IE832933L - 1-azolyl-2-aryl-3-fluoroalkan-2-ols. - Google Patents

1-azolyl-2-aryl-3-fluoroalkan-2-ols.

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IE832933L
IE832933L IE832933A IE293383A IE832933L IE 832933 L IE832933 L IE 832933L IE 832933 A IE832933 A IE 832933A IE 293383 A IE293383 A IE 293383A IE 832933 L IE832933 L IE 832933L
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foraula
hydrogen
fluorine
alkyl
phenyl
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IE832933A
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IE56378B1 (en
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Ciba Geigy
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Priority to IE2419/88A priority Critical patent/IE56379B1/en
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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

Abstract

1-Azolyl-2-aryl-3-fluoro-alkan-2- ols of the general formula I <IMAGE> in which Az is 1H-1,2,4-triazole, 4H-1,2,4-triazole or 1H-imidazole; Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl, phenoxyphenyl and naphthyl; R1 is hydrogen, C1-C4-alkyl, C3-C5-alkenyl or benzyl; R2 is hydrogen, fluorine or C1-C6-alkyl and R3 is hydrogen, fluorine, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, 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, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, nitro and/or cyano; including the acid addition salts, quaternary azolium salts and metal complexes, are useful for controlling phytopathogenic microorganisms. [EP0113640A2]

Description

b b J 7 B The present invention relates to novel, substituted. 1-azolyl~2-aryl-3-fluoroalkan-2-ols and ethers thereof, of the fornula I below, and to acid addition salts, quaternary axollua salts and aetal coaplexes thereof. The Invention 5 furtheraore relates to the preparation of these sub*?ances an.d alcroblcldal eoaposltlons containing at least one of these eoapounds as the active substance. The Invention also relates to the preparation of the above eoaposltlons and to the use of the active substances or of the eoaposltlons 10 for the control of haraful a1croorganlsas, preferably fungi which are haraful to plants.
The coapounds according to the Invention are those of the general formula X I*1 > > a rn^ f! | f tt) Ac *3 15 In whleh Az Is 1H-1,2,4-tr1azole, 4H-1,Z,V-*r1asole or 1H-laldazole; Ar Is an unaubstltuted or substituted aroaatlc radical froa the series coapnslng phenyl, blphenyl, phenoxy-phenyl and naphthyl; Rf Is hydrogen, C-j-C^-alkyl, C3-CJ-alkenyl or benzyl; Kj Is hydrogen, fluorine or 20 alkyl and Rj Is hydrogen, fluorine, C^-C^-alkyl, haloalkyl, C^-Cg-alkoxy, Cj-C^-allcy tthto, phenyl, phenoxy, phenylthlo or Cj-C7-cycloalkyl, and each aroaatlc substltuent or aroaatlc ao4fty of a substltuent Is unsubstltuted 3 or aono* or poly-substituted by halogen, C^-c^-alkyl, C^-C^~ alkoxy, C|-C4-haloalkyI, nltro and/or eyano; including the acid addition salts, quaternary azollum salts and metal complexes; with the proviso that Rj and Rj cannot each simultaneously be fluorine.
S The tern alkyl by Itself or as a constituent of ano ther 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, 10 Isobutyl, tert.-butyl, isopentyl and the like. Haloalkyl is a monohalogenated to perhalogenated alkyl substltuent, for example CHCl2, CHF2, CH2Cl, CCl3, CH2F, CH2CH2Cl CBjBr and the like. In particular CP^. Here and 4.n the following text, halogen is to be understood as meaning fluorine, 15 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 «- or 0-naphthyl.
The present Invention thus relates to the free com-20 pounds of the formula I and acid addition salts, quaternary azoHum salts and metal coaplexes thereof. The free compounds, In particular the 1H-1,2,4-tr1atole derivatives, are preferred In the context of formula I.
Examples of salt-forming acids are Inorganic acids, 25 such as hydrogen hallde acids, such as hydrofluoric acid, hydrochloric acid, hydrobromlc acid or hydrlodlc acid, as well as sulfuric, acid, phosphoric acid, phosphorous acid and nitric acid, and organic acids, such as acetic add, tr1-fluoroacetlc acid, trichloroacetic acid, propionic add, for-30 mlc add, benzenesulfontc add, p-toluenesulfon1c acid or methanesulfonlc acid.
Netal complexes of the formula I consist of the basic organic molecule and an Inorganic or organic metal salt, for example the halldes, nitrates, sulfates, phosphates, ace-35 tates* trlfluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, bensoates and.the like of the elements of the third and fourth main group, such as 4 • luilntuif tin or lead, and of the first to eighth sub-group, such as chroalui/ manganese. Iron, cobalt, nickel, zlrconlua, copper, zinc, silver, aercury and the like. The tub-group elements of the 4th period are preferred. The aetals can S be In the various valences with which they are associated. The metal coaplexes of the formula I can be mononuclear or polynuclear, I.e. they can contain one or nore organic molecule components as Uganda. Complexes with the aetals copper, zinc, aanganese, tin and zlrconiua are preferred. 10 The compounds of the foraula I are oils, resins or, chiefly solids, which are stable at room temperature and are distinguished by very useful microbicidal properties. They can be used prevent at ively and euratlveiy in the agricultural sector or related fields for controlling alcro-organlsas which daaage 15 plants, the trlazolylaethyl derivatives In the context of the foraula I being preferred. The active substances of the foraula X according to the Invention are distinguished by t wry good phytofunglcldal action and problea-free application when used In low concentrations. Moreover, they also have a 20 growth-regulating action, In particular a growth-Inhibiting action, especially on tropical cover crops.
The following groups of substances are preferred, because of their aarked microbicidal action, in particular their phytofunglcldal action: coapounds of the foraula I 25 in which Az Is 1H-1,2,4-triazole or 1H-1aidazole; Ar 1s an unsubstltuted or substituted aroaatlc radical from the st-." ries comprising phenyl, blphenyl and phenoxyphenyl, Rj Is hydrogen; Rj 1* hydrogen, fluorine or Cj-Cj-alkyl; and •*3 Is hydrogen, fluorine, Cj-C^-alkyl, C^-Cj-haloalkyl, 30 .Cj-Cj-alkoxy, Cj-Cj-alkyIthlo, phenyl, phenyloxy or phenylthio, each phenyl aolety being unsubstltuted or substituted by fluorine, chlorine, bromine, aethyl, a«-thoxy, CFj, NOj and/or cyano; including the acid addition salts, quaternary atollua salts and aetal coaplexes* provided that Rj and Rj are not simultaneously fluorine. 35 Particularly preferred coapounds of the foraula I within this group are those In which Ac Is 1H-1,2,4-tr1asole; Ar Is phenyl or phenoxyphenyl which is unsubstltuted or, prer* v; v firibl// substituted in the 2- and/or 4-position by aethyl or halogen, preferably fluorine or chlorine; R| is hydrogen; >2 1i hydrogen, fluorine or aethyl; and R3 is hydrogen, fluorine, C^-C^-alkyl or a radical froa the series coa-5 prising phenyl, phenoxy and phenylthio which is substituted by f luorine, chlorine and/or broaine ; provided' that R2 and R3 are nor simultanfous1y fluorine.
Examples of specific particularly preferred substances froa a fungicidal point of view are: 1-(1H-1,2,4-tri-azol-1-yI)-2-(2,4-dichlorophenyI)-3-fluorobutan-2-ol, 1-(1M-10 1,2,4-triazol-1-yl>-2-<2-chloro-4-fluorophenyl>-3-fluoro- butan-2-ol, 1 -11H-1 ,-2,4-t r1 azol-1 -y l>-2-l2,4-d1 ch loropheny I) -3-fluoropentan-2-oI, 1-(1H-1,2,4-triazol-1-yl)-2-(2,4-di-chlorophenyI)-3-fluoro-4-aethylpentan-2-ol, 1-C1H-1,2,4-tr1azol-1-yl)-2-<2-chloro-4-fluorophenyi>-3-fluoropentan-15 2-ol, 1-<1H-1,2,4-triazol-1-yl>-2-C2,4-d1chlorophenyl>-3-(4-chlorophenoxy)-3-fluoropropan-2-ol, 1-OH-.1 ,2,4-triazol-> 1-yl)-2-Cp-(4-chlorophenoxy>phenyl3-3-fluoropropan-2-ol, 20. i-( 1H— 1, 2,4-triasol'-l-yl)-2-(4- chlorophenyI)-3-fluorohexan-2-ol, 1-I1H-1,2,4-trlazol-1-yl>-Z-C2,4-d1chlorophenyI)-3-fluorohexan-2-ol, 1-tlH-1,2,4-tri-azol-1-yI)-2-<2,4-d1chloropheny1-3,3-di fluoropentan-2-oI, 1-(1H—1,2,4-tr1azol-1-yl)-2-(2,4-d1chlorophenyl)-3-fluoro-4-25 aethylpentan-2-ol, 1-(1H-1,2,4-tr1azol-1-yl)-2-Cp-(4-broao- phenoxy)phenyl]-3,3-difluoropropan-2-ol, 1 — <1H—1,2,4-tr1-a*ol-1-yl>-2-Cp-<4-fluorophanoxy)pheny13-3,3-dlfluoro-propan- 2-oI, 1-C1H-1,2,4-trlazol-l-yl)-2-Cp-(4-chlorophenoxy)phenyl3-3,3-dlfluoropropan-2-ol and 1-<1H-1,2,4-tr1azol-1-yl)-2-Cp- 30 (4-chlorophenoxy)-2-aethylphenyl3-2-hydroxy-3-fluoropropane.
The coapounds of the foraula I are prepared by a pro-cc„s which coaprlses first reacting an oxirane of the foraula II V Ar-C^CH *2^-R3 ? 2 (ID G with an ««U of the foraula 111 M—A* (III) to glvt a coapourid of the formula la OB Ar-C-CH "A* (la) I 2 F 5 and. If required, converting the alcohol la Into an ether of the foraula X In the conventional lanner, for exaaple by reaction with a compound of the foraula IV R1 - W (IV) In which foraulae la, XI, III and IV, the substltuent* 10 R2, R3, Ar and Az are as defined under foraula I, N 1s hydrogen or, preferably, a natal atom. In particular an alkali Metal atoa, such as LI, Na or K, and W Is OH or a conventional leaving group. Conventional leaving groups are known froa the literature. 15 If appropriate, the reaction of IX with XII to give la Is carried out 1n the presence of condensing agents or acid-binding agents. Suitable agents are organic and Inor-ganlc bases, for exanple tertiary aalnes, such as trlalkyl-aalnes (trlaethylaalne, trlethylamlne, trlpropylaalne and 20 the like), pyridine and pyridine bases (4-d1aethylaa1nopyr1~ dine, 4-pyrrolldylaalnopyrldlne and the like), oxides, hydrides and hydroxides, carbonates and blcarbonates of alkali aetals and alkaline earth aetals (CaO, BaO, NaOM, KOH, NaH, CaC0H>2» KHCO3, NaHC03, Ca(HC03)2, ICjCOj, 25 and NajCdj) and alkali aetal acetates, such as CMjCSONa or. CH3COOK. Moreover, alkali aetal alcoholates, such as CjNjONi, CjH7-nONa and the like, are also suitable.
In soae cases. It nay be advantageous If the free azole XXX The reaction (JZ tilth IXZ to give la) It preferably carried out 1n an organic solvent which It relatively polar 5 but Inert In the reaction, for example M,H-d1methyIformamide, N,N~d1methylacetam1de, dloethyIsulfoxlde, acetonitrlle, benzo-nltrlle 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 10 ether, ciilorobenzene, nitrobenzene and the like. The reaction temperatures are in a temperature range from 0° to 150°C, preferably 20° to 100°C.
This reaction (ZZ with ZZZ to give Za) can furthermore be carried out analogously to reactions which are al-15 ready known for other oxlranes with asolet tcf. tertian Offen-legungsschrlft 2,912,288).
Zn the part roactlona mentioned, the Intermediates can be Isolated from the reaction medium and, If desired, purified by one of the generally conventional methods, for 20 example by washing, digestion, extraction, crystallisation, chromatography, dlatlllatlon and the like, before the further reaction.
Zn cates where M In formula ZV Is a conventional leaving group, the further reaction of Za to give Z la car-25 rled out 1n the abaence or, preferably, In the pretence of a aolvent which la Inert In the reaction.
Examplet of tultable solvents are the following: N,N-d1methyIformamide, N,N-d1methylacetamide, hexamethyl-phosphoric acid trlamlde, dlmethyIsulfoxlde, 2-methyl-2-pen-30 tanone 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. Zn some cases It may prove advantageous to carry out the reaction In 35 the presence of a base, for exaaple an alkali metal hydride, hydroxide or carbonate. In order to accelerate the rate of reaction. However, It may also be advantageous first to 8 convert the alcohol of the formula le (R^ ■ OH) Into e suitable aetal salt. In e manner which is known per ief for example by reaction with a strong base.
Examples of suitable strong bases are alkali metal 5 hydrides and alkaline earth metal hydrides (NaH, KH, CeH2 and the like) and alkali aetal-organlc compounds, for example butyl-lithium or an alkali metal tert.-butoxlde, and alkali metal hydroxides, such as NaOH or KOH, can moreover also be used if the reaction 1s carried out In an aqueous 10 two-phase system In the presence of a phase transfer catalyst.
However, it 1s also possible first to convert the elcohol of the formula la Into an alkali metal alcoholate 1n a conventional manner before the further reaction, and 15 then to reect the alcoholete with a compound of the formula IV (In which H -1s a leaving group), the reaction advantageously being carried out 1n the presence of a crown ether. If M ■ K, 18-crown-6, In particular. Is present; and it N <■ Na, 15-erown-5, In particular, Is present. The reaction Is 20 advantageously carried out In a medium which 1s Inert 1n the reaction. Examples of suitable solvents are ethers and ether-like compounds, for example dl-lower alkyl ethers (diethyl ether, dllsopropyl ether, tert.-butyl methyl ether and the like), tetrahydrofuran and dloxane, and aromatic hydro-25 carbons, such as bensene, toluene or the xylenes.
The following solvents are examples of the organic water-1mn1sc1ble phase: aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, petroleum ether, Itg- roln, bensene, toluene, the xylenes and the like,' halogenated • "* 30 hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, ethylene dlchlorlde, 1,2-dlchloroethane, tetrachloroethylene and the like, or aliphatic ethers, such as diethyl ether, dllsopropyl ether, t-butyl methyl ether and the like. Examples of suitable phase transfer catalysts 35 are: tetraalkylammonlum halldes, blsulfates or hydroxides, such as tetrabutylammonlun chloride, bromide or Iodide;'trl-ethylbensylammonlum chloride or bromide; tetrapropylammonlum i 0 chloride, bromide or Iodide; and the like. Possible phase transfer catelysts Include phosphonlun salts. The reaction tenperetures ere 1n generel between 30° and 130°C, or at the boiling point of the solvent or solvent mixture. S In cases where U In foraula IV Is a hydroxyl group, a condensation reectlon Is advantageously carried out. The tuo reactants are refluxed in a suitable solvent.
In principle, any solvent which is inert towards the reactants and, advantageously, forms an azeotrope with water 10 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, cerbon tetrachloride, 1,2-dichloro-ethane, tetro-chloroethylene and chlorobenzene, as well as 15 ether-like coapounds, such os tert.-butyl methyl ether, dloxane end the like. In some cases, the compound of the foraula III Itself can be used as the solvent. This condensation reectlon Is edvantageously carried out In the presence of a strong ecid, for example paratoluenesulfonic 20 ecid, et the boiling point of the azeotroplc mixture.
To prepare the ethers of the foraula I, It Is also possible first to replace the free OH group in the compounds of the formula la by one of the above conventionel leaving groups H and then to reect the product with a compound of 25 the foraula IV (where H « OH).
The. starting substences of the formula III are gene-relly known, or they cen be prepered by methods which ere known per se.
The oxlrenes of the formula II are novel and are the subject of Divisional Patent Specification No. ''/. "Otey are 30 Intermediates which heve been developed particularly for the preperatlon of the useful ectlve substances of the foraule I. Because of their structurel nature, they can be converted Into the compounds of the foraule la In e simple menner, end, aoreover, some of the coapounds of the foraula II have e fun-35 glcidel activity touerds haraful fungi from the fenllles'of Ascoaycetes, Sasidloaycetes or Fungf imperfect*.
Epoxides of the foraule II cen be prepared froa 1 0 ketones of the foraula V h Ar-C-C-F (▼) II I OEj in »■ wanner which is known per se by reaction with dlaethyl-. sulfonlua aethyllde or diaethyloxosulfonlua aethyllde (Corey 5 and Chaykovsky, JACS, 1962, 84, 3782).
The ketones of the foraula V are accessible by ne-thods which are known per se froa the literature (Cf.J. L«-roy, J. Org. Chea. 46, 206 (1981) or Houben-Ueyl, voluae V/3, page 211), froa the corresponding known O-broao-ketones 10 by conventional replaceaent of the broalne by fluorine, or they can also be prepared by acylation of the aroaatlc on which they are based with fluorlnated carboxylic acid derivatives, for exaaple by a Friedel-Crafts reaction.
In principle, unless expressly specified in « parti-15 cular case, one or aore solvents or diluents which are inert In the reaction can be present in the preparation of.all the starting substances, interaediates and end products aentioned here. Examples of suitable solvents or diluents Are aliphatic and aroaatlc hydrocarbons, such as bensene, toluene, 20 the xylenes and petroleua ether; halogenated hydrocarbons, such as chlorobenzene, aethylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; ethers and ether-like coapounds, such as dialkyl ethers (diethyl ether, dllsopropyl ether, tert.-butyl methyl ether and 25 the like), anlsole, dloxane and tetrahydrofuran; nitriles, such as acetonitrile and proplonitrile; M,N-dialkylated aaides, such as diaethyIforaaaide; diaethyIsulfoxlde; ketones, such as acetone, diethyl ketone and aethyl ethyl ketone, and mixture* of these solvents with one another. In 30 soae cases, it nay also be edvantageous 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, hellua, argon or, in certain cases, also carbon dioxide.
I The compound* of the foraula X £ i2 — |-F (i) Ar ELj always have an asyaaetrlc C atoa C* in the position adjacent to the substituents Ar and OR^ and can therefore exist in 5 two enantiomeric forms. In general, a mixture of the two enantioners Is formed in the preparation of these substances, and this can be split into the pure optical antipodes in a conventional manner, "for exaaple by fractional crystallisation of salts with strong optically active acids. The enan-10 ttomers can have different biological actions; thus, for example, the fungicidal action can be In the foreground In one form end 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 15 radicals Rz an The present Invention relates to all the pure enan-20 tlomers and dlastereomers and mixtures thereof with one another.
The preparation process described, Including all the pert steps' Is sn Important component of the present Invention. 25 Xt has been found, surprisingly, that compounds of the formula X have a microbicidal spectrum against phyto-pathogenlc fungi and bacteria which 1s very favourable for practical requirements. They have very advantageous curative, systemic and, In particular, preventative properties and 30 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 J n of the foraula I, the additional future growth of parts of plants also regaining protected froa such alcroorganisax.
•The active substances of the foraula I are effective against phytopathogenle fungi belonging to the following S classes: Fungi laperfectl (for exaap-le, Botrytis, Helnln-thosporlun, Fusarlua, Septoria, Cercospora and Alternaria); and Basldlonycetes (for exaaple the genera Heniteia, Rhizoco-tonia and Puccinia); and they are particularly active against the class of Ascoaycetes (for exaaple Venturia, Podosphaere, 10 Erysiphe, Honillnia and Unclnula). Moreover, the coapounds of the foraula I have a systemic action. They can further-aore be used as dressings for the treataent of seed (fruit, tubers and seed) and plant seedlings# for protection froa fungal infections and against phytopathogenle fungi which IS occur 1n the soil.
The Invention thus also relates to alcroblcldal eoaposltlons and to the use of the coapounds of the foraula I for the control of phytopathogenle alcroorganlsas, In particular fungi which are haraful to plants, and for preventative Z0 prophylaxis of an attack on plants.
The present Invention furthernore also Includes the preparation of agrochealcal eoaposltlons which coaprlses 1nt1aate nixing of the active substence with one or tore carriers and adjuvants described In this Appli-. 25 cation. The present Invention also Includes a method of treating plants which coaprlses application of the coapounds of the foraula I or of the novel eoaposltlons.
The following plant species are examples of target crops 1n the context of this Invention for the fields of 1n-30 dlcatlon disclosed herein: cereals: (wheat, barley, rye, oats, rice, sorghum and related species); beet (sugar-beet *nd fodder beet); poaaceous fruit, stone fruit end berries: (apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry); pulse: (bean, lentil, pea, soya bean); 35 oil crops: (rape, mustard, poppy, olive, sunflower, coconut, caster, cacao and groundnut); cucumber erops: (puapkln, cucumber, aelon); fibre crops: (cotton, flex, heap and jute); 13 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 S. maize, tobacco, nut, coffee, sugar cane, tea, vine, bop 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 10 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 uhlch Influence plant growth. They can also hie, however, selective herbicides, Insecticides, fungicides, bactericides, 15 nematlcldes, mollusciddes or mixtures of several of these products. If necessary together with other carriers, surfactants or other application-promoting adjuvants conventionally used 1n the art of formulation.
Suitable carriers and adjuvants can be solid or 11-20 quid and correspond to the substances appropriate In the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackl-flers, thickeners, binders or fertilisers.
A preferred method of application of an active Sub-25 stance of the formula I or of an agrochemical composition containing at least one of these active substances Is application to the foliage (leaf application). The number of applications and the amount applied depend on the threat of attack by the corresponding pathogen (species of fungus). 30 However> the active substances of the formula I can also enter the plsnts 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 substsnces are incorporated into the soil in solid form, for exaaple In the form of granules 35 (soil application). The compounds of the formula X can, however, also be applied to seed (coating), by a method In which the seed is either soaked in a liquid formulation of the 14 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.
S The compounds of the formula I are used here in un modified form or, preferably, together with the assistants conventionally used in the art of formulation, and are thus processed in a known manner to, for example, emulsion concentrates, brushable pastes, directly sprayable or dilu-10 table 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, 1s chosen according to the Intended alms and the given c1r-15 cumstances, as Is the type of composition. Favourable application amounts are generally 50 g to 3 kg of active subatance US) per hectare; preferably 100 g to 2 kg of AS/tiectare, and In particular 200 g to 600 g of AS/hectare.
The formulations, I.e. the compositions, preparations 20 or mixtures, containing the active substance- of the formula X 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, sur-25 face-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably C8 to C12 fractions, for example xylene mixtures or substituted naphthalenes, phthallc acid esters, such as dlbutyl phthalate or dloctyl phthalate, aliphatic hydrocarbons, 30 such as cyclohexane or paraffins, alcohols and glycols and ethers and esters thereof, such as ethanol, ethylene g.lycol,. ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-aethyl-2-pyrrol1done, dlmethylsulfoxlde or dlmethylformamlde, and, 35 where relevant, epoxldlsed vegetable oils, such as epoxldlsed coconut oil or soya bean oil; or water. disperslble powders, are as a rule ground natural minerals, such as calclte, talc, kaolin, montmorlllonlte or attapulglte. Highly disperse si Ilea or highly disperse absorbent polymers may also be added to Improve the physical properties. Sul-S table granular, adsorptlve carriers for granules are porous types, for example pumice, broken brick, seplollte or ben-tonlte, and suitable non-adsorptive carriers are, for example, calclte or sand. A large number of pre-granulated materials of inorganic or organic nature, such as, in particular, dolo-10 mite or comminuted plant residues, can moreover be used. Further particularly advantageous adjuvants whic-h promote application and can lead to a large reduction In the amount applied are natural (animal or vegetable) or synthetic phospholipids of the cephalln and lecithin series, for exaaple 15 phosphatldylethanolamlne, phosphatldyIserlne, phosphatidylcholine, sphingomyelin, phosphatldyIinositol, phosphatidyl' glycerol, lysoledthln, plasma logons or cardlollpln, which can be Isolated, for example, from animal or vegetable cells. In particular from the brain, heart or liver or from egg yolks 20 or soya bean. Examples of commercial mixtures which can be used are phosphatidylcholine mixtures. Examples of synthetic phospholipids are dloctanoylphosphatldylchollne and d1paIm1toyIphosphatIdylcholine.
Suitable surface-active compounds, depending on the 25 nature of the active substance of the formula I to be formulated, are non-1on1c, catlonlc and/or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as meaning surfactant mixtures. 30 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 unsubstltuted or substituted ammonium salts of higher fatty 35 acids 'Ci0-C22^« *or tile Na or K salts of oleic acid or stearic acid, or of naturally occurring fatty add mixtures, which can be obtained, for example, from coconut oil or tallow oil. The fatty acid aethyl-laurln salts are ; also suitable.
However, so-called synthetic surfactants, 1n particular fatty sulfonates, fatty sulfates, sulfonated benzlal-S dazole derivatives or alkylsulfonates, are aore frequently used.
The fatty sulfonates or sulfates are as a rule In the fora of alkali aetal, alkaline earth aetal or unsubstltuted or substituted aaaonlua salts and contain an alkyl radical 10 having 8 to 22 C atoas, alkyl also Including the alkyl aoiety of acyl radicals, for exaaple the Na or Ca salt of llgnlnsul-fonic acid, dodecylsulfurlc acid ester or a fatty atcohol sulfate alxture prepared froa naturally occurring fatty acids. These coapounds also Include the salts of sulfuric add es-15 ters and sulfonic adds of fatty alcohol/ethylene oxide ad-ducts. The sulfonated benslaldazole derivatives preferably contain 2-sulfonlc add groups and a fatty acid radical having 8-22 C atoas. Exaaples of alkylarylsulfonates are the Na, Ca or trlethanolaalne salts of dodecylbenzeneftulfonlc acid, 20 dlbutylnaphthalenesulfonlc add or a naphthalenesulfonlc ac1d/foraaldehyde condensate.
Corresponding phosphates, for exaaple salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethylene oxide adduct, are also suitable. 25 Particularly suitable non-Ionic surfactants are poly- glycol ether derivatives of aliphatic or cycloallphatlc alcohols, saturated or unsaturated fatty acids and alkylphenols, which aay contain 3 to 30 glyeol ether groups and 8 to 20 carbon atoas In the (aliphatic) hydrocarbon radical andi to 30 18 carbon atoas In the alkyl radical of .the alkylphenols.
Other sultabl! non-Ionic surfactants are the water-soluble adducts, containing 20 to ZSQ ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide and polypropylene glyeol, ethylenedlaalnopoly-35 propylene glycol and an alkylpolypropylene glycol having 1 to 10 carbon atoas 1n the alkyl chain. The coapounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
EiaiplM of non-1onlc surfactants are nonylphenolpoly-ethoxyethanols, castor oil polyglycol ethers, polypropylene polyethylene oxide adducts, trlbutyIphenoxypolyethylene-5 ethanol, polyethylene glycol and octylphenoxypolyethoxy-ethanol.
Fatty acid esters of polyoxyethylene sorbltan, such as polyoxyethylene sorbltan trioleate, are also suitable.
The catlonlc surfactants are. In particular, quater-10 nary aaaonlun salts which contain at least one alkyl radical having 8 to 22 C atoms as N-substltuent and lower alkyl or benzyl radicals, which nay or may not be halogenated, or lower hydroxyalkyl radicals, as further substltuents. The salts are preferably In the form of halldes, methylsulfates 15 or ethyIsulfates, and are, for example, stearyltrlmethyl-ammonlum chloride or benzyldl(2-chloroethyl)ethylammonlum bromide.
The surfactants conventionally used In the art of formulation are deacrlbed, Inter alia, 1n the following 20 publications: "He Cutcheon's Detergents and Emulslflera Annual" SC Publishing Corp., Rldgewood New Jersey, 1981 and Helmut Stache "Tensld-Taschenbuch" ("Surfactant Handbook"), Carl Hauser-Verlag Munich/Vienna 1981. 25 The agrochemlcal formulations as a rule contain 0.1 to 99X, 1n particular 0.1 to 95Z, of aetlve substance of the formula Z, 99.9 to IS, in particular 99.8 to SS, of a solid or liquid adjuvant and 0 to 23X, In particular 0.1 to 2SX, of a surfactant. 30 - red aa commercial products, the final user as a rule employs dilute compositions.
The compositions can also contain other adjuvants, such aa atablUsers, antlfoama, viscosity regulators, binders, 35 tacklflers and fertilisers, or other aetlve substances, in order to achieve special effecta.
Such agrochemlcal compositions are a component of 18 the present Invention.
The examples which follow serve to Illustrate the Invention In more detail without restricting 1t. Temperatures are In degrees centigrade. Percentages and parts are 5 by weight. In addition, the following symbols are used: h « hour; d * day; ain. * minute; RT * room temperature; N * normality; abs ■ absolute, anhydrous; DHSO * dlmethylsulfoxide; and DHF '• dimethylformamlde. Pressures are given In millibar mb or bar b. 10 Preparation examples Example HI: Preparation of ✓C1 OH CI—( i-CW-C-H- rn TT2 W jl «2.4-Tr1axol-1-yl)-2-(2.4-dlchlorophenyI)-3-fluoro-oentan-2-ol 15 a) Preparation of the Intermediate Z1 CI—^ C-CHF-CjBJ — o 1-(2.4-P1ch lorophenyl)-2-fluorobutanone 31 g of dry potassium fluoride were added to a mixture of 77 g of 1-(2,4-d1chlorophonyl)-2-bromobutanone and 20 500 mg of 18-crown-d In 750 ml of absolute acetonltrlle and the.mixture was slowly heated to 100° to 110°C, while stirring. After about 48 hours, the reaction had ended (checked .by gas chromatography or by NRR). The reaction solution was than poured onto 2 litres of 1ce-water and extracted 25 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 SO Ns) Boiling point: 77-78°/0.008 mbar. b) Preparation of another Intermediate ID •e»« CI- 2-(2 #4-P i chlorophenyI)-2-(1-fluoropropyI)-ox1rane 8 g of 80Z sodiua hydride were suspended in 300 al of absolute DHSO. 68 g of triaethyloxosulfoniua iodide were 5 introduced into this suspension in portions under a nitrogen ataosphere, while stirring, when the evolution of h/drogen had ended and the exotheraic reaction had subsided/ the nlxture was stirred at RT for a further 2 hours. A solution of 57 g of 1-t2,4-d1chlorophenyl)-2-fluorobutanone in 100 al 10 of tetrah'ydrofuran uas thon added dropwlse in the course of 30 nlnutes, and the resulting Mixture was stirred for 3 hours and thon diluted to five tines Its voluae with Ice-water and extracted several tlaes with diethyl ether. The combined extracts were washed with water, dried over sodlua 15 sulfate and freed froa the solvent In vacuo. Yield: 55 & In the form of a brown oil. c) Preparation of the end product: A Mixture of 55 g of 2-<2,4-d1chlorophenyl)-2- Exaaple H2: Preparation of - ft II D ——a SO 1 —<1H—1.2.4-Tr1a»ole-1-»t>-2-(2.4-d1chlorophenyl)-3-<4-chloro-ohenoxy)-3-fluoropropan-2-ol a) Preparation of the Intermediate: Z®1 F ci—f >-c—ca \mS ii i • 0 Br 5 1-(2,4-01chlorophenyI)-2-broao-2-fluoroethanone A solution of 16 g of bronine In 100 al of carbon tetrachloride was added to a solution of 20.7 g of a-fluoro-2,4-dlchloroacetophenone In 100 al of carbon tetrachloride at 40° to 45°C. After about 1 hour, the brown solution 10 had decolourised. Stirring was continued for another hour and the Mixture was then extracted by shaking with aqueous, sodiua bicarbonate solution and evaporated In vacuo. The oily residue was then distilled under a high vacuun. Yield: 17 g. Boiling point: 89-92°C/0.02 abar. 15 b) Preparation of another Intermediate: /""v ci—f >-c-cm-o—Z >-cx \_y ii \./ 1-(2.4-0IchlorophenyI)-2-<4-chlorophenoxy)-2-fluoroethanone 12.8 g of chlorophenol and 13.8 g of potasslua carbonate were stirred 1n 200 al of acetone for 1 hour. 28 g 20 of 1-<2,4-d1chlorophenyl)-2-broao-2-fluoroethanone 1n SO al of acetone were added dropwlse to this suspension and the alxture was refluxed for 3 hours. After cooling to RT, the colourless salt precipitate was filtered off, the acetone was reaoved 1n vacuo and diethyl ether was added. The ether 25 solution was washed with water, dried over sodiua sulfate and filtered and the filtrate was concentrated. The oily crude product crystallises after digestion with n-hexane. Yield: 21.5 g In the fora of yellowish crystals. Melting point: 8S-87°C. 21 2-(2.4-0Ichlorophenyl)-2-(4-chlorophenoxyfluoromethrI)-o»1rane 5 1 g of 80Z sodiua hydride uas stirred In 80 al of 0HS0 under a nitrogen atmosphere and 10.3 g of trlaethyloxo-sulfonlum Iodide were added In portions. After the exother-■1c reaction had subsided, the alxture uas stirred at RT for a further hour> a solution of 2-<2,4-d1chlorophenyl)-2-10 <4-chlorophenoxy)-2-fluoroethanone In 30 al.of tetrahydro-furan was then added dropwlse and the resulting alxture was stirred at 23° to 30°C for a further 3 hours and then poured onto 1 litre of waters The product was extracted with diethyl ether, the extracts were washed with water, dried 15 over sodiua sulfate and filtered and the filtrate was concentrated. Yield: 15 g as a yellowish oil. d) Preparation of the end product: A solution of 13 g of 2-(2,4-d1chlorophenyl>-2-<4-chlorophenoxyfluoromethyl)-oxirane, 4 g of. 1,2,4-trlazole 20 and 0.5 g of potaaslua tert.-butylate 1n 100 al of DRF was stirred at 80° to 100°C for 15 hours. After cooling to RT,the reaction solution was poured Into 500 al of water, whereupon the crude product separated out as an oil. The mixture was extracted with diethyl ether, the coeblned ex-25 tracts were washed with water, dried over sodiua sulfate and filtered and the filtrate was concentrated. Yield: 11 g of an oily crude product, which crystallised on digestion with n-hexane. Yield of the purified product: 7 g. Melting point: 155-157°C. 30 The substances shown below can also be prepared In Table 1: Coapounds of the foraula u- OR. *, OMrf Coapound No.
Ar RI *1 *3 I Physical constant y~\ melting point 1 C6H3G12<2,4) H H o—^ p—ci #»• H 155-157* melting point 2 C6H3C12<2,4) H H C2»5 H 204-206* ■elting point 3 C6H3C12(2,4) H H H N 142-143* melting point 4 C6«aC1(4) H H Vr* N 149-151* melting point 5 c6H3ci(2)r(4) H H u N 132-133* /-v S~\ melting point 6 CI—' /— H H H N 118-120* melting point 7 CI II n « CU 156-157* 8 C6H3C1(2,4) H B a3 N melting point 202-204* Table 1 Continuation) Coapound Ar "l "2 R3 X Physical constant No. 9 II II II N melting point 87-100* IO ••• • H II H Cil melt ing point 100-105* 11 C6H3C12(2,4) C"j 11 C2M5 N 12 C6H3C12(2,4) Benzyl II II N melting point 13 C&II3C1(2)P(4) II II c2u5 N 171-171* 14 "■<><> itta ••• .-/l II II H N melting point 160-161* 15 H II II CH 16 C6U3C1(2)F(4) ai2oi-ai2 H C2»5 N Resin Ti4 Table 1 (Continuation) Coapound NO. *r «t 27 Blph«nyl-4-yl ii 2 ft C6»3C12(2,4) ii 29 C6H3C12(2.) n 30 C^CIU) u 31 C6H}C1(2)F(4) ii 32 C6U3CI(2)F(4) ii 33 ••• • Ci-.( >-o~> •■1 ••• ii 34 J k i V «-< >-«-< •a* • •• ii Physical constant CM.
OC^j SC3»l7-n OC1I -f> a«, 3 -ci cu.
Cll.
Cll melting point 163-165* nelting point 146-147* melting point 173-174* Table 1 (fontinuation) Coapound Ho.
Ar 35 CjHjdjU.A) 36 C6H4Cl<4> 37 C6H4C1(2)F(4) 38 C6II3CI(2)F(4) 3.9 C6H3«(2)F(4) 40 C6H4Cl2<2,4> Physical constant H II H H Cll.
W c6ii4«(«) Cll.
Cll, S~\ o-.^ ^.-Cl c2h5 H' N n H H melt ing point 186-198* nelting ooint 141-143° Table 1 (Coitfnuatlon) C expound No. *1 42 43 <.4 45 46 47 4ft Ar Wl2(J'4) C6H3C12(2,A) C6«3C12(2,4) Br \ / y I A \ A Br~"\ >-®-< / C,ll, (4) 6 H V c6»3F2<2'4> Ci- /"V s »■< * /"i \ "2 *3 X Physical constant U CH.
CH 2 S melting point u CH-n H 141-142* II 3 7 w N .
™UirSlP0102* meltinq point II H N 118-119* melting point II II Cll 120-125* meltinq point II C.ll.
H 141-141* II 2 S c2ii5 N melting point . 154-156* u u H . viscous oil Table 1 (Continuation) Coapounc No.
Ar "l *2 *3 X Physical constant 49 f'~\ S~\ Br-«f >*~®~\ •a* H r H N ireltinj^oint 50 K >-°-< >" ««• U t H N meltinq point 70-72* 51 H r H N ■siting point 125-127* 52 «■<>(> ■/*» «1 P U N viscous oil 53 / \ C«3 ii CHj N Resin 54 ci-< >-o-< >- /»3 dijCH-aij H ch3 H 55 ••• ••• ii H C2»5 H Table 1 (Cort inuatlon) Coapound Ar *2 «3 X Physical constant no.
S6 c6u3c|j(2.*) u H C6U5 N 57 C.H.CKO /'"v «-< >-o-\ ii ii VS N SS ii ii a,3 N 59 y~\ ii H C2U5 N 60 ci-< >-o-< >- /»3 CM2-C6M5 ii N 61 ci-< >-o-< >-. ^ ai2"C6U5 U c2«5 H 62 A* \ / \ ii ii a,3 N 30 Formulation example* for Hauid active »ub>tinc» of the formula 1 (>* per cent by weight) F1. Emulsion concentrates a) b) c) Active substance from the table 2SX 40X SOX 5 Ca Dodecylbenzenesulfonate Castor oil polyethylene glycol ether sx 8Z 6X (36 mol of ethylene oxide) 5X - - TrlbutyIphenol polyethylene glycol ether (30 mol of ethylene oxide) - 12Z 4Z 10 Cyclohexanone - 1SX 20Z Xylene mixture 65Z 25Z 20Z ' Emulsions of any desired concentration can be pre- pared from such concentrates by dilution with water.
F2. Solutions a) b) c) d) 15 Active substance from the table 80% 10X $t 95X Ethylene glycol monomethyl ether 20Z a « - Polyethylene -glycol Nt) 400 - 70X - - N-Hethyl-2-pyrro 11 done - 2QX - Epoxldlsed coconut oil - IX SX 20 Benzine (boiling range 160-190°C) (HW ■ molecular weight) • 94X The solutions are suitable for application 1n th« form of very small drops.
F3. Granules a) b) 25 Active substance from the table 5Z 10X Kaolin 94X - Highly dlaperae alllca 1X Attapulglte - 90S The active substance Is dissolved 1n methylene chlo-30 ride, the solution Is sprayed onto the carrier and the solvent Is then evaporated off In vacuo.
F4. Busts a)- b) Active substance from the table 2X 5X Highly disperse silica 1X 5X 35 Talc 97X Kaolin - 90S Ready-to-use dusts ar* obtained by Intimate mixing 31 of the carrier* with the active substance.
Formulation examples for solid active substances of the formula I (X ■ per cent by weloht) F5. Wettable powders a) b) c) S Active substance from the table 25Z 50Z 7SZ Na Lignlnsulfonate SZ SZ Na Laurylsulfate 3Z - SZ Na ftiisobutyInaphthalenesulfonate - 6Z 10Z Octylphenol polyethylene glycol ether 10 (7-8 mol of ethylene oxide) - 2Z - Highly disperse silica 5Z 10Z 10Z Kaolin 62Z 27Z The active substance 1a mixed thoroughly with the adjuvants and the mixture la ground thoroughly in a suitable 15 mill. Vettable powdara are obtained, which can be diluted with water to give auapen»1ons of any desired concentration. F6. Emulsion concentrate Active substance from the table 10Z Octylphenol polyethylene glycol ether 20 (4-5 mol of ethylene oxide) 3Z Ca ftodecylbenzeneaulfonate 3X Castor oil polyglycol ether (35 mol of ethylene oxide Cyclohexanone 30Z 25 Xylene mixture 50Z Emulsions of any desired concentration can be prepared from this concentrate by dilution with water. FT. Busts a) b) Active aubstance from the table SZ 8Z 30 Talc 95Z Kaolin - 92Z Ready-to-uae duata are obtained by mixing the active substance with the carrier and grinding the mixture on a suitable mill. 35 F8. Extruded granules Active subatanee froa the table 10X Na Lignlnsulfonate 2Z 33 Carboxymethylcellulose 1S Kaolin IX The active substance is mixed with the adjuvants and the mixture is ground and moistened with water. This mix-S ture is extruded and subsequently dried in a stream of air. f9. Coated granules Active substance from the table 3X Polyethylene glyeol (MW 200) 3% Kaolin 94X 10 (NVI ■ 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. 15 F10. Suspension concentrate Active substance from the table 408 Ethylene glycol 10Z Nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6Z 20 Na Lignlnsulfonate 10S Carboxymethylcellulose IX 37X Aqueous formaldehyde solution 0.2X Silicone oil in the form of a 75Z aqueous emulsion 0.8Z 25 Water 32X 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. 30 Biological examples: Example 81: Action against Puccinia graminis on wheat a) Residual-orotectlve action 6 days after sowing, wheat plants were sprayed with a spray liquor (0.02Z of active substance) prepared from a 35 wettable powder of the active substance. After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation at 95-1008 relative atmos- 3'J pheric hualdlty and about 20°C for 48 hours, the Infected plants were placed in a greenhouse at about 22°C. The development of rust pustules uas evaluated 12 days after the Infection.
S b) Systemic action 5 days after sowing, wheat plants were watered with a spray liquor (0.006Z 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 10 with a uredospore suspension of the fungus. After incubation at 95-100Z relative atmospheric huaidity 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 12 days after the infection. 15 Compounds from the table had a very good action against Puceinia fungi. Untreated but Infected control plants displayed a Puceinia attack of 100X. Inter alia, the compounds 1 to 10, 13, 14,16 ,18 ,19 ,24 , 32 -34 ,40 - 46 and 48 - 52 inhibited the Puccinia attack to 0 to SZ. 20 Example B2; Action against Cercospora-arachidicola on groundnut plants Residual-protective action Groundnut plants 10 - 15 cm high uere sprayed uith a spray liquor (0.006Z of active substance) prepared from 25 a wettable powder of the active substance, and 48 hours later uere infected uith a conidla suspension of the fungus. The Infected plants uere incubated at about 21°C at a high atmospheric humidity for 72 hours and uere then placed in a greenhouse until the typical leaf spots appeared. The fun-30 gicidal.. action uas evaluated, on the basis of the number and size of the spots uhich had appeared, 12 days after the infection.
In comparison with untreated but infected control plants (number and size of spots ■ 100Z), groundnut plants 35 uhich had been treated uith active substances from the table shoued a greatly reduced Cercospora attack. Thus, compounds 1 to ?, 13, 18, 19, 24, 32, 37, 40-46 and 49-53 almost 34 completely prevented the occurrence of spot* in the above experiments (0-10*).
Exaaple 83: »ction aoainat Eryslphe qraminls on barley a? Residual-protective action S Barley plants abo-jt 8 cm high were sprayed with • spray liquor (0.002X 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 uere placed in a greenhouse at 10 about 22°C and the fungal attack uas evaluated after 10 days. b) Systemic action Barley plants abn-t.8 cm high were watered uith a spray liquor (0.006X of active substance# based on the volume 1S of soil) prepared from a wettable powder of the active substance. Care was thereby taken that the spray liquor did not cone into contact with the above-ground parts of th« plants. After 48 hours# the treated plants were dusted with conidia of the fungus.. The infected barley plants were 20 placed in a greenhouse at about 22°C and the fungal attack was evaluated after 10 days.
Compounds of the foraula I showed a good action against Eryslphe fungi. Untreated but infected control plants displayed an Eryslphe attack of 100%. Amongst other 25 compounds from the table# coapounds 1 to 10# 13# 14#16 #18 # 19# 24 #32 *34 *37 #40 -46 and 48 - S3 Inhibited the fungal attack on barley to 0 to 5X# and# in particular# coapound No. 2 effected complete reduction of attack.
Exam'ble 84: Residual-protective action aoainst Venturia 30 tnaequalis on apple shoots Apple seedlings with fresh shoots 10 - 20 ca long were sprayed with a spray liquor (0.006X of 'active substance) prepared from a wettable powder of the active substance.
After 24 hours, the treated plants were infected uith a 35 conidia suspension of the fungus. The plants uere then Incubated at 90 - 100X relative atmospheric humidity- for S days -and placed-in a greenhouse at 20-24°C for a further 10 days. 35 The scab attack was evaluated 15 days after the infection. Coapounds 1 to 6, 8, 9, 13/16 , 18# 19/ 32/ 40/ 42, 44 - 46 and 48 ~ 52 inhibited the disease infestation to less than 10%. In contrast, untreated but Infected control shoots showed 100% attack. 5 Exaaple 85; Action against Botrytis cinerea on beans Residual-protective action Bean plants about 10 ca high were sprayed uith a spray liquor (0.02Z of active substance) prepared froa a 10 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 95-100Z relative ataospheric humidity at 21°C for 3 days, the fungal attack was evaluated. The coapounds froa the 15 table in many cases very greatly inhibited the fungal Infection. At a concentration of 0.02Z, coapounds '1 to 6, 8, 9, 13, 14, 19, 24, 32, 34, 40, 42, 44, 45, 46 and .48-52, for exaaple, proved to be coapletely effective. The disease infestation was 0 to 8Z. 20 The Botrytis attack of untreated but Infected bean plants was 100X.
Exaaple B6: Action against Piricularia oryiae on rice plants Residual-protective action After being grown for two weeks, rice plants were 25 sprayed with a spray liquor (0.002Z of active substance) prepared froa 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 -95-100Z relative ataospheric huaidlty at 24°C for 5 days, the 30 fungal attack uas evaluated.
Rice plants which had been treated with a spray liquor containing one of the coapounds froa Table 1, such as, for exaaple. No. 13 or 32, as the active substance, showed a fungal attack of less than 1QZ, in comparison with the 35 untreated control plants <100% attack). 3G

Claims (18)

CLAIMS:
1. A coapound of the general foraula X I"* I* A*—CHj C C F (I) Ar Rj in which Az is 1H-1,2,4-triazole, 4H-1,2,4-triazole or 1H-5 imidazole; Ar is an unsubstltuted or substituted aromatic radical froa the series coaprising phenyl, biphenyl, phenoxyphenyl and naphthyl; R^ is hydrogen, C^C^-alkyl, Cj-C5-alkenyl or benzyl; Rj is hydrogen, fluorine or ~Cj-alkyl and Rj is hydrogen, fluorine, Cj-C^-alkyl, C^-C^- 10 haloalkyl, Cj-C^-alkoxy, Cj-Cg-alkylthio, phenyl, phenoxjr^. phenylthio or C^-C^-cyc loa Iky I, and each aromatic substituent or aroaatic aoiety of a substituent is unsubstltuted or aono- or poly-substituted by halogen,■Cj-C^-alkyl, C^-C^-alkoxy, C1-C^-haloalkyI, nitro and/or cyano; 15 including the acid addition salts, quaternary azoliua salts and metal coaplexes; provided that R^ and Rj cannot each simultaneously be fluorine.
2. A coapound of the foraula I according to claia 1, in uhich Az is 1 H-1,2,4-triaz.ole or iH-iaidazole; Ar is an unsubstltuted or substituted aroaatic radical froa the se- 20 ries coaprising phenyl, biphenyl and phenoxyphenyl; Rj is hydrogen; Ij is hydrogen, fluorine or C^-C3~alkyl; and R3 is hydrogen, fluorine, Cj-C^alkyl, Cj-Cj-haloalkyl, C^-Cj-alkoxy, C^-Cj-alkylthio, phenyl, phenoxy or phenylthio, each phenyl aoiety being unsubstituted 25 or substituted by fluorine, chlorine, broaine, methyl, ae-thoxy, CFj, MOj and/or cyano; including the acid addition salts, quaternary azoliua salts and aetal coaplexes. -
3. A coapound of the foraula I according to claia 2, in which Az Is 1H-1,2,4-triazole; Ar Is phenyl or phenoxy- 30 phenyl uhich Is unsubstltuted or substituted In the 2- and/or 4-position by aethyl or halogen; Rj Is hydrogen; Rj is hydrogen, fluorine or aethyl; and is hydrogen, fluorine, Cj-C^-alkyl or a radical from the series coaprising phenyl, phenoxy and phenylthio uhich 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-(1H-1,2,4-tr1azol-1-yI)-2-(2,4-dichlorophenyI)-3-fluorobutan-2-oI, 1 -C1 H-1,2,4- t r1azol-1-yl)-2-C2-chloro-4-fluoropheny I)-3-fluorobutan-2-ol, 1-ClH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoro-pentan-2-ol, 1-<1H-1,2,4-triazol-1-yl)-Z-(2,4-dichloro-phenyI)-3-fluoro-4-nethyIpentan-Z-ol, 1-(1H-1,2,4-trlazol- 1-yL)-Z-(2-chloro-4-fluorophenyI)-3-fluoropentan-2-oI, 1 - C1 H-1,2,4-t r1azol-1-yI)-2-Cp-l4-chlorophenoxy)phenyl]-3-fluoropropan-Z-olor1 —(1H—1,Z,4-tr1azol-1-yl)-2-(2,4-d1-chlorophenyI)-3-<4-chlorophenoxy )-3-fluoropropan-2-ol.
5. A compound of the formula I according to claim 1, chosen from the series: 1-(1H-1,2,4-tr1azol-1-yl)-2-<4- chlorophenyl>-3-fluorohexan-2-oI, 1-(1H-1,2,4-tria*ol-1-yl>- 2-(2,4-dichlorophenyIJ-3-fluorohexan-2-ol, 1-ClH-1,2,4-tri-azo1-1-yl)-2-(2,4-d1ehloropheny1-3,3-dlfluoropentan-2-ol, 1-<1H-1,2,4-tr1azol-1-yI)-2-C2,4-d1chlorophenyI)-3-fluoro-4-methylpentan-2-ol, 1-11H-1,2,4-triazol-1-yl>-2-Cp-<4-bromo-phenoxy)phenyl3-3,3-difluoropropan-2-ol, 1-(1H-1,2,4-triazol- . 1-yl)-2-Cp-(4-fluorophenoxy)pheny13-3,3-difluoropropan-2-ol, 1-
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 II VC-Rj F 3 9 with' an azole of the foraula XXI M—Ar to give, a coapound of the foraula la OH I Ar-C-CH-~A* (la) I 2 V?-*3 F 5 and, if required, converting the alcohol la into an ether of the foraula I in the conventional aanner, for exaaple by reaction with a coapound of the foraula IV R1 - W CIV) in which fornulae la, XI, XXX and IV, the substltuent* Rj, 10 Rj, Rj, Ar and Az are as defined under foraula X, N Is hydrogen or a aetal atoa and W is OH or a conventional leaving group.
7. A composition for controlling or preventing attack by aicroorganisns, uhich contains, in addition to convcn- 15 tional carriers, a coapound of the foraula I according to claia 1 as at least one active coaponent.
8. A composition according to claia 7, which contains 0.1 to 99% of an active substance of the foraula I, 99.9 to ■ 1X of a.solid or liquid adjuvant and 0 to ZSX of a surfac-20 tant.
9. A aethod of controlling or preventing attack on crop plants by phytopathogenle alcroorganisas, which coaprlses applying a coapound of the foraula I as defined in claia 1 to the plants or their location.
10. Compounds of foraula I substantially as described uith reference to any of the preparation Exaapl-es.
11. Process for producing compounds of foraula I substantially as described uith reference to any of the 5 preparation Examples.
12. Composition for controlling or preventing attack by microorganisms according to claia 7 substantially as described uith reference to any of the formulation Examples. 10
13. 1-<1H-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)- 3-<4-chlorophenoxy)-3-fluoropropan-2-ol.
14. 1-(1H-1,Z,4-triazol-1-yD-2-(4-ehlorophenyl>-3-fluorohexan-2-ol.
15. 1-I1H-1,2,4-triazo1-1-y0-2-Cp-(4-chlorophenoxy) 15 phenyl3-3-fluoropropan-2-ol.
16. 1-(1M—1,2,4-triazoI-1-y0-2-<2-chloro-4-fluorophenyI)-2-propenyloxy-3-fluoropentane.
17. 1-C1H-1,2,4-t riazo 1-1-y l)-2-(4-f luoropheny I) -2-(4-chlorobenzyloxy)-3-fluoropropane. 20
18. 1-(1H-1,2,4-triazo1-1-yU-2-(2,4-di ehlorophenyI)- 2-methoxy-3-fluorobufcane. F. R. KKTJ.Y a 00., AGENTS FOR THE APPLICANTS.
IE2933/83A 1982-12-14 1983-12-13 1-azolyl-2-aryl-3-fluoroalkan-2-ols as microbicides IE56378B1 (en)

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IL70422A0 (en) 1984-03-30
TR22109A (en) 1986-04-21
CA1209152A (en) 1986-08-05
SU1326194A3 (en) 1987-07-23
PL139146B1 (en) 1986-12-31
PH22949A (en) 1989-02-03
IL70422A (en) 1989-05-15
CS250237B2 (en) 1987-04-16
NZ206562A (en) 1989-02-24
KR840006979A (en) 1984-12-04
HU196891B (en) 1989-02-28
NO834592L (en) 1984-06-15
EP0113640B1 (en) 1990-05-23
AR240810A2 (en) 1991-02-28
GB2166729A (en) 1986-05-14
PL245063A1 (en) 1985-10-22
MA19972A1 (en) 1984-07-01
ES8504151A1 (en) 1985-04-16
AU603417B2 (en) 1990-11-15
DE3381589D1 (en) 1990-06-28
GB2132195A (en) 1984-07-04
BG48681A3 (en) 1991-04-15

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