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GB2132195A - 1-Azolyl-2-aryl-3-fluoroalkan- 2-ols as microbicides - Google Patents

1-Azolyl-2-aryl-3-fluoroalkan- 2-ols as microbicides Download PDF

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GB2132195A
GB2132195A GB08332617A GB8332617A GB2132195A GB 2132195 A GB2132195 A GB 2132195A GB 08332617 A GB08332617 A GB 08332617A GB 8332617 A GB8332617 A GB 8332617A GB 2132195 A GB2132195 A GB 2132195A
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triazol
phenyl
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hydrogen
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Elmar Sturm
Alfred Meyer
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • C07D233/56—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals

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  • Life Sciences & Earth Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

SPECIFICATION 1 -Azolyl-2-aryl-3-fluoroalkan-2-ols as microbicides The present invention relates to novel, substituted 1 -azoyl-2-aryl-3-fluroalkan-2-ols and ethers thereof, of the formula I below, and to acid addition salts, quaternary azolium salts and metal complexes thereof. The invention furthermore relates to the preparation of these substances and microbial compositions containing at least one of these compounds as the active substance. The invention also relates to the preparation of the above compositions and to the use of the active substances or of the compositions for the control of harmful microorganisms, preferably fungi which are harmful to plants.
The compounds according to the invention are those of the general formula I
in which Az is 1 H-1 ,2,4-triazole, 4H-1 ,2,4-triazole or 1 H-imidazole; Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl, phenoxyphenyl and naphthyl; R1 is hydrogen, C,-C4-alkyl, C3-C5-alkenyl or benzyl;R2 is hydrogen, fluorine or C,-C6-alkyl and R3 is hydrogen, fluorine, C,-C6-alkyl, C,-C6-haloalkyl, C,-C6-alkoxy, C,-C6alkylthio, phenyl, phenoxy, phenylthio or C3-C7-cycloalkyl, and each aromatic substituent or aromatic moiety of a substituent is unsubstituted or mono- or poly-substituted by halogen, C,-C6-alkyl, C,-C4-alkoxy, C,-C4-haloalkyl, nitro and/or cyano; including the acid addition salts, quaternary azolium salts and metal complexes.
The term alkyl by itself or as a constituent of another substituent is to be understood as meaning, for example, one of the following groups, depending on the number of carbon atoms stated: methyl, ethyl, propyl, butyl, pentyl, hexyl and the like and their isomers, for example isopropyl, isobutyl, tert.-butyl, isopentyl and the like. Haloalkyl is a monohalogenated to perhalogenated alkyl substituent, for example CHCl2, CHF2, CH2CL, CCl3, CH2F, CH2CH2CI CH2Br and the like, in particular CF3. Here and in the following text, halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Alkenyl is, for example, prop-1-enyl, allyl, but-1-enyl, but-2-enyl or but-3-enyl.Naphthyl is a- or naphthyl The present invention thus relates to the free compounds of the formula I and acid addition salts, quaternary azolium salts and metal complexes thereof. The free compounds, in particular the 1 H-1 2,4-triazole derivatives, are preferred in the context of formula I.
Examples of salt-forming acids are inorganic acids, such as hydrogen halide acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, as well as sulfuric acid, phosphoric acid, phosphorous acid and nitric acid, and organic acids, such as acetic acid, trifiuoroacetic acid, trichloroacetic acide, propionic acid, formic acid, benzenesulfonic acid, ptoluenesulfonic acid or methanesulfonic acid.
Metal complexes of the formula I consist of the basic organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates and the like of the elements of the third and fourth main group, such as aluminium, tin or lead, and of the first to eight sub-group, such as chromium, manganese, iron, cobalt, nickel, zirconium, copper, zinc, silver, mercury and the like. The sub-group elements of the 4th period are preferred. The metals can be in the various valences with which they are associated. The metal complexes of the formula I can be a mononuclear or polynuclear, i.e. they can obtain one or more organic molecule components as ligands. Complexes with the metals copper, zinc, manganese, tin and zirconium are preferred.
The compounds of the formula I are oils, resins or, chiefly solids, which are stable at room temperature and are distinguished by very useful microbial properties. They can be used preventatively and curatively in the agricultural sector or related fields for controlling microorganisms which damage plants, the triazolymethyl derivatives in the context of the formula I being preferred. The active substances of the formula I according to the invention are distinguished by a very good phytofungicidal action and problem-free application when used in low concentrations. Moreover, they also have a growth-regulating action in particular a growthinhibiting action, especially on tropical cover crops.
The following groups of substances are preferred, because of their marked microbicidal action, in particular their phytofungicidal action: compounds of the formula I in which Az is 1 H-1,2,4- triazole or 1 H-imidazole; Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl and phenoxyphenyl, R, is hydrogen; R2 is hydrogen, fluorine or C,-C3-alkyl; and R3 is hydrogen, fluorine, C,-C4-alkyl, C,-C3-haloalkyl, C,-C3-alkoxy, C,-C3- alkylthio, phenyl, phenyloxy or phenylthio, each phenyl moiety being unsubstituted or substituted by fluorine, chlorine, bromine, methyl, methoxy, CF3, NO2 and/or cyano; including the acid addition salts, quaternary azolium salts and metal complexes.
Particularly preferred compounds of the formula I within this group are those in which Az is 1H-1,2,4-triazole; Ar is phenyl or phenoxyphenyl which is unsubstituted or, preferably, substituted in the 2- and/or 4-position by methyl or halogen, preferably fluorine or chlorine; R, is hydrogen; R2 is hydrogen, fluorine or methyl; and R3 is hydrogen, fluorine, C,-C4-alkyl or a radical from the series comprising phenyl, phenoxy and phenylthio which is substituted by fluorine, chlorine and/or bromine.
Examples of specific particularly preferred substances from a fungicidal point of view are: 1 (1H-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluorobutan-2-ol, 1-(1H-1,2,4-triazol-1-yl)-2-(2chloro-4-fluorophenyl)-3-fluorobutan-2-ol, 1-(1H-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoropentan-2-ol, 1 -(1 H-i , 2,4-triazol- 1 -yl)-2-(2, 4-dichlorophenyl)-3-fluoro-4-methylpentan-2-ol, 1 (1 H- 1,2, 4-triazol-1 -yl)-2-(2-chloro-4-fluorophenyl)-3-fluoropentan-2-ol. 1-(1 H-1,2,4-triazol-1 -yl)-2 (2,4-dichlorophenyl)-3-(4-chlorophenoxy)-3-fluoropropan-2-ol, 1-(1 H-1,2,4-triazol-l -yl)-2-[p-(4- chlorophenoxy)phenyl]-3-fluoropropen-2-ol, 1-(1H-1,2,4-triazol-1-yl)-2-(4-dfludorophenyl)-3,3,3trifluoropropan-2-ol, 1(1 H-i , 2,4-triazol-1 -yl)-2-(2,4-dichlorophenyl)-3,3,3-trifluoropropan-2-ol. 1 (1H-1,2,4-triazol-1 -yl)-2-(4-chlorophenyl)-3-fluorohexan-2-ol, 1-(1 H- 1, 2,4-triazol- 1 -yl)-2-(2, 4-di chlorophenyl)-3-fluorohexan-2-ol, 1-(1 H- , 2,4-triazol- 1 -yl)-2-(2,4-dichlorophenyl-3, 3-difluoropen- tan-2-ol, 1-(1 H-1 ,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoro-4-methylpentan-2-ol, 1 -(1 H- 1,2,4-triazol-1-yl)-2-[p-(4-bromophenoxy)phenyl]-3,3-difluoropropan-2-ol, 1-(1H-1,2,4-triazol-1yl)-2-[p-(4-fluorophenoxy)phenyl]-3,3-difluoro-propan-2-ol, 1-(1H-1,2,4-triazol-1-yl)-2-[p-(4-chlorophenoxy)phenyl]-3,3-difluoropropan-2-ol and 1 -(i H-i , 2,4-triazol- 1 -yl)-2-[p-(4-chlorophenoxy)2-methylphenyl]-2-hydroxy-3-fluoropropane.
The compounds of the formula I are prepared by a process which comprises first reacting an oxirane of the formula II
with an azole of the formula Ill M-Az (III) to give a compound of the formula la
and, if required, converting the alcohol la into an ether of the formula I in the conventional manner, for example by reaction with a compound of the formula IV R1-W (IV) in which formulae la, 11, Ill and IV, the substituents R1, R2, R3, Ar and Az are as defined under formula I, M is hydrogen or, preferably, a metal atom, in particular an alkali metal atom, such as Ei Na or K, and W is OH or a conventional leaving group. Conventional leaving groups are known from the literature.
If appropriate, the reaction of II with Ill to give la is carried out in the presence of condensing agents or acid-binding agents. Suitable agents are organic and inorganic bases, for example tertiary amines, such as trialkylamines (trimethylamine, triethylamine, tripropylamine and the like), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine and the like), oxides, hydrides and hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals (CaO, BaO, NaOH, KOH, NaH, Ca(OH)2, KHC03, NaHC03, Ca(HcO3)2, K2CO3, and Na2CO3) and alkali metal acetates, such as CH3COONa or CH3COOK. Moreover, alkali metal alcoholates, such as C2H50Na, C3H7-nONa and the like, are also suitable.In some cases, it may be advantageous if the free azole Ill (M = hydrogen) is first converted into the corresponding salt, for example in situ with an alcoholate, and then to react the salt with the oxirane of the formula 11. In the preparation of the 1,2,4-triazole derivatives, 1,3,4-triazolyl isomers are generally also formed in a parallel reaction, and these can be separated from one another in a conventional manner, for example with different solvents.
The reaction (II with Ill to give la) is preferably carried out in an organic solvent which is relatively polar but inert in the reaction, for example N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and the like. Such solvents can be used in combination with other solvents which are inert in the reaction, for example benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene and the like. The reaction temperatures are in a temperature range from 0" to 1 50 C, preferably 20 to 1 00 C.
This reaction (II with Ill to give la) can furthermore be carried out analogously to reactions which are already known for other oxiranes with azoles (cf. German Offenlegungsschrift 2,912,288).
In the part reactions mentioned, the intermediates can be isolated from the reaction medium and, if desired, purified by one of the generally conventional methods,. for example by washing, digestion, extraction, crystallisation, chromatography, distillation and the like, before the further reaction.
In cases where W in formula IV is a conventional leaving group, the further reaction of la to give I is carried out in the absence or, preferably, in the presence of a solvent which is inert in the reaction.
Examples of suitable solvents are the following: N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoric acid triamide, dimethylsulfoxide, 2-methyl-2-pentanone and the like.
Mixtures of these solvents with one another or with other conventional inert organic solvents, for example with aromatic hydrocarbons, such as benzene, toluene, the xylenes and the like, can also be used. In some cases it may prove advantageous to carry out the reaction in the presence of a base, for example an alkali metal hydride, hydroxide or carbonate, in order to accelerate the rate of reaction. However, it may also be advantageous first to convert the alcohol of the formula la (R, = OH) into a suitable metal salt in a manner which is known per se, for example by reaction with a strong base.
Examples of suitable strong bases are alkali metal hydrides and alkaline earth metal hydrides (Na H, KH, CaH2 and the like) and alkali metal-organic compounds, for example butyl-lithium or an alkali metal tert.-butoxide, and alkali metal hydroxides, such as NaOH or KOH, can moreover also be used if the reaction is carried out in an aqueous two-phase system in the presence of a phase transfer catalyst.
However, it is also possible first to convert the alcohol of the formula la into an alkali metal alcoholate in a conventional manner before the further reaction, and then to react the alcoholate with a compound of the formula IV (in which W is a leaving group), the reaction advantageously being carried out in the presence of a crown ether. If M = K, 1 8-crown-6, in particular, is present; and if M = Na, 1 5-crown-5, in particular, is present. The reaction is advantageously carried out in a medium which is inert in the reaction. Examples of suitable solvents are ethers.
and ether-like compounds, for example di-lower alkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether and the like), tetrahydrofuran and dioxane, and aromatic hydrocarbons, such as benzene, toluene or the xylenes.
The following solvents are examples of the organic water-immiscible phase: aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, the xylenes and the like, halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, 1,2-dichloroethane, tetrachloroethylene and the like, or aliphatic ethers, such as diethyl ether, diisopropyl ether, t-butyl methyl ether and the like. Examples of suitable phase transfer catalysts are: tetraalkylammonium halides, bisulfates or hydroxides, such as tetrabutylammonium chloride, bromide or iodide; triethylbenzylammonium chloride or bromide; tetrapropylammonium chloride, bromide or iodide; and the like. Possible phase transfer catalysts include phosphonium salts.The reaction temperatures are in general between 30 and 1 30 C, or at the boiling point of the solvent or solvent mixture.
In cases where W in formula IV is a hydroxyl group, a condensation reaction is advantage ously carried out. The two reactants are refluxed in a suitable solvent.
In principle, any solvent which is inert towards the reactants and, advantageously, forms an azeotrope with water can be used here. Examples of suitable solvents here are aromatic hydrocarbons, such as benzene, toluene and the xylenes, or halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetra-chloroethylene and chlorobenzene, as well as ether-like compounds, such as tert.-butyl methyl ether, dioxane and the like. In some cases, the compound of the formula Ill itself can be used as the solvent.
This condensation reaction is advantageously carried out in the presence of a strong acid, for example paratoleunesulfonic acid, at the boiling point of the azetropic mixture.
To prepare the ethers of the formula I, it is also possible first to replace the free OH group in the compounds of the formula la by one of the above conventional leaving groups W and then to react the product with a compound of the formula IV (where W= OH).
The starting substances of the formula Ill are generally known, or they can be prepared by methods which are known per se.
The oxiranes of the formula II are novel, and are intermediates which have been developed particularly for the preparation of the useful active substances of the formula I. Because of their structural nature, they can be converted into the compounds of the formula la in a simple manner, and, moreover, some of the compounds of the formula II have a fungicidal activity towards harmful fungi from the families of Ascomycetes, Basidiomycetes or Fungi imperfecti.
Epoxides of the formula Il can be prepared from ketones of the formula V
in a manner which is known per se by reaction with dimethylsulfonium methylide or dimethyloxosulfonium methylide (Corey and Chaykovsky, JACS, 1962, 84, 3782).
The ketones of the formula V are accessible by methods which are known per se from the literature (cf. J. Leroy, J. Org. Chem. 46, 206 (1981) or Houben-Weyl, volume V/3, page 211), from the corresponding known abromo-ketones by conventional replacement of the bromine by fluorine, or they can also be prepared by acylation of the aromatic on which they are based with fluorinated carboxylic acid derivatives, for example by a Friedel-Crafts reaction.
In principle, unless expressly specified in a particular case, one or more solvents or diluents which are inert in the reaction can be present in the preparation of all the starting substances, intermediates and end products mentioned here. Examples of suitable solvents or diluents are aliphatic and aromatic hydrocarbons, such as benzene, toluene, the xylenes and petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; ethers and ether-like compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether and the like), anisole, dioxane and tetrahydrofuran; nitriles, such as acetonitrile and propionitrile;N,N-dialkylated amides, such as dimethylformamide; dimethylsulfoxide; ketones, such as acetone, diethyl ketone and methyl ethyl ketone, and mixtures of these solvents with one another. In some cases, it may also be advantageous to carry out the reaction or part steps of a reaction under a protective gas atmosphere and/or in absolute solvents. Suitable protective gases are inert gases, such as nitrogen, helium, argon or, in certain cases, also carbon dioxide.
The compounds of the formula I
always have an asymmetric C atom c* in the position adjacent to the substituents Ar and ORa and can therefore exist in two enantiomeric forms. In general, a mixture of the two enantiomers is formed in the preparation of these substances, and this can be split into the pure optical anitipodes in a conventional manner, for example by fractional crystallisation of salts with strong optically active acids. The enantiomers can have different biological actions; thus, for example, the fungicidal action can be in the foreground in one form and the plant growth-regulating action can be in the foreground in the other form. A gradual difference in activity may also occur in the same action spectrum.If the radicals R2 and R3 are different, the molecule contains a further centre of asymmetry (*), which leads to the existence of diastereomeric mixtures (threoand erythro-forms), which can be separated by means of physical methods.
The present invention relates to all the pure enantiomers and diastereomers and mixtures thereof with one another.
The preparation process described, including all the part steps' is an important component of the present invention.
It has been found, surprisingly, that compounds of the formula I have a microbicidal spectrum against phytopathogenic fungi and bacteria which is very favourable for practical requirements.
They have very advantageous curative, systemic and, in particular, preventative properties and can be used for protecting numerous crop plants. The microorganisms which occur on plants or parts of plants (fruit, blossom, foliage, stems, tubers and roots) of various useful crops can be checked or destroyed with the active substances of the formula I, the additional future growth of parts of plants also remaining protected from such microorganisms.
The active substances of the formula I are effective against phytopathogenic fungi belonging to the following classes: Fungi imperfecti (for example, Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); and Basidiomycetes (for example the general Hemileia, Rhizocotonia and Puccinia); and they are particularly active against the class of Ascomycetes (for example Venturia, Podosphaera, Erysiphe, Monilinia and Uncinula). Moreover, the compounds of the formula I have a systemic action. They can furthermore be used as dressings for the treatment of seed (fruit, tubers and seed) and plant seedlings, for protection from fungal infections and against phytopathogenic fungi which occur in the soil.
The invention thus also relates to microbicidal compositions and to the use of the compounds of the formula I for the control of phytophathogenic microorganisms, in particular fungi which are harmful to plants, and for preventative prophylaxis of an attack on plants.
The present invention furthermore also includes the preparation of agrochemical compositions which comprises intimate mixing of the active substance with one or more substances or groups of substances described in this Application. The present invention also includes a method of treating plants which comprises application of the compounds of the formula I or of the novel compositions.
The following plant species are examples of target crops in the context of this invention for the fields of indication disclosed herein: cereals: (wheat, barley, rye, oats, rice, sorghum and related species); beet (sugar-beet and fodder beet); pomaceous fruit, stone fruit and berries: (apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry); pulse: (bean, lentil, pea, soya bean); oil crops: (rape, mustard, poppy, olive, sunflower, coconut, castor, cacao and groundnut); cucumber crops: (pumpkin, cucumber, melon); fibre crops: (cotton, flax, hemp and jute); citrus fruits: (orange, lemon, grapefruit and mandarin); vegetable varieties: (spinach, lettuce, asparagus, cabbage varieties, carrot, onion, tomato, potato and paprika); laurel crops: (avocado, cinnamon and camphor); or plants such as maize, tobacco, nut, coffee, sugar cane, tea, vine, hop and banana and natural rubber crops, and ornamental plants (composites).
Active substances of the formula I are usually employed in the form of formulations and can be applied to the area or plant to be treated at the same time as or after other active substances.
These other active substances can be fertilisers, carriers of trace elements or other products which influence plant growth. They can also be, however, selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these products, if necessary together with other carriers, surfactants or other application-promoting adjuvants conventionally used in the art of formulation.
Suitable carriers and adjuvants can be solid or liquid and correspond to the substances appropriate in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
A preferred method of application of an effective substance of the formula I or of an agrochemical composition containing at least one of these active substances is applications to the foilage (leaf application). The number of applications and the amount applied depend on the threat of attack by the corresponding pathogen (species of fungus). However, the active substances of the formula I can also enter the plants through the root via the soil (systemic action) by a method in which the location of the plant is soaked with a liquid formulation or the substances are incorporated into the soil in solid form, for example in the form of granules (soil application). The compounds of the formula I can, however, also be applied to seed (coating), by a method in which the seed is either soaked in a liquid formulation of the active substance or coated with a solid formulation.Moreover, other types of application are possible in particular cases, thus, for example, controlled treatment of the plant stems or the buds.
The compounds of the formula I are used here in unmodified form or, preferably, together with the assistants conventionally used in the art of formulation, and are thus processed in a know manner to, for example, emulsion concentrates, brushable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, by encapsulation in, for example, polymeric substances. The methods of application, such as spraying, misting, dusting, scattering, brushing or watering, is chosen according to the intended aims and the given circumstances, as is the type of composition. Favourable application amounts are generally 50 g to 5 kg of active substance (AS) per hectare; preferably 100 g to 2 kg of AS/hectare, and in particular 200 9 to 600 g of AS/hectare.
The formulations, i.e. the compositions, preparations or mixtures, containing the active substance of the formula I and, if appropriate, a solid or liquid adjuvant are prepared in a known manner, for example by intimate mixing and/or grinding of the active substances with extenders, for example with solvents, solid carriers and, if necessary, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably C8 to C12 fractions, for example xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2pyrrolidone, dimethylsulfoxide or dimethylformamide, and, where relevant, epoxidised vegetable oils, such as epoxidised coconut.oil or soya bean oil; or water.
The solid carriers used, for example for dust and dispersable powders, are as a rule ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silica or highly disperse absorbent polymers may also be added to improve the physical properties. Suitable granular, adsorptive carriers for granules are porous types, for example pumice, broken brick, sepiolite or bentonite, and suitable non-adsorptive carriers are, for example, calcite or sand. A large number of pre-granulated materials of inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues, can moreover be used.
Further particularly advantageous adjuvants which promote application and can lead to a large reduction in the amount applied are natural (animal or vegetable) or synthetic phospholipids of the cephalin and licithin series, for example phosphatidylethanolamine, phosphatidylserine, phosphatidylcholine, sphingomyelin, phosphatidylinosital, phosphatidylglycerol, lysolecithin, plasmalogens or cardiolipin, which can be isolated, for example, from animal or vegetable cells, in particular from the brain, heart or liver or from egg yolks or soya bean. Examples of commercial mixtures which can be used are phosphatidylcholine mixtures. Examples of synthetic phospholipids are dioctanoylphosphatidylchloine and dipalmitoylphosphatidylcholine.
Suitable surface-active compounds, depending on the nature of the active substance of the formula I to be formulated, are non-ionic, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as meaning surfactant mixtures.
Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
Soaps are the alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), for example the Na or K salts of oleic acid or stearic acid, or of naturally occurring fatty acid mixtures, which can be obtained, for example, from coconut oil or tallow oil. The fatty acid methyl-laurin salts are also suitable.
However, so-called synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylsulfonates, are more frequently used.
The fatty sulfonates or sulfates are as a rule in the form of alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts and contain an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acryl radicals, for example the Na or Ca salt of ligninsulfonic acid, dodecylsulfuric acid ester or a fatty alcohol sulfate mixture prepared from naturally occurring fatty acids. These compounds also include the salts of sulfonic acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid radical having 8-22 C atoms. Examples of alkylarylsulfonates are the Na, Ca or triethanolmine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid/formaldehyde condensate.
Corresponding phosphates, for example salts of the phosphoric acid ester of a p-nonylphenol (4-14)-ethylene oxide adduct, are also suitable.
Particularly suitable non-ionic surfactants are polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 1 8 carbon atoms in the alkyl radical of the alkylphenols.
Other suitable non-ionic surfactants are the water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide and polypropylene glycol, ethylenediaminopolypropylene glycol and an alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.
The cationic surfactants are, in particular, quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 C atoms as N-substituent and lower alkyl or benzyl radicals, which may or may not be halogenated, or lower hydroxyalkyl radicals, as further substituents.
The salts are preferably in the form of halides, methylsulfates or ethylsulfates, and are, for example, stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants conventionally used in the art of formulation are described, inter alia, in the following publications: "Mc Cutcheon's Detergents and Emulsifiers Annual" BC Publishing Corp., Ridgewood New Jersey, 1981 and Helmut Stache "Tensid-Taschenbuch" ("Surfactant Handbook"), Carl Hauser-Verlag Munich/Vienna 1981.
The agrochemical formulations as a rule contain 0.1 to 99%, in particular 0.1 to 95%, of active substance of the formula 1, 99.0 to 1%, in particular 99.8 to 5%, of a solid or liquid adjuvant and 0 to 25%, in particular 0.1 to 25%, of a surfactant.
Whilst concentrated compositions are rather preferred as commercial products, the final user as a rule employs dilute compositions.
The compositions can also contain other adjuvants, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers and fertilisers, or other active substances, in order to achieve special effects.
Such agrochemical compositions are a component of the present invention.
The examples which follow serve to illustrate the invention in more detail without restricting it.
Temperatures are in degrees centigrade. Percentages and parts are by weight. In addition, the following symbols are used: h = hour; d = day; min. = minute; RT = room temperature; N = normality; abs = absolute, anhydrous; DMSO = dimethylsulfoxide; and DMF = dimethylformamide.
Pressures are given in millibar mb or bar b.
Preparation examples Example H7: Preparation of
1(1 H- 1,2, 4-Triazol- 1 -yl)-2-(2, 4-dichlorophenyl)-3-fluoropentan-2-ol a) Preparation of the intermediate
1 -(2, 4-Dichlorophenyl)-2-fluorobutanone 31 g of dry potassium fluoride were added to a mixture of 77 g of 1-(2,4-dichlorophenyl)-2bromobutanone and 500 mg of 1 8-crown-6 in 750 ml of absolute acetonitrile and the mixture was slowly heated to 100" to 11 0 C, while stirring. After about 48 hours, the reaction had ended (checked by gas chromatography or by NMR). The reaction solution was then poured onto 2 litres of ice-water and extracted several times with diethyl ether.The combined extracts were washed with water, dried over sodium sulfate and evaporated. Yield: 57 g of the oily product. (H-F coupling constant 50 Hz) boiling point: 77-78"/0.008 mbar.
b) Preparation of another intermediate
2-(2, 4-Dichlorophenyl)-2-( 1 -fluoropropyl)-oxirane 8 g of 80% sodium hydride were suspended in 300 ml of absolute DMSO. 68 g of trimethyloxosulfonium iodide were introduced into this suspension in portions under a nitrogen atmosphere, while stirring. Then the evolution of hydrogen had ended and the exothermic reaction had subsided, the mixture was stirred at RT for a further 2 hours. A solution of 57 g of 1-(2,4-dichlorophenyl)-2-fluorobutanone in 100 ml of tetrahydrofuran was then added dropwise in the course of 30 minutes, and the resulting mixture was stirred for 3 hours and then diluted to five times its volume with ice-eater and extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and freed from the solvent in vacuo.Yield: 55 g in the form of a brown oil.
c) Preparation of the end product: A mixture of 55 g of 2-(2,4-dichlorophenyl)-2-(1-fluoropropyl)-oxirane, 30 9 of 1,2,4-triazole and 3.5 g of potassium tert.-butylate in 500 ml of DMF was stirred at 80'C for 20 hours. The reaction solution was then cooled to RT, poured onto 2 litres of ice-water and extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and concentrated. Yield of 1-(1 H-1 ,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-34luoropentan- 2-ol: 26 9 in the form of colourless crystals. Melting point: 204-206"C.
Example H2: Preparation of
1-(1H-1,2,4-Triazole-1-yl)-2-(2,4-dichlorophenyl)-3-(4-chlorophenoxy)-3-fluoropropen-2-ol a) Preparation of the intermediate:
1 -(2, 4-Dichlorophenyl)-2-bromo-2-fluoroethanone A solution of 1 6 g of bromine in 100 ml of carbon tetrachloride was added to a solution of 20.7 g of a-fluoro-2,4-dichloroacetophenone in 100 ml of carbon tetrachloride at 40" to 45"C.
After about 1 hour, the brown solution had decolourised. Stirring was continued for another hour and the mixture was then extracted by shaking with aqueous sodium bicarbonate solution and evaporated in vacuo. The oily residue was then distilled under a high vacuum. Yield: 1 7 g.
Boiling point: 89-92"C/0.2 mbar.
b) Preparation of another intermediate:
1 -(2, 4-Dichlorophenyl)-2-(4-chlorophenoxy)-2-fluoroethanone 1 2.8 g of chlorophenol and 1 3.8 g of potassium carbonate were stirred in 200 ml of acetone for 1 hour. 28 g of 1-(2,4-dichlorophenyl)-2-bromo-2-fluoroethanone in 50 ml of acetone were added dropwise to this suspension and the mixture was refluxed for 3 hours. After cooling to RT, the colourless salt precipitate was filtered off, the acetone was removed in vacuo and diethyl ether was added. The ether solution was washed with water, dried over sodium sulfate and filtered and the filtrate was concentrated. The oily crude product crystallises after digestion with n-hexane. Yield: 21.5 g in the form of yellowish crystals. Melting point: 85-87"C.
c) Preparation of another intermediate:
2-(2, 4-Dichlorophenyl)-2-(4-chlorophenoxyfluoromethyl)-oxirane 1 g of 80% sodium hydride was stirred in 80 ml of DMSO under a nitrogen atmosphere and 10.3 9 of trimethyloxosulfonium iodine were added in portions. After the exothermic reaction had subsided, the mixture was stirred at RT for a further hour, a solution of 2-(2,4dichlorophenyl)-2-(4-chlorophenoxy)-2-fluoroethanone in 30 ml of tetrahydrofuran was then added dropwise and the resulting mixture was stirred at 25 to 30"C for a further 5 hours and then poured onto 1 litre of water. The product was extracted with diethyl ether, the extracts were washed with water, dried over sodium sulfate and filtered and the filtrate was concentrated. Yield: 1 5 9 as a yellowish oil.
d) Preparation of the end product: A solution of 1 3 g of 2-(2,4-dichlorophenyl)-2-(4-chlorophenoxyfluoromethyl)-oxirane, 4 9 of 1,2,4-triazole and 0.5 9 of potassium tert.-butylate in 100 ml of DMF was stirred at 80 to 100"C for 1 5 hours. After cooling to RT, the reaction solution was poured into 500 ml of water, whereupon the crude product separated out as an oil. The mixture was extracted with diethyl ether, the combined extracts were washed with water, dried over sodium sulfate and filtered and the filtrate was concentrated. Yield: 11 9 of an oily crude product, which crystallised on digestion with n-hexane. Yield of the purified product: 7 9. Melting point: 155-157"C.
The substances shown below can also be prepared in an analogous manner: Table 1: Compounds of the formula
Compound Ar R1 R2 R3 X Physical constant No.
1 C6H3Cl2(2,4) H H # N metting point 155-157 2 C6H3Cl2(2,4) H H C2H5 N metting point 204-206 3 C6H3Cl2(2,4) H H H N metting point 142-143 4 C6H4Cl(4) H H C3H7-n N metting point 149-151 5 C6H3Cl(2)F(4) H H H N metting point 132-133 6 # H H H N metting point 118-120 7 # H H H CH metting point 156-157 8 C6H3Cl(2,4) H H CH3 N metting point 202-204 Table 1 (Continuation)
Compound Ar R1 R2 R3 X Physical constant No.
9 # H H H N melting point 87-100 10 # H H H CH melting point 100-105 11 C6H4F(4) H F F N melting point 128-130 12 C6H3Cl2(2,4) CH3 H C2H5 N 13 C6H3Cl2(2,4) Benzyl H H N melting point 14 C6H3Cl(2)F(4) H H C2H5 N 171-173 melting point 15 # H H H N 160-163 16 # H H H CH 17 C6H3Cl(2)F(4) CH2CH=CH2 H C2H5 N Resin Table 1 (Continuation)
Compound Ar R1 R2 R3 X Physical constant No.
18 C6H3Cl2(2,4) H H CH2-CH(CH3)2 N melting point 19 C6H3Cl2(2,4) H H CH(CH3)2 N 175-176 20 C6H3F(4) # H H N Resin 21 C6H3F(4) # H H CH 22 C6H3F(4) H H CH2CH2Cl N 23 C6H3F(4) H H # N 24 C6H3Cl2(2,4) H CH3 # N 25 C6H3Cl2(2,4) CH3 H CH3 N Resin 26 C6H4Br(4) H H C2H5 N 27 C6H4Br(4) CH3 H C2H5 N Table 1 (Continuation)
Compound Ar R1 R2 R3 X Physical constant No.
28 Biphenyl-4-yl H H CH3 N 29 C6H3Cl2(2,4) H H OC2H5 N 30 C6H3Cl2(2,) H H SC3H7-n N 31 C6H4Cl(2) H H OCH3 N 32 C6H3Cl(2)F(4) H H # N melting point 33 C6H3Cl(2)F(4) H H CH3 N 163-165 melting point 34 # H H CH3 CH 146-147 melting point 35 # H H CH3 N 173-174 Table 1 (Continuation)
Compound Ar R1 R2 R3 X Physical constant No.
36 C6H3Cl2(2,4) H H C4H9-n N 37 C6H4Cl(4) H H C6H4Cl(4) N* melting point 38 C6H4Cl(2)F(4) H H CH3 N 186-198 39 C6H3Cl(2)F(4) CH3 H CH3 N 40 C6H3Cl(2)F(4) H CH3 # N melting point 41 C6H4F(4) H F F N 128-130 42 C6H3Cl2(2,4) H F F N Resin 43 # H F F N 44 # H F F N melting point 45 C6H4Cl2(2,4) H F C2H5 N 141-143 Table 1 (Continuation)
Compound Ar R1 R2 R3 X Physical constant No.
melting point 46 C6H3Cl2(2,4) H H C2H5 CH 195-196 melting point 47 C6H3Cl2(2,4) H H C3H7-n N 141-142 melting point 48 C6H3Cl2(2,4) H H C4H9-n N 101-102 melting point 49 # H H H N 118-119 melting point 50 # H H H CH 120-125 melting point 51 C6H4F(4) H H C2H5 N 141-143 melting point 52 C6H3F2(2,4) H H C2H5 N 154-156 53 # H H H N viscous oil Table 1 (Continuation)
Compound Ar R1 R2 R3 X Physical constant No.
melting point 54 # H F H N 130 melting point 55 # H F H N 70-72 melting point 56 # H F H N 125-127 57 # CH3 F H N viscous oil 58 # CH3 H CH3 N Resin 59 # CH2CH=CH2 H CH3 N 60 # H H CH3 N Table 1 (Cortinuation)
Compound Ar R1 R2 R3 X Physical constant No.
61 C6H3Cl2(2,4) H H C6H5 N 62 C6H4Cl(4) H H C6H5 N 63 # H H CH3 N 64 # H H C2H5 N 65 # CH2-C6H5 H CH3 N 66 # CH2-C6H5 H C2H5 N 67 # H H CH3 N Formulation examples for liquid active substances of the formula I (% = per cent by weight) Fl. Emulsion concentrates a) b) c) Active substance from the table 25% 40% 50% Ca Dodecylbenzenesulfonate 5% 8% 6% Castor oil polyethylene glycol ether (36 mol of ethylene oxide) 5% - - Tributylphenol polyethylene glycol ether (30 mol of ethylene oxide) - 12% 4% Cyclohexanone - 15% 20% Xylene mixture 65% 25% 20% Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
F2. Solutions a) b) c) d) Active substance from the table 80% 10% 5% 95% Ethylene glycol monomethyl ether 20% - - Polyethylene glycol MW 400 - 70% - N-Methyl-2-pyrrolidone - 20% - Expodised coconut oil - - 1% 5% Benzine (boiling range 160-190"C) - - 94% (MW = molecular weight) The solutions are suitable for application in the form of very small drops.
F3. Granules a) b) Active substance from the table 5% 10% Kaolin 94% Highly disperse silica 1% Attapulgite - 90% The active substance is dissolved in methylene chlorie, the solution is sprayed onto the carrier and the solvent is then evaporated off in vacuo.
F4. Dusts a) b) Active substance from the table 2% 5% Highly disperse silica 1% 5% Talc 97% Kaolin - 90% Ready-to-use dusts are obtained by intimate mixing of the carriers with the active substance.
F. 5 Wettable powders a) b) c) Active substance from the table 25% 50% 75% Na Ligninsulfonate 5% 5% Na Laurylsulfate 3% - 5% Na Diisobutylnaphthalenesulfonate - 6% 10% Octylphenol polyethylene glycol ether (7-8 mol of ethylen oxide) - 2% Highly disperse silica 5% 10% 10% Kaolin 62% 27% The active substance is mixed thoroughly with the adjuvants and the mixture is ground thoroughly in a suitable mill. Wettable powders are obtained, which can be diluted with water to give suspensions of any desired concentration.
F6. Emulsion concentrate Active substance from the table 10% Octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3% Ca Dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol of ethylene oxide Cyclohexanone 30% Xylene mixture 55% Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
F7. Dusts a) b) Active substance from the table 5% 8% Talc 95% Kaolin - 92% Ready-to-use dusts are obtained by mixing the active substance with the carrier and grinding the mixture on a suitable mill.
F8. Extruded granules Active substance from the table 10% Na Ligninsulfonate 2% Carboxymethylcellulose 1 % Kaolin 1% The effective substance is mixed with the adjuvants and the mixture is ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
F9. Coated granules Active substance from the table 3% Polyethylene glycol (MW 200) 3% Kaolin 94% (MW = molecular weight) The finely ground active substance is uniformly applied, in a mixer, to the kaolin, which has been moistened with polyethylene glycol. Dust-free coated granules are obtained in this manner.
F 10. Suspension concentrate Active substance from the table 40% Ethylene glycol 10% Nonylohenol polyethylene glycol ether (15 mol of ethylene oxide) 6% Na Ligninsulfonate 10% Carboxymethylcellulose 1 % 37% Aqueous formaldehyde solution 0.2% Silicone oil in the form of a 75% aqueous emulsion 0.8% Water 32% The finely ground active substance is intimately mixed with the adjuvants. A suspension concentrate is thus obtained, from which suspensions of any desired concentration can be prepared by dilution with water.
Biological examples: Example B1: Action against Puccinia graminis on wheat a) Residual-protective action 6 days after sowing, wheat plants were sprayed with a spray liquor (0.02% of active substance) prepared from a wettable powder of the active substance. After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation at 95-100% 5 relative atmospheric humidity and about 20"C for 48 hours, the infected plants were placed in a greenhouse at about 22on. The development of rust pustules was evaluated 1 2 days after the infection.
b) Systematic action 5 days after sowing, wheat plants were watered with a spray liquor (0.006% of active substance, based on the volume of soil) prepared from a wettable powder of the active substance. After 48 hours, the treated plants were infected with a uredospore suspension of the fungus, After incubation at 95-100% relative atmospheric humidity at about 20"C for 48 hours, the infected plants were placed in a greenhouse at about 22"C. The development of rust pustules was evaluated 1 2 days after the infection.
Compounds from the table had a very good action against Puccinia fungi. Untreated but infected control plants displayed a Puccinia attack of 100%. Inter alia, the compounds 1 to 10, 14, 15, 17, 19, 20, 25, 33-35, 45-51 and 53-57 inhibited the Puccinia attack to Oto 5%.
Example B2: Action against Cercospora arachidicola on groundnut plants Residual-protective action Groundnut plants 10-15 cm high were sprayed with a spray liquor (0.006% of active substance) prepared from a wettable powder of the active substance, and 48 hours later were infected with a conidia suspension of the fungus. The infected plants were incubated at about 21 "C at a high atmospheric humidity for 72 hours and were then placed in a greenhouse until the typical leaf spots appeared. The fungicidal action was evaluated, on the basis of the number and size of the spots which had appeared, 1 2 days after the infection.
In comparison with untreated but infected control plants (number and size of spots = 100%), groundnut plants which had been treated with active substances from the table showed a greatly reduced Cercospora attack. Thus, compounds 1 to 9, 14, 19, 20, 25, 33, 38, 45-51 and 54-58 almost completely prevented the occurrence of spots in the above experiments (0-10%).
Example B3: Action against Erysiphe graminis on barley a) Residual-protective action Barley plants about 8 cm high were sprayed with a spray liquor (0.002% of active substance) prepared from a wettable powder of the active substance. After 3-4 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22"C and the fungal attack was evaluated after 10 days.
b) Systemic action Barley plants about 8 cm high were watered with a spray liquor (0.006% of active substance, based on the volume of soil) prepared from a wettable powder of the active substance. Care was thereby taken that the spray liquor did not come into contact with the above-ground parts of the plants. After 48 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22"C and the fungal attack was evaluated after 10 days.
Compounds of the formula I showed a good action against Erysiphe fungi. Untreated but infected control plants displayed an Erysiphe attack of 100%. Amongst other compounds from the table, compounds 1 to 10, 14, 15, 17, 19, 20, 25, 33, 35, 38, 45-51 and 53-58 inhibited the fungal attack on barley to O to 5%, and, in particular, compound No. 2 effected complete reduction of attack.
Example B4: Residual-protective action against Venturia inaequalis on apple shoots Apple seedlings with fresh shoots 10-20 cm long were sprayed with a spray liquor (0.006% of active substance) prepared from a wettable powder of the active substance. After 24 hours, the treated plants were infected with a conidia suspension of the fungus. The plants were then incubated at 90-100% relative atmospheric humidity for 5 days and placed in a greenhouse at 20-24"C for a further 10 days. The scab attack was evaluated 1 5 days after the infection.
Compounds 1 to 6, 8, 9, 14, 17, 19, 20, 33, 45, 47, 49-51 and 53-57 inhibited the disease infestation to less than 10%. In contrast, untreated but infected control shoots showed 100% attack.
Example B5: Action against Botrytis cinerea on beans Residual-protective action Bean plants about 10 cm high were sprayed with a spray liquor (0.02% of active substance) prepared from a wettable powder of the active substance. After 48 hours, the treated plants were infected with a conidia suspension of the fungus. After incubation of the infected plants at 95-100% relative atmospheric humidity at 21 "C for 3 days, the fungal attack was evaluated.
The compounds from the table in many cases very greatly inhibited the fungal infection. At a concentration of 0.02%, compounds 1 to 6, 8, 9, 14, 15, 20, 25, 33, 35, 45, 47, 49, 50, 51 and 53- 57, for example, proved to be completely effective. The disease infestation was 0 to 8%.
The Botrytis attack of untreated but infected bean plants was 100%.
Example B6: Action against Piricularia oryzae on rice plants Residual-protective action After being grown for two weeks, rice plants were sprayed with a spray liquor (0.002% of active substance) prepared from a wettable powder of the active substance. After 48 hours, the treated plants were infected with a conidia suspension of the fungus. After incubation at 95-100% relative atmospheric humidity at 24"C for 5 days, the fungal attack was evaluated.
Rice plants which had been treated with a spray liquor containing one of the compounds from Table 1, such as, for example, No. 14 or 33, as the active substance, showed a fungal attack of less than 10%, in comparison with the untreated control plants (100% attack).

Claims (11)

1. A compound of the general formula I
in which Az is 1H-1,2,4-triazole, 4H-1,2,4-triazole, or 1 H-imidazole; Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl, phenoxyphenyl and naphthyl; R, is hydrogen, C1-C6-alkyl, C3-C5-alkenyl or benzyl; R2 is hydrogen, fluorine or C,-C6-alkyl and R3 is hydrogen, fluorine, C,-C6-alkyl, C,-C6-haloalkyl, C,-C6-alkoxy, C,-C6- alkykthio, phenyl, phenoxy, phenylthio or C3-C7-cycloalkyl, and each aromatic substituent or aromatic moiety of a substituent is unsubstituted or mono- or poly-substituted by halogen, C,-C4-alkyl, C,-C4-alkoxy, C,-C4-haloalkyl, nitro and/or cyano; including the acid addition salts, quaternary azolium salts and metal complexes.
2. A compound of the formula I according to claim 1, in which Az is 1 H-1 ,2,4-triazole or 1 H-imidazole; Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl and phenoxyphenyl; R, is hydrogen; R2 is hudrogen, fluorine or C,-C3-alkyl; and R3 is hydrogen, fluorine, C1-C4-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, C,-C3-alkylthio, phenyl, phenoxy or phenylthio, each phenyl moiety being unsubstituted or substituted by fluorine, chlorine, bromine, methyl, methoxy, CF2, NO2 and/or cyano; including the acid addition salts, quaternary azolium salts and metal complexes.
3. A compound of the formula I according to claim 2, in which Az is 1 H-1 ,2,4-triazole, Ar is phenyl or phenoxyphenyl which is unsubstituted or substituted in the 2- and/or 4-position by methyl or halogen; R, is hydrogen; R2 is hydrogen, fluorine or methyl; and R3 is hydrogen, fluorine, C,-C4-alkyl or a radical from the series comprising phenyl, phenoxy and phenylthio which is substituted by fluorine, chlorine and/or bromine.
4. A compound of the formula I according to claim 1, selected from the group comprising: 1-(1 H-1,2,4-triazole-1-yl)-2-(2,4-dichlorophenyl)-3-fluorobutan-2-ol, 1-(1 H-1 2,4-triazol-l -yl)-2-(2- chloro-4-fluorophenyl)-3-fluorobutan-2-ol. 1-(1 H- 1, 2, 4-triazol- 1 -yl)-2-(2, 4-dichlorophenyl)-3-fluo- ropentan-2-ol, 1-(1H-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoro-4-methylpentan-2-ol, 1 ( 1 H- 1, 2,4-triazol-1 -yl)-2-(2-chloro-4-fluorophenyl)-3-fluorophentan-2-ol, 1-(1 H- 1, 2, 4-triazol- 1 -yl)2-[p-(4-chlorophenoxy)phenyl]-3-fluoropropan-2-ol, 1-(1H-1,2,4-triazol-1-yl)-2-(2,4-dichlorphenyl)-3-(4-chlorophenoxy)-3-fluoropropan-2-ol. 1-(1H-1,2,4-triazol-1-yl)-2-(4-fluorophenyl)-3,3,3trifluoropropan-2-ol, l-(1H-l ,2,4-triazol-l -yl)-2-(2,4-dichlorophenyl)-3, 3, 3-trifluoropropan-2-ol.
5. A compound of the formula I according to claim 1, chosen from the series: 1-(1 H-1,2,4- triazol- 1 -yl)-2-(4-chlorphenyl)-3-fluorohexan-2-ol. 1-(1 H- 1, 2, 4-triazol- 1 -yl)-2-(2, 4-dichlorophenyl)- 3-fluorohexan-2-ol. 1-(1H-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl-3,3-difluoropropan-2-ol, 1 ( 1 H- 1, 2,4-triazol- 1 -yl)-2-(2,4-dichlorophenyl)-3-fluoro-4-methylpentan-2-ol, 1-(1 H- 1, 2,4-triazol- 1- yl)-2-[p-(4-bromophenoxy)phenyl]-3,3-difluoropropan-2-ol, 1-(1H-1,2, 4-triazol-l -yl)-2-[p-(4-f luoro- phenoxy)phenyl]-3, 3-difluoropropan-2-ol, 1-(1 H- 1, 2, 4-triazol- 1 -yl)-2-[p-(4-chlorophenoxy)phenyl]- 3, 3-difluorpropan-2-ol and 1 -(1 H-i , 2,4-triazol- 1 -yl)-2-[p-(4-chlorophenoxy)-2-methylphenyl]-2-hy- droxy-34luoropropane.
6. A process for the preparation of a compound of the formula I as defined in claim 1, which comprises first reacting an oxirane of the formula Il
with an azole of the formula Ill M-Az (III) to give a compound of the formula la
and, if required, converting the alcohol la into an ether of the formula I in the conventional manner, for example by reaction with a compound of the formula IV R,-W (IV) in which formulae la, II, Ill and IV, the substituents R1, R2, R3, Ar and Az are as defined under formula I, M is hydrogen or a metal atom and W is OH or a conventional leaving group.
7. A composition for controlling or preventing attack by microorganisms, which contains, in addition to conventional carriers, a compound of the formula I according to claim 1 as at least one active component.
8. A composition according to claim 7, which contains 0.1 to 99% of an active substance of the formula 1, 99.9 to 1% of a solid or liquid adjuvant and 0 to 25% of a surfactant.
9. A method of controlling or preventing attack on crop plants by phytopathogenic microorganisms, which comprises applying a compound of the formula I as defined in claim 1 to the plants or their location.
10. An oxirane of the formula II
in which R1, R2, R3 and Ar are as defined under formula I in claim 1.
11. Compounds of formula I substantially as described with reference to any of the preparation Examples.
1 2. Process for producing compounds of formula I substantially as described with reference to any of the preparation Examples.
1 3. Composition for controlling or preventing attack by microorganisms according to claim 7 substantially as described with reference to any of the formulation Examples.
GB08332617A 1982-12-14 1983-12-07 1-azolyl-2-aryl-3-fluoroalkan-2-ols as microbicides Expired GB2132195B (en)

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US5366989A (en) * 1991-12-09 1994-11-22 Toyama Chemical Co., Ltd. Triazole derivatives and salts thereof and antifungal agent containing the same
US5605921A (en) * 1991-12-09 1997-02-25 Toyama Chemical Co., Ltd. Triazole derivatives and salts thereof, and antifungal agent containing the same
US10358426B2 (en) 2011-07-13 2019-07-23 BASF Agro B.V. Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
US9137996B2 (en) 2011-07-15 2015-09-22 Basf Se Fungicidal alkyl- and aryl-substituted 2[-2-chloro-4-(dihalo-phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
US9173402B2 (en) 2011-07-15 2015-11-03 Basf Se Fungicidal alkyl-substituted 2[2-chloro-4-(4-chioro-phenoxy)-phenyl]-1[1,2,4]triazol-1-yl-ethanol compounds
US9247747B2 (en) 2011-08-15 2016-02-02 Basf Se Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-2-alkynyl/alkenyl-ethyl}-1H-[1,2,4]triazole compounds
US9247746B2 (en) 2011-08-15 2016-02-02 Basf Se Fungicidal substituted 1-{2-cyclyloxy-2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-ethyl}-1H-[1,2,4]triazole compounds
US9295259B2 (en) 2011-08-15 2016-03-29 Basf Se Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-3-methyl-butyl}-1H [1,2,4]triazole compounds
US10759767B2 (en) 2012-12-20 2020-09-01 BASF Agro B.V. Compositions comprising a triazole compound
CN105008332A (en) * 2013-01-08 2015-10-28 巴斯夫欧洲公司 Substituted imidazole and (1,2,4)triazole compounds as fungicides
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US10519122B2 (en) 2013-01-09 2019-12-31 BASF Agro B.V. Process for the preparation of substituted oxiranes and triazoles
US10512267B2 (en) 2013-07-08 2019-12-24 BASF Agro, B.V. Compositions comprising a triazole compound and a biopesticide
US10212934B2 (en) 2014-06-25 2019-02-26 BASF Agro B.V. Pesticidal compositions
US10206403B2 (en) 2014-07-14 2019-02-19 Basf Se Pesticidal compositions
US10779536B2 (en) 2014-11-07 2020-09-22 Basf Se Pesticidal mixtures
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US10905122B2 (en) 2016-03-16 2021-02-02 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on cereals
US11241012B2 (en) 2016-03-16 2022-02-08 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on soybean
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