucleophile, in which case the reaction is preferably carried out in the presence of a base (for example an alkali metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate), or the reaction is carried out by Alcohols, thiols, carboxylic acids or amines with a base (for example an alkali metal hydride) of alkali metal salts of these compounds.
  • a base for example an alkali metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate
  • Alcohols, thiols, carboxylic acids or amines with a base for example an alkali metal hydride
  • Aprotic organic solvents e.g. Tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, or hydrocarbons such as toluene and n-hexane, are considered.
  • the reaction is carried out at a temperature between the melting point and the boiling point of the reaction mixture, preferably at 0 to 100 ° C.
  • the reaction temperature is usually 0 to 120 ° C.
  • Dimethyl sulfoxide for example, is suitable as a solvent.
  • I A ⁇ X R 6 CHO ⁇ olefination
  • IA ⁇ X (un) substituted ethene-1, 2-diyl ⁇
  • the olefination is preferably carried out by the Wittig method or one of its modifications, phosphorylides, phosphonium salts and phosphonates being suitable as reactants, or by aldol condensation.
  • a phosphonium salt or a phosphonate it is advisable to work in the presence of a base, alkali metal alkyls such as n-butyllithium, alkali metal hydrides and alcoholates such as sodium hydride, sodium ethanolate and potassium tert-butanolate, and also alkali metal and alkaline earth metal hydroxides such as calcium hydroxide, are particularly well suited.
  • reaction temperature is -40 to 150 ° C.
  • the phosphonium salts, phosphonates or phosphorylides required as reactants are known or can be prepared in a manner known per se ⁇ cf. see, for example, Houben-Weyl, Methods of Organic Chemistry, Vol. El, ⁇ . 636ff. and Vol. E2, pp. 345ff., Georg Thieme Verlag Stuttgart 1982; Chem. Ber. 95, 3993 (1962) ⁇ .
  • R 1 , R 2 , R 4 and R 5 have the meanings mentioned above.
  • oxidizing agents for this reaction are hydrogen peroxide or organic peracids, e.g. Performic acid, peracetic acid, trifluoroperacetic acid or m-chloroperbenzoic acid.
  • Suitable solvents are organic solvents which are inert to oxidation, such as, for example, hydrocarbons such as toluene or hexane, ethers such as diethyl ether, dimethoxyethane, methyl t-butyl ether, dioxane or THF, alcohols such as methanol or ethanol, or else mixtures of such solvents with one another or with water.
  • the solvent used is preferably the underlying organic acid, for example formic, acetic or trifluoroacetic acid, optionally in a mixture with one or more of the abovementioned solvents.
  • Suitable halogenating agents are phosphoryl halides such as P0C1 3 or POBr 3 , phosphorus halides such as PC1 5 , PBr 5 , PC1 3 or PBr, phosgene or organic or inorganic acid halides such as trifluoromethanesulfonic acid chloride, acetyl chloride, bromoacetyl bromide, acetyl bromide, benzoyl chloride, benzoyl chloride, benzoyl chloride, benzoyl chloride, benzoyl chloride, benzoyl chloride, benzoyl chloride, benzoyl chloride, benzoyl chloride, Toluenesulfonic acid chloride, thionyl chloride or sulfuryl chloride are considered. It may be advantageous to carry out the reaction in the presence of a
  • Base e.g. Trimethyl- or triethylamine or hexamethyl-disilazane is used to perform.
  • Suitable solvents are inert organic solvents, such as hydrocarbons such as toluene or hexane, ethers such as diethyl ether, diethoxyethane, methyl t-butyl ether, dioxane or THF, amides such as DMF, DMA or NMP, or mixtures thereof. If a reaction is carried out with a liquid halogenating agent, this can preferably also be used as a solvent, possibly in a mixture with one of the abovementioned.
  • the reaction temperature is normally between the melting point and the boiling point of the reaction mixture, preferably at 50-150 ° C.
  • halogenating agent or base in up to about a five-fold molar excess, based on the IX used.
  • Nitroalkanes such as nitromethane, malonic acid derivatives such as diethyl malonate or cyanoacetic acid derivatives such as ethyl cyanoacetate are considered. What was said under C.3 applies to carrying out this reaction.
  • Sections A and B can also be used to prepare the compounds IC and ID or can be used to prepare suitable starting compounds.
  • the compounds IC-1, IC-2, ID-1 and ID-2 can be obtained in known processes by ring closure reaction from the corresponding ortho-aminophenols or ort o-mercaptoanilines of the formulas IA-1, IA-2, IA- 3 or IA-4 can be built; numerous methods for this are known from the literature (see, for example, Houben-Weyl, Methods of Organic Chemistry, vol. E8a, pp. 1028ff., Georg-Thieme-Verlag, Stuttgart 1993 and vol. E8b, pp. 881ff., Georg-Thieme- Verlag, Stuttgart 1994).
  • the variables R 1 , R 2 , R 4 and R 5 have the abovementioned meanings.
  • the variables X 1 , X 2 , X 3 and X 4 stand independently for OH or SH.
  • This process comprises the reaction of an aminophenylimidazole of the formula IA-5, IA-6, IA-7 or IA-8 with halogen and ammonium thiocyanate or with an alkali metal or ⁇ rdalkalimetalthiocyanat.
  • This gives compounds of the general formulas IC-la, IC-lb or ID-la or ID-lb (compounds IC-1 or ID-1 in which R 19 is NH 2 ).
  • Preferred halogen is chlorine or bromine; among the alkali / alkaline earth metal thiocyanates, sodium thiocyanate is preferred.
  • the reaction is carried out in an inert solvent / diluent, e.g. in a hydrocarbon such as toluene and hexane, in a halogenated hydrocarbon such as dichloromethane, in an ether such as tetrahydrofuran, in an alcohol such as ethanol, in a carboxylic acid such as acetic acid, or in a polar aprotic solvent / diluent such as dimethylformamide, acetonitrile and dimethyl sulfoxide.
  • an inert solvent / diluent e.g. in a hydrocarbon such as toluene and hexane, in a halogenated hydrocarbon such as dichloromethane, in an ether such as tetrahydrofuran, in an alcohol such as ethanol, in a carboxylic acid such as acetic acid, or in a polar aprotic solvent / diluent such as dimethylformamide,
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably from 0 to 150 ° C.
  • halogen and ammonium thiocyanate or alkali metal / alkaline earth metal thiocyanate are preferably used in an approximately equimolar amount or in excess, up to about 5 times the molar amount, based on the amount of IA-5, IA-6 , IA-7 or IA-8.
  • the conversion of the amino group in the aminophenylimidazoles of the formula IA-5, IA-6, IA-7 or IA-8 into an azide group usually takes place in two stages, i.e. by diazotization of the amino group and subsequent treatment of the diazonium salt thus obtained with an azide.
  • diazotization the information given in process l) applies.
  • the conversion into the arylazides is preferably carried out by reacting diazonium salts with an alkali metal or alkaline earth metal azide such as sodium azide or by reaction with trimethylsilyl azide.
  • an inert organic solvent for example in hydrocarbons such as toluene or hexane, in halogenated hydrocarbons such as dichloromethane or chloroform, in ethers such as diethyl ether , Dimethoxyethane, methyl t-butyl ether, dioxane or T
  • the reaction is preferably carried out at elevated temperature, for example at the boiling point of the mixture.
  • those compounds of formula I in which XR 6 forms a chain -0-C (R 16 , R 17 ) -CO-N (R 18 ) - with R 5 or with R 7 in formula II, also from the nitrophenoxyes - Acetic acid derivatives of the formulas IA-9, IA-10, IA-11 and IA-12 are prepared.
  • the conversion is achieved by reducing the nitro groups in IA-9, IA-10, IA-11 or IA-12, with a ring-closing reaction to the compounds of the formula IC-3a, IC-3b, ID-3a generally occurring simultaneously with the reduction or ID-3b occurs.
  • R 1 , R 2 , R 4 , R 5 , R 16 and R X7 has the meanings given above.
  • R a is a nucleophilically displaceable leaving group, for example a C 1 -C 4 -alkyl radical such as methyl or ethyl.
  • reaction products can be converted into further compounds of the formula IC-3 or ID-3 by alkylation.
  • the statements made in Section C.4 apply analogously to the implementation of these reactions.
  • reaction mixtures are generally worked up in a manner known per se. Unless stated otherwise in the processes described above, the valuable products are obtained e.g. after dilution of the reaction solution with water by filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable organic solvent and working up the organic phase onto the product.
  • the 4-aryl-1-difluoromethoxyimidazoles of the formula I can be obtained in the preparation as isomer mixtures which, however, if desired, can be separated into the largely pure isomers by the customary methods such as crystallization or chromatography, including on an optically active adsorbate. Pure optically active isomers can advantageously be prepared from corresponding optically active starting products.
  • Agricultural salts of the compounds I can be formed by reaction with a base of the corresponding cation, preferably an alkali metal hydroxide or hydride, or by reaction with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • a base of the corresponding cation preferably an alkali metal hydroxide or hydride
  • an acid of the corresponding anion preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Salts of I can also be prepared in a customary manner by salting the corresponding alkali metal salt, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, maize, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the 4-aryl-l-difluoromethoxyimidazoles and their agriculturally useful salts are also suitable for the desiccation and / or defoliation of plants.
  • desiccants they are particularly suitable for drying out the aerial parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables a fully mechanical harvesting of these important crops.
  • the waste promoted by the use of compounds of the formula I according to the invention and their agriculturally useful salts is based on the formation of separating tissue between the fruit or leaf and shoot part of the plants.
  • Cotton demonstration is of particular economic interest because it makes harvesting easier.
  • the shortening of the time interval in which the individual plants mature leads to an increased quality of the harvested fiber material.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicides are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients grow on the leaves below them unwanted plants or the uncovered floor area (post-directed, lay-by).
  • the compounds I or the herbicidal compositions comprising them can be sprayed, atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, old-dispersions, pastes, dusts, sprays or granules , Dusting, scattering or pouring.
  • 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.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, for example amides such as N-methylpyrrolidone or water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons eg paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the 4-aryl-l-difluoromethoxyimidazoles I as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, 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 Formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphen
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and ma
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the 4-aryl-l-difluoromethoxyimidazoles I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2-aroyl come as mixing partners -l, 3-cyclohexanediones, hetaryl-aryl-ketones, benzylisoxazolidinones, meta-CF 3 -phenyl derivatives, carbamates, quinoline carboxylic acid and its derivatives, chloroacetanilides, cyclohexane-l, 3-dione derivatives, diazines, dichloropropionic acid and
  • the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria.
  • the miscibility with mineral salt solutions which are used to remedy nutritional and trace element deficiencies.
  • Non-phytotoxic oils and oil concentrates can also be added.
  • the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (see p.).
  • Example 1 4- (4-chlorophenyl) -l-difluoromethoxy-2-methyl-1H-imidazole (compound no. IAb.l; see Table 1)
  • Example 8 Methanesulfonic acid- (2,4-dichloro-5- (5-chloro-l-di-fluoromethoxy-2-methyl-lH-imidazol-4-yl) anilide) (compound no. IAb.306)
  • Example 12 5-chloro-4- (2,4-dichlorophenyl) -1-difluoro-methoxy-2-isopropyl-lH-imidazole (Compound No. IAd.6)
  • the compounds I according to the invention can be formulated, for example, as follows:
  • I 20 parts by weight of the compound of Example 1 are dissolved in a mixture which consists of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight. parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
  • aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
  • Example 4 20 parts by weight of the active ingredient Example 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
  • Example 10 20 parts by weight of the active ingredient Example 10 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
  • V 3 parts by weight of the active ingredient Example 7 are mixed with 97 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 3% by weight of the active ingredient.
  • VI 20 parts by weight of the active ingredient Example 8 are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condesate and 68 parts by weight of a paraffinic mineral oil.
  • a stable oily dispersion is obtained.
  • VII 1 part by weight of the compound Example 12 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil.
  • a stable emulsion concentrate is obtained.
  • Plastic pots with loamy sand with about 3.0% humus as substrate served as culture vessels. ' The seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the tubes were lightly sprinkled to promote germination and growth, and then covered with transparent plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • test plants were first grown to a height of 3 to 15 cm, depending on the growth habit, and then treated with the active ingredients suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the application rate for post-emergence treatment was 0.125 and 0.063 kg a.S./ a.
  • the plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated. Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types:
  • Compound No. IAb.6 from Example 4 shows very good herbicidal activity against the harmful plants SETFA, ABUTH, AMARE and POLPE at application rates of 0.125 kg / ha a.S. and from 0.063 kg / ha a.S. Postemergence application.

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Abstract

L'invention concerne des 4-aryl-1-difluorométhoxyimidazoles de la formule (I) Dans ladite formule (I), les variables R?1, R2 et R3¿ ont les significations données dans la description. Les composés de la formule (I) sont des herbicides efficaces et peuvent être utilisés pour lutter contre la pousse de végétaux indésirables. Lesdits composés sont en outre adaptés à la dessiccation et/ou la défoliation de plantes, en particulier du coton. L'invention concerne également des moyens pour lutter contre des plantes parasites et des moyens pour la dessiccation et/ou la défoliation de plantes.
EP01939981A 2000-01-07 2001-01-05 4-aryl-1-difluoromethoxyimidazole Withdrawn EP1244635A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10000366 2000-01-07
DE10000366 2000-01-07
PCT/EP2001/000077 WO2001049668A2 (fr) 2000-01-07 2001-01-05 4-aryl-1-difluoromethoxyimidazole

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EP1244635A2 true EP1244635A2 (fr) 2002-10-02

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EP (1) EP1244635A2 (fr)
JP (1) JP2003519216A (fr)
AU (1) AU2845301A (fr)
CA (1) CA2396583A1 (fr)
WO (1) WO2001049668A2 (fr)

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AT511828B1 (de) 2012-01-10 2013-03-15 Adria Wien Pipeline Gmbh Verfahren und vorrichtung zur reparatur einer fehlstelle einer rohrleitung

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CA2106337C (fr) * 1992-09-26 1998-06-16 Hiroyuki Nakanishi Derives phenylimidazole, procedes pour leur production, herbicides les comprenant, et leurs usages a titre d'herbicides
US5861359A (en) * 1995-07-25 1999-01-19 Fmc Corporation Herbicidal phenylmethoxphenyl heterocycles

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Title
See references of WO0149668A3 *

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WO2001049668A2 (fr) 2001-07-12
CA2396583A1 (fr) 2001-07-12
WO2001049668A3 (fr) 2002-02-14
JP2003519216A (ja) 2003-06-17
AU2845301A (en) 2001-07-16

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