EP2235005A2 - Azolylméthyloxiranes, leur utilisation et agents les contenant - Google Patents

Azolylméthyloxiranes, leur utilisation et agents les contenant

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Publication number
EP2235005A2
EP2235005A2 EP08861314A EP08861314A EP2235005A2 EP 2235005 A2 EP2235005 A2 EP 2235005A2 EP 08861314 A EP08861314 A EP 08861314A EP 08861314 A EP08861314 A EP 08861314A EP 2235005 A2 EP2235005 A2 EP 2235005A2
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EP
European Patent Office
Prior art keywords
compounds
corresponds
case
row
combination
Prior art date
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German (de)
English (en)
Inventor
Jochen Dietz
Thomas Grote
Bernd Müller
Jan Klaas Lohmann
Jens Renner
Sarah Ulmschneider
Alice GLÄTTLI
Marianna Vrettou
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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
    • 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
    • C07D405/06—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 linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/10—Antimycotics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00

Definitions

  • B is phenyl containing one substituent L in the 2-position and one, two or three further independently selected substituents L; where L means:
  • L is halogen, cyano, nitro, cyanato (OCN), C -C 8 -alkyl, C 8 - haloalkyl, phenyl-Ci-C 6 alkyloxy, C 2 -C 8 -alkenyl, C 2 -C 8 halo-alkenyl, C 2 -C 8 -alkyl kinyl, C 2 -C 8 haloalkynyl, C4-Cio-alkadienyl, C 4 - Cio-Halogenalkadienyl, Ci-C8-alkoxy, Ci-C8-haloalkoxy, Ci C8 - alkylcarbonyloxy, Ci-C 8 alkylsulfonyloxy, C 2 -C 8 alkenyloxy, C 2 -C 8 - haloalkenyloxy, C 2 -C 8 alkynyloxy, C 2 -C 8 haloalkynyloxy,
  • n 0, 1 or 2;
  • a 1 is hydrogen, hydroxy, Ci-C 8 alkyl, Ci-C8-haloalkyl, amino, Ci-C8-alkylamino or di-Ci-C 8 alkylamino
  • a 2 is one of the groups mentioned at A 1 or C 2 -C 8 -alkenyl, C 2 -C 8 -haloalkenyl, C 2 -C 8 -alkynyl, C 2 -C 8 -haloalkynyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkoxy , C 2 -C 8 -alkenyloxy, C 2 -C 8 -haloalkenyloxy, C 2 -C -alkynyloxy, C 2 -C 8 -haloalkynyloxy, Cs-C 8 -
  • Cycloalkyl Cs-Cs-halocycloalkyl, C3-C 8 cycloalkoxy, or Cs-Cs-halocycloalkoxy;
  • a 4 are independently hydrogen, Ci-Cs-alkyl, Ci-C 8 -alkyl, C 2 -C 8 haloalkenyl, C 2 -C 8 -alkyl kinyl,
  • R L is halogen, cyano, nitro, Ci-C8 -alkyl, Cs-haloalkyl, Ci-C 8 - alkoxy, Ci-C8-haloalkoxy, C3-C8 cycloalkyl, C3-C 8 -Halogencyclo- alkyl, C3-C8 cycloalkenyl, C3-C8-cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci-Cs-alkylcarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-C 8 - alkoxycarbonyl, amino, Ci-Cs-alkylamino, di -C-Cs-alkylamino;
  • R 3 is Ci-Cs-alkyl, d-Cs-haloalkyl, Ci-Cs-alkoxy, Ci-C 8 -
  • R 4 is Ci-Cs-alkyl, phenyl-Ci-C 8 -alkyl or phenyl, wherein the
  • Each phenyl group is unsubstituted or substituted by one, two or three groups independently selected from halogen and d-d-alkyl;
  • R 1 , R 2 independently of one another are C 1 -C 6 -alkyl, C 1 -C 5 -haloalkyl, C 1 -C 5 -alkoxy, C 1 -C 5 -alkoxy-C 1 -C 5 -alkoxy, C 1 -C 8 -haloalkoxy, C 1 -C 8 - alkoxy-Ci-C 8 alkyl, Ci-C 8 -alkyl thio, C 2 -C 8 -alkenylthio, C 2 -C 8 -alkyl kinyl- thio, Cs-Cs-cycloalkyl, C 3 -C 8 cycloalkylthio , phenyl, phenyl-Ci-C 4 - alkyl, phenoxy, phenylthio, phenyl-Ci-C4-alkoxy or NR 5 R 6, wherein
  • R 5 is H or C 1 -C 8 -alkyl and R 6 is C 1 -C 8 -alkyl, phenyl-C 1 -C 4 -alkyl or phenyl or R 5 and R 6 together represent an alkylene chain having four or five C atoms or form a radical of the formula -CH 2 -CH 2 -O-CH 2 -CH 2 - or -CH 2 -CH 2 -NR 7 -CH 2 -CH 2 - form, in which R 7 is hydrogen or C C 4 alkyl; where the aromatic
  • Groups in the aforementioned groups are each independently unsubstituted or substituted by one, two or three groups selected from halogen and C 1 -C 4 -alkyl; or a group SM, where M means:
  • M is an alkali metal cation, one equivalent of an alkaline earth metal cation, one equivalent of a copper, zinc, iron or nickel cation or an ammonium cation of the formula (E) Z 2
  • Z 1 and Z 2 are independently hydrogen or C 1 -C 8 -alkyl
  • Z 3 and Z 4 are independently hydrogen, C 1 -C 8 -alkyl, benzyl or phenyl; wherein the phenyl groups are each unsubstituted or are substituted by one, two or three groups independently selected from halogen and C 1 -C 4 alkyl;
  • the invention relates to azolylmethyloxiranes of the formula I.
  • A is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -haloalkenyl, C 2 -
  • B is phenyl which contains a substituent L in the 2-position and a substituent L * in the 4-position, or phenyl which has one substituent L in the 2-position and one further independently selected substituent L in the 3-, 5- or 6-position contains, or
  • L * fluorine, bromine, iodine, cyano, nitro, cyanato (OCN), C alkyloxy 8 alkyl, Ci-C ⁇ -haloalkyl, phenyl-Ci-C 6, C 2 -C 8 -alkenyl -alkyl, C 2 -C 8 -
  • n 0, 1 or 2;
  • a 1 is hydrogen, hydroxy, C 1 -C 8 -alkyl, C 1 -C -haloalkyl, amino, C 1 -C 8 -alkylamino or C 1 -C -alkylamino,
  • a 2 is one of the groups mentioned under A 1 or C 2 -C 8 -alkenyl, C 2 -C 8 -haloalkenyl, C 2 -C 8 -alkynyl, C 2 -C 8 -haloalkynyl, C 1 -C 5 -alkoxy, C 1 -C 8 -haloalkoxy, C2-C8-alkenyloxy, halo-C 2 -C 8 alkenyloxy, C2-Cs-alkynyloxy, C2-C8 haloalkynyloxy, Cs-C 8 -
  • Cycloalkyl Cs-Cs-halocycloalkyl, C3-Cs-cycloalkoxy or Cs-Cs-halocycloalkoxy;
  • a 4 are independently hydrogen, Ci-Cs-alkyl, Ci-C 8 -alkyl, C 2 -C 8 haloalkenyl, C 2 -C 8 -alkyl kinyl,
  • R L is halogen, cyano, nitro, Ci-Cs-alkyl, d-Cs-haloalkyl, Ci-C 8 - alkoxy, Ci-Cs-haloalkoxy, C3-C8 cycloalkyl, Cs-Cs-halocycloalkyl, C3-C 8 Cycloalkenyl, Cs-Cs-cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci-Cs-alkylcarbonyl, Ci-Cs-alkylcarbonyloxy, Ci-C 8 - alkoxycarbonyl, amino, Ci-Cs-alkylamino, di-Ci-Cs-alkylamino; i
  • R 3 is C 1 -C 8 -alkyl, C 1 -C 5 -haloalkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -haloalkoxy or NA 3 A 4 ; and R 4 is C 1 -C 5 -alkyl, phenyl-C 1 -C 8 -alkyl or phenyl, wherein the phenyl groups are each unsubstituted or substituted by one, two or three groups independently selected from halogen and C 1 -C 4 -alkyl;
  • R 1 , R 2 independently of one another are C 1 -C 6 -alkyl, C 1 -C 5 -haloalkyl, C 1 -C 5 -alkoxy, C 1 -C 5 -alkoxy-C 1 -C 5 -alkoxy, C 1 -C 8 -haloalkoxy, C 1 -C 8 - alkoxy-Ci-C 8 alkyl, Ci-C 8 -alkyl thio, C 2 -C 8 -alkenylthio, C 2 -C 8 -alkyl kinyl- thio, Cs-Cs-cycloalkyl, C 3 -C 8 cycloalkylthio , phenyl, phenyl-Ci-C 4 - alkyl, phenoxy, phenylthio, phenyl-Ci-C4-alkoxy or NR 5 R 6, wherein R 5 is H or Ci-C 8 alkyl and R 6 is
  • R 7 is hydrogen or Ci-C 4 -alkyl; wherein the aromatic groups in the aforementioned radicals are each independently unsubstituted or substituted by one, two or three groups selected from halogen and C 1 -C 4 -alkyl; or a group SM, where M means:
  • M is an alkali metal cation, one equivalent of an alkaline earth metal cation, one equivalent of a copper, zinc, iron or nickel cation or an ammonium cation of the formula (E) z 2
  • Z 1 and Z 2 are independently hydrogen or Ci-Cs-alkyl
  • Z 3 and Z 4 are independently hydrogen, C 1 -C 8 alkyl, benzyl or phenyl; wherein the phenyl groups are each unsubstituted or substituted by one, two or three groups independently selected from halogen and C 1 -C 4 alkyl;
  • D * represents : - R, wherein R has the meaning defined above;
  • the invention relates to the preparation of the compounds I, the intermediates for the preparation of the compounds I and their preparation and the use of the compounds according to the invention for controlling phytopathogenic fungi and agents containing them.
  • Triazolylmethyloxiranes with a substituted triazole group are known, for example, from WO 96/38440, WO 97/41107, WO 97/42178, WO 97/43269, WO 97/44331, WO 97/443332, WO 99/05149 and WO 99/21853.
  • the fungicidal action of the compounds known from the prior art leaves something to be desired, in particular at low application rates in some cases. It is an object of the present invention to provide novel compounds which preferably have improved properties, such as a better fungicidal action and / or better toxicological properties. This object has surprisingly been achieved with the compounds of the formula I described herein.
  • the compounds I are able to form salts or adducts with inorganic or organic acids or with metal ions. This also applies to most of the precursors for compounds I described herein, of which the salts and adducts are also subject of the present invention.
  • inorganic acids examples include hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, carbonic acid, sulfuric acid, phosphoric acid and nitric acid.
  • Suitable organic acids are, for example, formic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid and other arylcarboxylic acids, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids with straight-chain or branched alkyl radicals with 1 to 20 carbon atoms), arylsulfonic acids or disulfonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or diphosphonic acids (aromatic Radicals such as phenyl and naphthyl which carry one or two phospho
  • the metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main groups, in particular aluminum, tin and lead, and the first to eighth transition groups, in particular chromium, manganese, iron, cobalt, nickel, copper, Zinc and others in consideration. Particularly preferred are the metal ions of the elements of the subgroups of the fourth period.
  • the metals can be present in the various valences that belong to them.
  • the compounds of the formula I according to the invention can be prepared in various ways in analogy to known processes of the prior art (see, for example, the cited prior art and crop protection news Bayer 57/2004, 2, pages 145-162). For example, the compounds of the invention can be prepared by the syntheses shown in the following Schemes.
  • Suitable bases are all suitable bases known to those skilled in the art for such reactions.
  • strong alkali metal bases such as n-butyl lithium, lithium diisopropylamide, sodium hydride, sodium amide or potassium tert-butoxide are used. It may be preferred to react in the presence of an additive such as e.g. Tetramethylethylenediamine (TMEDA) to perform.
  • TEDA Tetramethylethylenediamine
  • Suitable solvents are all inert organic solvents which are customary for such reactions, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane or liquid ammonia or strongly polar solvents such as dimethyl sulfoxide preferably being usable.
  • Sulfur is preferably used as a powder.
  • Hydrolysis is carried out using water, optionally in the presence of an organic or inorganic acid, e.g. Acetic acid, dilute sulfuric acid or dilute hydrochloric acid.
  • an organic or inorganic acid e.g. Acetic acid, dilute sulfuric acid or dilute hydrochloric acid.
  • the reaction temperature is preferably between -70 0 C and + 20 0 C, in particular between -70 0 C and 0 0 C.
  • the reaction is generally carried out under atmospheric pressure. In general, 1 to 3 equivalents, preferably 1 to 2.5 equivalents, of strong base and then an equivalent amount or an excess of sulfur are used per mole of the compound of the formula II.
  • the reaction can be carried out under a protective gas atmosphere, for example under nitrogen or argon.
  • the workup is carried out according to methods generally known to the person skilled in the art. Usually, the reaction mixture is extracted with a suitable organic solvent and the residue is optionally purified by recrystallization and / or chromatography.
  • an aprotic, polar solvent e.g. an amide (such as dimethylformamide (DMF)) or N-alkylpyrrolidone (such as N-octylpyrrolidone, N-dodecylpyrrolidone or N-methylpyrrolidone (NMP)
  • the reaction is usually carried out at temperatures in the range of 140 0 C to 160 0 C.
  • the reaction components are usually employed in amounts such that about 1 to 6 moles of sulfur are used per mole of compound II.
  • Sulfur is usually used in the form of powder. During the reaction, air is passed over the reaction mixture.
  • Suitable bases are all suitable bases known to those skilled in the art for such reactions.
  • strong alkali metal bases such as n-butyl lithium, lithium diisopropylamide, sodium hydride, sodium amide or potassium tert-butoxide are used. It may be preferable to carry out the reaction in the presence of an additive such as tetramethylethylenediamine (TMEDA).
  • TEDA tetramethylethylenediamine
  • the disulfides are commercially available or synthesized by known manufacturing methods.
  • a special disulfide is the Dirhodan NC-S-S-CN.
  • Suitable solvents are all inert organic solvents which are customary for such reactions, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane or liquid ammonia or strongly polar solvents such as dimethyl sulfoxide preferably being usable.
  • the reaction temperature is preferably between -70 0 C and + 20 0 C, in particular between -70 ° C and 0 0 C.
  • the reaction is generally carried out under atmospheric pressure. In general, 1 to 3 equivalents, preferably 1 to 2.5 equivalents, of strong base and then an equivalent amount or an excess of disulfide are used per mole of the compound of the formula II.
  • the reaction can be carried out under a protective gas atmosphere, for example under nitrogen or argon.
  • the workup is carried out according to methods generally known to the person skilled in the art. Usually, the reaction mixture is extracted with a suitable organic solvent and the residue is optionally purified by recrystallization and / or chromatography.
  • Z is a leaving group X (Compounds III.1, see below) or OH (Compounds III.2, see below) and A and B are as defined below, are important starting compounds to ultimately arrive at the compounds of the invention.
  • X is a leaving group, such as halogen (eg Cl or Br) or OSO 2 R, wherein R is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, aryl or substituted aryl, in particular stands OSO 2 R for a mesylate, triflate, phenyl or toluenesulfonate group.
  • compounds of the formula III.1 are reacted with 1, 2,4-triazole and a base such as, for example, sodium hydride in, for example, DMF. See also eg EP 0 421 125 A2.
  • Compounds of the formula III.1 are partly new.
  • An object of the invention are therefore also compounds of formula III.1, wherein A and B are as defined for formula I or are preferably defined, and X is a leaving group, in particular halogen (eg Cl or Br) or OSO 2 R, wherein R is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, aryl or substituted aryl, where the compounds are 2-bromomethyl-2- (4-chlorophenyl) -3- (2,4-dichlorophenyl) oxirane, 2-bromomethyl-2- (4-bromophenyl) -3- (2,4-dichlorophenyl) oxirane, 2-bromomethyl-2- (tert-butyl) -3- (2,4-dichlorophenyl) oxirane, 2- Bromomethyl-2- (methyl) -3- (2,4-dichlorophenyl) oxirane, 2-bromomethyl-2- (4- (tert-buty
  • Another object of the invention are compounds of formula III.1, wherein A and B are as defined for formula I or are preferably defined, and X is a leaving group, in particular halogen (eg Cl or Br) or OSO 2 R, wherein R is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, aryl or substituted aryl, where the compounds are 2-bromomethyl-2- (4-chlorophenyl) -3- (2-chloro-4-fluorophenyl) oxirane, 2 Bromomethyl-2- (phenyl) -3- (2-chloro-4-fluorophenyl) oxirane, 2-bromomethyl-2- (4-fluorophenyl) -3- (2-chloro-4-fluorophenyl) oxirane, 2-bromomethyl -2- (4-chlorophenyl) -3- (2-chloro-4-fluorophenyl) oxirane, 2-bromomethyl
  • A is phenyl which contains one, two or three independently selected substituents L with the exceptions just mentioned.
  • compounds III.1 are excluded, in which A and B are
  • A is phenyl which contains one, two or three independently selected substituents L with the exceptions just mentioned.
  • compounds III.1 are additionally excluded, in which A and B are
  • A phenyl
  • B 2-chloro-5-NO 2 -phenyl or 2,4-dimethylphenyl
  • B 2-chloro-5-NO 2 -phenyl, 2-chloro-4-methoxyphenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 2-fluoro-3-fluorophenyl or 2,4-dimethylphenyl.
  • A is phenyl which contains one, two or three independently selected substituents L with the abovementioned exceptions.
  • the phenyl ring A contains two or three substituents L.
  • the phenyl ring A contains a substituent L in the 4-position which is selected from C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy , Ci-C4-haloalkoxy and Ci-C4-haloalkylthio and no further substituent L or one or two further independently selected substituents L.
  • X is OSO 2 R, wherein R is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, aryl or substituted aryl, in particular OSO 2 R is a mesylate, triflate , Phenyl or toluenesulfonate group.
  • Z is Br and B is phenyl which contains a substituent L in the 2-position and exactly one further substituent L, wherein each L is independently selected from F, Br, cyano, nitro , cyanato (OCN), C -C 8 -alkyl, C 8 alkyloxy haloalkyl, phenyl-Ci-C 6, C 2 -C 8 - alkenyl, C 2 -C 8 haloalkenyl, C 2 -C 8 -Al kinyl, C 2 -C 8 haloalkynyl, C4-Cio-alkadienyl, C4-Cio-Halogenalkadienyl, Ci-C8-alkoxy, Ci-C8-haloalkoxy, Ci-C 8 alkylcarbonyl oxy, Ci- C 8 alkylsulfonyloxy, C 2 -C 8 alkenyloxy, C 2 -C 8 alkenyloxy, C 2
  • Z is mesylate or tosylate and B is phenyl which contains a substituent L in the 2-position and exactly one further substituent L, where L is in each case independently selected from F, Br , cyano, nitro, cyanato (OCN), C -C -alkyl 8 -alkyl, d-Cs-haloalkyl, phenyl-d-Ce-alkyloxy, C 2 -C 8 alkenyl, C 2 -C 8 -I Ialogenalkenyl, C 2 -C 8 -alkyl kinyl, C 2 -C 8 - haloalkynyl, C4-Cio-alkadienyl, C4-Cio-Halogenalkadienyl, Ci-C8-alkoxy, Ci-C 8 - haloalkoxy, Ci-Cs-alkylcarbonyloxy, Ci -C 8 alkyl
  • a and B in III.1 have the meanings as specified for Formula I herein, taking into account the excluded compounds.
  • X is as for formula III.1 and A and B are as defined or preferably defined for formula I.
  • Suitable epoxidation processes are known to the person skilled in the art. For example, hydrogen peroxide / maleic anhydride can be used for this purpose.
  • the double bond can be in both (E) and (Z) configurations. This is represented by the jagged bond between B and the double bond.
  • a further subject of the present invention are compounds of the formula IVa in which A and B are as defined or preferably defined for formula I, where the compounds are 1- (2,4-dichlorophenyl) -2- (4-chlorophenyl) - 3-bromo-prop-1-ene, 1- (2,4- Dichlorophenyl) -2- (4-bromophenyl) -3-bromo-prop-1-ene, 1- (2,4-dichlorophenyl) -2- (tert-butyl) -3-bromo-prop-1-ene, 1 - (2,4-dichlorophenyl) -2- (methyl) -3-bromo-prop-1-ene, 1- (2,4-dichlorophenyl) -2- (4-tert-butyl-phenyl) -3-bromo -prop
  • B is not 2,4-dichlorophenyl.
  • B is not 2,4-dichlorophenyl, not 2-chloro-4-fluorophenyl and not 2-chloro-6-fluorophenyl.
  • A is phenyl which contains one, two or three independently selected substituents L with the exceptions just mentioned.
  • the phenyl ring A contains two or three substituents L.
  • the phenyl ring A contains a substituent L in the 4-position which is selected from C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, Ci-C4-haloalkoxy and Ci-C4-haloalkylthio and no further substituent L or one or two further independently selected substituents L contains.
  • a and B and X in IVa have the meanings as specified for Formula I or III.1 herein, taking into account the excluded compounds.
  • Compounds of the formula III.1 can also be prepared from compounds of the formula III.2, by introducing the leaving group X by methods known to those skilled in the art. Accordingly, a compound of the formula III.2 is reacted, for example, with R-SO 2 Y, where R is as defined for formula III.1 and Y is halogen, where R-SO 2 Y is, for example, mesyl chloride, in the presence of a base (for example NEt.3). implemented (see also EP386557).
  • A is phenyl which contains one, two or three independently selected substituents L.
  • the phenyl ring A contains two or three substituents L.
  • the phenyl ring A contains a substituent L in the 4-position which is selected from C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 haloalkoxy and C 1 -C 4 -haloalkylthio and no further substituent L or one or two further independently selected substituents L.
  • compounds III.2 are excluded, wherein A and B are:
  • compounds III.2 are furthermore excluded, in which A and B are
  • A phenyl
  • B 2-chloro-5-NO 2 -phenyl, 2-chloro-4-methoxyphenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 2-fluoro-3-fluorophenyl or 2,4-dimethylphenyl.
  • A is phenyl which contains one, two or three substituents L.
  • a and B in III.2 have the meanings specified for Formula III.1 herein.
  • Each R y is independently C 1 -C 4 -alkyl.
  • Suitable oxidizing agents and conditions are known to those skilled in the art. For example, a reaction according to Swern (Australian Journal of Chemistry, 57 (6), 537-548, 2004), reactions with hypervalent iodine compounds (Organic Letters, 5 (17), 2989-2992, 2003), with chromium compounds such as, for example, pyridinium di chromate (cf. Tetrahedron, 45 (1), 239-58, 1989) or with manganese oxides such as MnO 2 (Journal of the American Chemical Society, 107 (13), 3963-71, 1985).
  • the oxidation can also be carried out via a Dess-Martin oxidation in a solvent such as CH 2 Cl 2.
  • the double bond can be in both (E) and (Z) configurations. This is represented by the serrated bond between B and the double bond.
  • Compounds of the formula VII can be prepared from ⁇ , ⁇ -unsaturated acrylic acid esters of the formula VIII:
  • esters of the formula VIII are reduced to the alcohol VII.
  • Suitable reduction methods are well known to those skilled in the art.
  • the double bond may be in both (E) and (Z) configurations. This is represented by the serrated bond between B and the double bond.
  • Compounds of formula VIII may also be reduced in one step to the acrolein of formula V, e.g. with metal hydrides, e.g. Diisobutylaluminum hydride at low temperatures.
  • metal hydrides e.g. Diisobutylaluminum hydride at low temperatures.
  • metal hydrides e.g. Diisobutylaluminum hydride at low temperatures.
  • aluminum hydrides preferably lithium alanate (European Journal of Medicinal Chemistry, 40 (6), 529-541, 2005) or dialkylaluminum hydrides, such as e.g. DIBAL-H (Synlett, (18), 3182-3184, 2006) can be used here.
  • the acrylic acid esters of the formula VIII are obtainable from glyoxalic acid esters of the formula IX by reaction with phosphorus compounds, e.g. Horner-Emmons type or Wittig connections.
  • Suitable phosphorus compounds can be prepared by known standard methods, for example from a compound of the following type:
  • X 1 represents a leaving group such as a halide, preferably chlorine or bromine.
  • a leaving group such as a halide, preferably chlorine or bromine.
  • the reaction of such halides to the desired Horner-Emmons or Wittig reagents can be carried out as described, for example, in Chemistry of Materials, 13 (9), 3009-3017; 2001, European Journal of Organic Chemistry, (7), 1247-1257; 2005 or WO1992 / 05145.
  • alkyl halides are either commercially available or can be prepared by standard methods, e.g. by halogenation of the corresponding methyl compound.
  • Suitable halogenating agents for this reaction are N-bromosuccinimide (Chemistry-A European Journal, 12 (21), 5632-5641, 2006) and N-chlorosuccinimide (Tetrahedron Letters, 47 (37), 6607-6609, 2006).
  • the double bond may exist in both (E) and (Z) configurations. This is represented by the jagged bond between B and the double bond.
  • Another object of the present invention are compounds of formula IVb, wherein A and B are as defined or preferably defined for formula I.
  • A is phenyl which contains one, two or three independently selected substituents L.
  • the phenyl ring A contains two or three substituents L.
  • the phenyl ring A contains a substituent L in the 4-position, which is selected from Ci-C 4 -AlkVl, Ci-C4-haloalkyl, CrC 4 -Akoxy , -C 4 - haloalkoxy and Ci-C 4 haloalkylthio and no further substituent L, or one or two further independently selected substituents L.
  • compounds IVb are excluded, wherein A and B are:
  • compounds Vb are also excluded, wherein A and B are
  • A phenyl
  • B 2-chloro-5-NO 2 -phenyl, 2-chloro-4-methoxyphenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 2-fluoro-3-fluorophenyl or 2,4-dimethylphenyl
  • A is phenyl which contains one, two or three substituents L.
  • a and B in IVb have the meanings specified for formula III.1 herein.
  • Compounds of formula IVb can be obtained by reacting a compound of formula IVa as described above with 1, 2,4-triazole and a base.
  • the reaction conditions can be selected as described above in the preparation of compounds II starting from compounds III.
  • a further possibility for preparing compounds of the formula I consists, starting with compounds of the formula III (see above), first with hydrazine to give compounds of the formula IIIa
  • An object of the present invention are also compounds of the formula IIIa, wherein A and B are as defined or preferably defined for formula I.
  • An object of the present invention are also compounds of the formula INb, wherein A and B are as defined or preferably defined for formula I.
  • compounds IIIa may be reacted with formaldehyde ((CH 2 O) n ) and a thiocyanate (YSCN, supra) to give
  • An object of the present invention are also compounds of the formula INc, wherein A and B are as defined or preferably defined for formula I.
  • R x1 and R x2 are preferably both methyl (compounds IIId-1). See also DE19744401 and WO99 / 18086.
  • An object of the present invention are furthermore compounds of the formula INd, wherein A and B are as defined or preferably defined for formula I.
  • Halogen fluorine, chlorine, bromine and iodine
  • Haloalkyl alkyl as mentioned above, wherein in these groups partially or completely replaces the hydrogen atoms by halogen atoms as mentioned above are; in particular C 1 -C 2 -haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl , 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1, 1 ,
  • Alkenyl and the alkenyl moieties in compounded groups such as alkenyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6 or 2 to 8 carbon atoms and a double bond in any position.
  • alkenyl groups such as (C 2 -C 4) -alkenyl
  • larger alkenyl groups such as (C 5 -C 8) -alkenyl.
  • alkenyl groups are e.g.
  • C2-C6 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, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-ethyl-1-propen
  • Haloalkenyl alkenyl as defined above, wherein in these groups the hydrogen atoms are partially or completely replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Alkadienyl unsaturated, straight-chain or branched hydrocarbon radicals having 4 to 6 or 4 to 8 carbon atoms and two double bonds in any position;
  • Alkynyl and the alkynyl moieties in assembled groups straight-chain or branched hydrocarbon groups having 2 to 4, 2 to 6 or 2 to 8 carbon atoms and one or two triple bonds in any position, for example C 2 -C 6 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl,
  • Haloalkynyl alkynyl, as defined above, wherein in these groups the hydrogen atoms are partially or completely replaced by halogen atoms, as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Cycloalkyl and the cycloalkyl moieties in assembled groups mono- or bicyclic, saturated hydrocarbon groups having 3 to 8, in particular 3 to 6, carbon ring members, e.g. C3-C6 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;
  • Halogencycloalkyl cycloalkyl as defined above, wherein in these groups the hydrogen atoms are partially or completely replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Cycloalkenyl monocyclic, monounsaturated hydrocarbon groups having preferably 3 to 8 or 4 to 6, in particular 5 to 6 carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, Cyclohexene-4-yl and the like;
  • Halocycloalkenyl cycloalkenyl as defined above, wherein in these groups the hydrogen atoms are partially or completely replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • Alkoxy for an oxygen-bonded alkyl group as defined above, preferably having 1 to 8, more preferably 2 to 6 carbon atoms. Examples are: methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy; and also, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2- Ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-
  • Examples of these are OCH 2 F, OCHF 2 , OCF 3 , OCH 2 Cl, OCHCl 2 , OCCl 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2 Difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC 2 Fs , 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 2-bromopropoxy,
  • Alkylene divalent linear chains of CH 2 groups. Preference is given to (C 1 -C 6) -alkylene, more preferably (C 2 -C 4) -alkylene, and furthermore it may be preferable to use (C 1 -C 3 ) -alkylene groups.
  • Examples of preferred alkylene radicals are CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 (CH 2 ) 2 CH 2 , CH 2 (CH 2 ) 3 CH 2 and CH 2 (CH 2 ) 4 CH 2 ;
  • tri- or four-membered saturated heterocycle (hereinafter also Heterocyc IyI) containing one or two heteroatoms from the group O, N and S as ring members; - five- or six-membered saturated or partially unsaturated heterocycle containing one, two, three or four heteroatoms from the group O, N and S as ring members: e.g. monocyclic saturated or partially unsaturated heterocycles comprising, in addition to carbon ring members, one, two or three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2
  • hexahydrooxepinyl such as 2,3,4,5-tetrahydro [1 H] oxepin-2, -3, -4, -5, -6 or -7-yl, 2,3,4, 7-tetrahydro [1 H] oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro [1 H] oxepin 2-, -3-, -A-, -5-, -6- or -7-yl, hexahydroazepine-1, -2-, -3- or -4-yl, tetra- and hexahydro-1, 3 diazepinyl, tetra- and hexahydro-1,4-diazepinyl, tetra- and hexahydro-1,3-oxazepinyl, tetra- and hexahydro-1,4-o
  • the respective heterocycle can via a Carbon atom or via a nitrogen atom, if contained, be attached. It may be preferred according to the invention that the respective heterocycle is bonded via carbon, on the other hand it may also be preferred that the heterocycle is bonded via nitrogen.
  • the heterocycle means in particular: -5-membered heteroaryl containing one, two, three or four nitrogen atoms or one, two or three nitrogen atoms and / or a sulfur or oxygen atom, which heteroaryl may be attached via C or N, if present 5-ring heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one, two or three nitrogen atoms and / or one sulfur or oxygen atom as ring members, eg furyl, thienyl, pyrrolyl,
  • -6-membered heteroaryl containing one, two, three or four, preferably one, two or three nitrogen atoms, wherein the heteroaryl can be attached via C or N, if present: 6-ring heteroaryl groups which contain, in addition to carbon atoms, one to four or .
  • One, two or three nitrogen atoms may contain as ring members, eg Pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1, 2,3-triazinyl, 1, 2,4-triazinyl, 1, 3,5-triazinyl, especially 2-pyridinyl, 3-pyridinyl, 4-
  • novel compounds of this invention contain chiral centers and are generally obtained in the form of racemates or as diastereomeric mixtures of erythro and threo forms.
  • the erythro and threo diastereomers can be separated in the compounds of the invention, for example, due to their different solubility or by column chromatography and isolated in pure form. From such uniform pairs of diastereomers can be obtained by known methods uniform enantiomers.
  • antimicrobial agents can be used both the uniform diastereomers or enantiomers as well as their resulting in the synthesis of mixtures. The same applies to the fungicides.
  • the invention therefore relates both to the pure enantiomers or diastereomers and to mixtures thereof.
  • the (R) and (S) isomers and the racemate are the Compounds according to the invention, in particular of the formula I or II, having chiral centers.
  • Suitable compounds according to the invention, in particular of the formula I or II also include all possible stereoisomers (cis / trans isomers) and mixtures thereof.
  • the compounds according to the invention in particular of the formula I or II, can be present in various crystal modifications whose biological activity can be different. These are included in the scope of the present invention.
  • B is phenyl which contains one substituent L in the 2-position and one, two or three further independently selected substituents L.
  • B is according to a preferred B-1
  • # represents the point of attachment of the phenyl ring to the oxirane ring
  • L 1 is selected from halogen, Ci-C 4 -alkyl, Ci-C4-haloalkyl, -C 4 -alkoxy, C d- 4 -haloalkoxy and Ci-C4-haloalkylthio, preferably selected from F, Cl, methyl, ethyl, methoxy, ethoxy, CF 3, CHF 2, OCF 3, OCHF 2 and SCF 3;
  • L 2 is selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C 4 alkoxy, C d- 4 -haloalkoxy and Ci-C4-haloalkylthio, preferably selected from F, Cl, methyl , ethyl, methoxy, ethoxy, CF 3, CHF 2, OCF 3, OCHF 2 and SCF 3;
  • L 3 is independently selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, -C 4 - alkoxy, Ci-C4 haloalkoxy, and Ci-C4-haloalkylthio, preferably selected from F, Cl, methyl, ethyl, methoxy, ethoxy, CF 3, CHF 2, OCF 3, OCHF 2 and SCF 3; and m is O, 1 or 2.
  • L 1 is F. According to another preferred embodiment, L 1 is Cl. According to another preferred embodiment, L 1 is methyl. According to yet another preferred embodiment, L 1 is methoxy. According to yet another preferred embodiment, L 1 represents CF 3 . According to yet another preferred embodiment, L 1 is OCF 3 or OCHF 2 . According to a preferred embodiment, in the compounds of the formula I according to the invention therefore B is phenyl which in the 2-position is a substituent selected from F, Cl, CH 3 , OCH 3 , CF 3 , CHF 2 , OCF 3 and OCHF 2 , and one or two further independently selected substituents L. In a preferred embodiment, L 2 is F. According to another preferred embodiment, L 2 is Cl. According to a further preferred embodiment, L 2 is methyl. According to yet another preferred embodiment, L 2 is methoxy. In yet another preferred embodiment, L 2 is CF 3. According to yet another preferred embodiment, L 2 is OCF 3 or OCHF 2 .
  • L 3 is F. According to another preferred embodiment, L 3 is Cl. According to a further preferred embodiment, L 3 is methyl. In yet another preferred embodiment, L 3 is methoxy. In yet another preferred embodiment, L 3 is CF 3 . According to yet another preferred embodiment, L 3 is OCF 3 or OCHF 2 .
  • B is therefore a disubstituted phenyl ring.
  • B is a 2,3-disubstituted phenyl ring.
  • the phenyl ring B is 2,4-disubstituted.
  • the phenyl ring B is 2,5-disubstituted.
  • the phenyl ring is 2,6-disubstituted.
  • B is phenyl which contains one substituent L in the 2-position and exactly one further substituent L, where L is in each case independently selected from F, Br, cyano, nitro, cyanato (OCN), C 1 -C 8 -alkyl, ci C 8 haloalkyl, phenyl-Ci-C 6 alkyloxy, C 2 -C 8 - alkenyl, C 2 -C 8 haloalkenyl, C 2 -C 8 -alkyl kinyl, C 2 -C 8 haloalkynyl, C4-Cio -alkadienyl, C4-Cio-Halogenalkadienyl, Ci-C8-alkoxy, Ci-C8-haloalkoxy, Ci-C8-alkylcarbonyl oxy, Ci-C 8 alkylsulfonyloxy, C 2 -C 8 alkenyloxy, C 2 - C 8 haloalkeny
  • the phenyl ring B is 2,3,5-trisubstituted.
  • the phenyl ring B is 2,3,4-trisubstituted.
  • the phenyl ring B is 2,4,5-trisubstituted. Preference is given to the compounds of the formula I in which B is phenyl, which is a
  • Lo 2 represents L or hydrogen, with the proviso that Lm 1 , Lp, Lm 2 and Lo 2 are not all hydrogen at the same time.
  • Lo 1 is preferably F, Cl, CH 3 , C 2 H 5 , CF 3 , OCH 3 , OC 2 H 5 , OCF 3 , OCHF 21 SCF 3 ; most preferably F, Cl, CH 3, OCH 3, CF 3, CHF 2, OCF 3 and OCHF 2; particularly preferably F, Cl, CH 3 .
  • Lm 1 is preferably hydrogen, F, Cl, CH 3 , C 2 H 5 , CF 3 , OCH 3 , OC 2 H 5 , OCF 3 ,
  • OCHF 21 SCF 3 particularly preferably hydrogen, F, Cl, CH 3 , OCH 3 , CF 3 , CHF 2 , OCF 3 and OCHF 2 ; particularly preferably hydrogen, F, Cl, CH 3 .
  • Lp is preferably hydrogen, F, CH 3 , C 2 H 5 , CF 3 , OCH 3 , OC 2 H 5 , OCF 3 ,
  • OCHF 21 SCF 3 particularly preferably hydrogen, F, CH 3 , OCH 3 , CF 3 , CHF 2 , OCF 3 and OCHF 2 ; particularly preferably F, CH 3 .
  • L m 2 is preferably hydrogen, F, Cl, CH 3 , C 2 H 5 , CF 3 , OCH 3 , OC 2 H 5 , OCF 3 ,
  • OCHF 21 SCF 3 particularly preferably hydrogen, F, Cl, CH 3 ; particularly preferably hydrogen.
  • Lo 2 is preferably hydrogen, F, Cl, CH 3 , C 2 H 5 , CF 3 , OCH 3 , OC 2 H 5 , OCF 3 ,
  • OCHF 21 SCF 3 particularly preferably hydrogen, F, Cl, CH 3 ; particularly preferably hydrogen.
  • the respective independently selected substituents L are selected from F, Cl, CH3, OCH3, CF3, CHF2, OCF3 and OCHF2, with the proviso that L in the 4-position of B is not chlorine.
  • variable B is phenyl which contains in the 2-position a substituent selected from F, Cl, CH3, OCH3, CF3, CHF2, OCF3 and OCHF2 and (1) either in the 4-position a substituent L * or (2) in the 3, 5- or 6-position a substituent L or
  • each independently selected variable L in the compounds of the formula I selected from halo- gen, Ci-C 4 -alkyl, Ci-C4-haloalkyl, -C 4 -alkoxy, Ci-C4 haloalkoxy, and C1 -C4- haloalkylthio
  • L * is selected from fluorine, bromine, iodine, Ci-C4-alkyl, Ci-C 4 -HaIo- genalkyl, Ci-C 4 alkoxy, Ci-C4-haloalkoxy and Ci-C 4 haloalkylthio.
  • the respectively independently selected variable L is selected from F, Cl, CH 3 , C 2 H 5 , CF 3 , OCH 3 , OC 2 H 5 , OCF 3 , OCHF 2 and SCF 3, L * and selected from F, CH 3, C 2 H 5, CF 3, OCH 3, OC 2 H 5, OCF 3, OCHF 2 and SCF.
  • A is C 1 -C 8 -alkyl, in particular methyl or ethyl.
  • A is Ci-Cs-haloalkyl, in particular CF 3 .
  • A represents unsubstituted phenyl.
  • A represents phenyl containing one, two, three or four, especially one, two or three, independently selected substituents L.
  • the phenyl ring is monosubstituted with a substituent L, where L is selected according to a specific embodiment of this embodiment. is located in the para position to the point of attachment of the phenyl ring with the oxirane ring.
  • the phenyl ring is disubstituted with two independently selected substituents L.
  • A is a phenyl ring which contains a substituent L in the para position and also has another independently selected substituent L.
  • the phenyl ring is 2,4-disubstituted.
  • the phenyl ring is 3,4-disubstituted.
  • A is a phenyl ring which contains a substituent L in the para position and also contains two further independently selected substituents L.
  • the phenyl ring is 2,3,4-trisubstituted.
  • the phenyl ring is 2,4,6-trisubstituted.
  • L independently has the following preferred meanings:
  • a 1 is hydrogen, hydroxy, Ci-C 4 -alkyl, Ci-C4-haloalkyl;
  • a 2 is one of the groups mentioned at A 1 or C 1 -C 4 -alkoxy, C 1 -C 4 -
  • Haloalkoxy Cs-C ⁇ -cycloalkyl, Cs-C ⁇ -halocycloalkyl, C3-C6-cycloalkoxy or Cs-C ⁇ -halocycloalkoxy;
  • a 3 , A 4 independently of one another are hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl;
  • R L is halogen, cyano, nitro, Ci-C 4 -alkyl, C-4 haloalkyl, Ci-C 4 - alkoxy, Ci-C4-haloalkoxy, Cs-C ⁇ cycloalkyl, Cs-C ⁇ -halocycloalkyl, amino , Ci-Cs-alkylamino, di-Ci-Cs-alkylamino.
  • L is independently selected from halogen, NO2, amino, Ci-C 4 - alkyl, Ci-C4-haloalkyl, -C 4 -alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylamino, di- Ci-C4-alkylamino , Thio and C 1 -C 4 -alkylthio.
  • L is independently selected from halogen, Ci-C4-alkyl, Ci-C 4 - haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and Ci-C4-halogenoalkylthio.
  • L is independently selected from F, Cl, Br, CH 3, C 2 H 5, iC 3 H 7, tC 4 H 9, OCH 3, OC 2 H 5, CF 3, CCl 3, CHF 2 , CCIF 2 , OCF 3 , OCHF 2 and SCF 3 , in particular selected from F, Cl, CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , CF 3 , CHF 2 , OCF 3 , OCHF 2 and SCF 3 , especially selected from F, Cl, CH 3, C 2 H 5, CF 3, OCH 3, OC 2 H 5, OCF 3, OCHF 2 and SCF.
  • L is independently selected from F, Cl, CH 3, OCH 3, CF 3, OCF 3 and OCHF. 2 It may be preferred that L is independently F or Cl.
  • D is a group SR, where R is hydrogen (compounds 1-1).
  • D is a group SR, where R is C 1 -C 4 -alkyl, in particular methyl or ethyl, preferably methyl.
  • R 3 is hydrogen.
  • R 3 is C 1 -C 4 -alkyl, in particular methyl or ethyl, preferably methyl.
  • R 3 is C 1 -C 4 -haloalkyl, in particular trifluoromethyl.
  • R 3 is C 1 -C 4 alkoxy, especially methoxy or ethoxy.
  • R 3 is methylamino, dimethylamino, ethylamino, diethylamino or phenylamino.
  • D is a group SR, where R is CN.
  • D is a group SR, where R is SO 2 R 4 and R 4 is C 1 -C 4 -alkyl, phenyl-C 1 -C 4 -alkyl or phenyl, where each of the phenyl groups is unsubstituted or substituted are independently selected from halo and C 1 -C 4 alkyl by one, two or three groups.
  • D is a group SM, wherein M is an alkali metal cation, one equivalent of an alkaline earth metal cation, one equivalent of a copper, zinc, iron or nickel cation or an ammonium cation of the formula (E )
  • Z 1 and Z 2 are independently hydrogen or C 1 -C 4 -alkyl; and Z 3 and Z 4 are independently hydrogen, C 1 -C 4 alkyl, benzyl or phenyl.
  • M represents Na, 1 ⁇ 2Cu, 3Fe, HN (CH 3 ) S, HN (C 2 H 5 ) S, N (CHs) 4 or H 2 N (C 3 HT) 2 , in particular Na, 1/2 Cu, HN (CHs) 3 or HN (C 2 Hs) 3 , especially Na, 1/2 Cu, HN (CHs) 3 or HN (C 2 Hs) 3 .
  • D stands for a group D1
  • both A and B have the same meaning in compounds 1-2.
  • D is a group Dil, where # is the point of attachment to the triazolyl ring and Q, R 1 and R 2 are as defined herein or preferably defined:
  • a and D corresponds in each case to one line of Table A (compounds I.16aA-1 to I.16aA-2295) Table 17a
  • a and D corresponds in each case to one row of Table A (Compounds I.17aA-1 to I.17aA-2295).
  • Table 18a Compounds I, wherein B is 2-fluoro-5-methylphenyl and the combination of
  • a and D corresponds in each case to one row of Table A (compounds I.34aA-1 to I.34aA-2295)
  • Table 39a Compounds I, where B is 2-fluoro-3- (trifluoromethyl) phenyl and the combination of A and D corresponds in each case to one row of Table A (compounds I.39aA-1 to I.39aA-2295) Table 40a
  • Table 47a Compounds I in which B is 2-fluoro-4- (trifluoromethoxy) phenyl and the combination of A and D corresponds in each case to one row of Table A (Compounds I.47aA-1 to I.47aA-2295)
  • Table 60a Compounds I, where B is 2-fluoro-3- (trifluoromethylthio) phenyl and the combination of A and D corresponds in each case to one row of Table A (Compounds 1.6OaA-I to 1.60aA-2295) Table 61a
  • a and D corresponds in each case to one row of Table A (compounds I.103aA-1 to I.103aA-2295) Table 104a
  • a and D corresponds in each case to one line of Table A (Compounds I.104aA-1 to I.104aA-2295).
  • Table 105a Compounds I, wherein B is 2-chloro-4-methylphenyl and the combination of
  • Table 1 18a Compounds I in which B is 2-chloro-3-methoxyphenyl and the combination of A and D corresponds in each case to one row of Table A (compounds 1,118aA-1 to 1,118aA-2295)
  • Table 123a Compounds I in which B is 2- (trifluoromethyl) -5-chlorophenyl and the combination of A and D corresponds in each case to one row of Table A (Compounds I.123aA-1 to I.123aA-2295) Table 124a
  • Table 126a Compounds I in which B is 2-chloro-4- (trifluoromethyl) phenyl and the combination of A and D corresponds in each case to one row of Table A (Compounds I.126aA-1 to I.126aA-2295)
  • Table 139a Compounds I, where B is 3- (difluoromethoxy) -4-chlorophenyl and the combination of A and D corresponds in each case to one row of Table A (compounds I.139aA-1 to I.139aA-2295)
  • Table 144a Compounds I, where B is 2- (trifluoromethylthio) -4-chlorophenyl and the combination of A and D corresponds in each case to one line of Table A (compounds I.144aA-1 to I.144aA-2295) Table 145a
  • Table 152a Compounds I, where B is 2,3,6-trichlorophenyl and the combination of A and D corresponds in each case to one row of Table A (compounds I.152aA-1 to I.152aA-2295)
  • Table B corresponds (Compounds 1-2.1 bB-1 to 1-2.1 bB-255) Table 2b
  • Line of Table B corresponds (compounds I-2.65bB-1 to I-2.65bB-255)
  • Line of Table B corresponds (compounds I-2.70bB-1 to I-2.70bB-255)
  • Line of Table B corresponds (compounds I-2.75bB-1 to I-2.75bB-255)
  • Line of Table B corresponds (compounds I-2.79bB-1 to I-2.79bB-255)
  • Table 106b Compounds I-2, in which both B are 2-chloro-5-methylphenyl and A corresponds in each case to one row of Table B (Compounds 1-2.106bB-1 to 1-2.106bB-255)
  • Table 141b Compounds I-2, wherein both B are 2-chloro-4- (difluoromethoxy) phenyl and A corresponds in each case to one row of Table B (Compounds 1-2.141 bB-1 to I-2)
  • Table 157b Compounds I-2, wherein both B are 2,3,6-trimethylphenyl and A corresponds in each case to one row of Table B (Compounds 1-2.157bB-1 to 1-2.157bB-255)
  • Table B corresponds (compounds N.2cB-1 to N.2cB-255)
  • Table 12c Compounds II, wherein B is 2-methyl-3-fluorophenyl and A corresponds in each case to one row of Table B (Compounds N.12cB-1 to N.12cB-255)
  • Table 40c Compounds II, wherein B is 2-fluoro-4- (trifluoromethyl) phenyl and A corresponds in each case to one row of Table B (Compounds N.40cB-1 to N.40cB-255)
  • Table B corresponds (compounds N.63cB-1 to N.63cB-255)
  • Table B corresponds (compounds N.68cB-1 to N.68cB-255)
  • Table B corresponds (compounds N.72cB-1 to N.72cB-255)
  • Table B corresponds (compounds N.77cB-1 to N.77cB-255)
  • Line of Table B corresponds (compounds N.86cB-1 to N.86cB-255)
  • Line of Table B corresponds (compounds N.91cB-1 to N.91 cB-255)
  • Table 1 10c Compounds II, wherein B is 2-ethyl-3-chlorophenyl and A corresponds in each case to one row of Table B (Compounds 11.11 OcB-1 to 11.110cB-255)

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  • Agronomy & Crop Science (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne des azolylméthyloxiranes de formule (I) dans laquelle les variables A, B et D ont les significations indiquées dans les revendications et la description de l'invention.
EP08861314A 2007-12-19 2008-12-15 Azolylméthyloxiranes, leur utilisation et agents les contenant Withdrawn EP2235005A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08861314A EP2235005A2 (fr) 2007-12-19 2008-12-15 Azolylméthyloxiranes, leur utilisation et agents les contenant

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Application Number Priority Date Filing Date Title
EP07123713 2007-12-19
PCT/EP2008/067545 WO2009077500A2 (fr) 2007-12-19 2008-12-15 Azolylméthyloxiranes, leur utilisation et agents les contenant
EP08861314A EP2235005A2 (fr) 2007-12-19 2008-12-15 Azolylméthyloxiranes, leur utilisation et agents les contenant

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EP2235005A2 true EP2235005A2 (fr) 2010-10-06

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US (1) US20100273651A1 (fr)
EP (1) EP2235005A2 (fr)
JP (1) JP2011506543A (fr)
CN (1) CN101952279A (fr)
AR (1) AR069836A1 (fr)
BR (1) BRPI0821746A2 (fr)
CL (1) CL2008003867A1 (fr)
PE (1) PE20091179A1 (fr)
TW (1) TW200930300A (fr)
UY (1) UY31562A1 (fr)
WO (1) WO2009077500A2 (fr)

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Also Published As

Publication number Publication date
JP2011506543A (ja) 2011-03-03
WO2009077500A2 (fr) 2009-06-25
CN101952279A (zh) 2011-01-19
PE20091179A1 (es) 2009-09-03
CL2008003867A1 (es) 2010-01-11
UY31562A1 (es) 2009-07-17
AR069836A1 (es) 2010-02-24
TW200930300A (en) 2009-07-16
WO2009077500A3 (fr) 2009-11-12
US20100273651A1 (en) 2010-10-28
BRPI0821746A2 (pt) 2015-06-16

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