IE56378B1 - 1-azolyl-2-aryl-3-fluoroalkan-2-ols as microbicides - Google Patents
1-azolyl-2-aryl-3-fluoroalkan-2-ols as microbicidesInfo
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- IE56378B1 IE56378B1 IE2933/83A IE293383A IE56378B1 IE 56378 B1 IE56378 B1 IE 56378B1 IE 2933/83 A IE2933/83 A IE 2933/83A IE 293383 A IE293383 A IE 293383A IE 56378 B1 IE56378 B1 IE 56378B1
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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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
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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Abstract
Es werden 1-Azolyl-2-aryl-3-fluor-alkan-2-ole der allgemeinen Formel I beschrieben, worin Az für 1H-1,2,4-Triazol, 4H-1,2,4-Triazot oder 1H-Imidazol steht; Ar einen unsubstituierten oder substituierten aromatischen Rest aus der Reihe Phenyl, Biphenyl, Phenoxyphenyl und Naphthyl bedeutet; R, für Wasserstoff, C,-C4-Alkyl, C3-C5-Alkenyl oder Benzyl steht; R2 Wasserstoff, Fluor oder C1-C6-Alkyl bedeutet; und R3 Wasserstoff, Fluor, C1-C6-Alkyl, C1-C6-Haloalkyl, C1-C6-Alkoxy, C,-C6-Alkylthio, Phenyl, Phenoxy, Phenylthio oder C3-C7-Cycloalkyl steht, wobei jeder aromatische Substituent oder aromatische Anteil eines Substituenten unsubstituiert oder ein- oder mehrfach durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, C,-C4-Haloalkyl, Nitro und/oder Cyanosubstituiert ist; unter Einschluss der Säureadditionssalze, quaternären Azoliumsalze und Metallkomplexe. Es werden ferner Methoden zur Herstellung dieser Produkte offenbart sowie agrochemische Mittel, die als Wirkstoff eine dieser Verbindungen enthalten. Ferner wird ein Verfahren zur Bekämpfung phytopathogener Mikroorganismen mit Hilfe dieser Substanzen beschrieben.
Description
Th· present invention relates to noveL, substituted. 1-azolyl-2-aryl-3-fluoroalkan-2-ols end ethers thereof, of the formula I below, and to acid addition salts, quaternary azoliua salts and metal complexes thereof· The invention furthermore relates to the preparation of these substances and microbicidal conpositions 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 conpositions for the control of harmful o1croorganlsms, preferably fungi which are harmful to plants.
The compounds according to the Invention are those of the general formula I Aa—CBjr* t.
(I) ft d 1n which Az Is 1H-1,2,4-trlazole, 4H-1,2,4-trlazole or 1HImldasole; Ar Is an unsubstituted or substituted aromatic radical froa the series comprising phenyl, biphenyl, phenoxy phenyl and naphthyl; RY Is hydrogen, C-j-€4-0IkyI, C3-C5alkenyl or benzyl; Rj Is hydrogen, fluorine or alkyl and R3 Is hydrogen, fluorine, C^-C^-alkyl, C-j-C^haloalkyl, t^-C^-alkoxy, C^-C^-alhylthlo, phenyl, phenoxy, phenylthlo or C3-C7~cycloalkyl, and each* aromatic substituent or aromatic moiety of a substituent Is unsubstltutsd or flono* or poly-substituted by halogen, C-j-c^-alkyI, C^-C^alkoxy, Cs-C^-haloalkyI, nitro and/or cyano; including the acid addition salts, quaternary azollum salts and metal complexes; with the proviso that Rj and Rj cannot each simultaneously he fluorine· The tern alkyl by itself or as a constituent of another substituent is to be understood as neanlng, for exanple, one of the following groups, depending on the number of carbon atons stated: methyl, ethyl, propyl, butyl, pentyl, w hexyl and the like and their isoners, for exanple isopropyl, isobutyl, tert.-butyl, isopentyl and the like. Haloalkyl is a nonohalogenated to perhalogenated alkyl substituent, for * example CHCl2, CHF2, CH2Cl, CCIj, CH2F, CH2CH2Cl CB^Br and the like, in particular CF^. Here and *.n the following text, halogen is to be understood as neanlng fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Alkenyl Is, for exanple, prop-1-enyl, allyl, but-1-enyl, but-2-enyl or but-3-enyl. Naphthyl is a- or finaphthyl.
The present invention thus relates to the free corn20 pounds of the formula X and add addition salts, quaternary azollum salts and metal eonplexes thereof. The free conpounds, In particular the 1H-1,2,4-triazole derivatives, are preferred In the context of fornula X.
Examples of salt-forning acids are Inorganic acids, such as hydrogen halide acids, such as hydrofluoric add, hydrochloric add, hydrobronic add or hydrlodlc add, as well as sulfuric add, phosphoric add, phosphorous add and nitric add, and organic adds, such as acetic add, trifluoroacetic acid, trichloroacetic add, propionic add, for30 nlc add, benzenesulfonic add, p-toluenesulfon1c add or methanesulfonic add.
* Ratal complexes of the formula X consist of the basic orgsnic molecule end an Inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, ace35 tates, 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 eighth sub-group, such as chromium, aanganese, iron, cobalt, nickel, zlreoniua, copper, zinc, silver, mercury end the like. The sub-group elements of the 4th period are preferred. The octal· can be In the various valences with which they are associated.
The aetal complexes of the formula X can be mononuclear or polynuclear, i.e. they can contain one or nore organic molecule components as ligands. Complexes with the metals copper, zinc, aanganese, tin and zirconium are preferred.
The compounds of the formula X 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 i vely and euratively in the agricultural sector or related fields for controlling micro-organisms which damage plants, the triazolylmethyl derivatives In the context of the formula X being preferred. The active substances of the formula X according to the invention are distinguished by a ury good phytofungicldal action and problem-free application when used In low concentrations. Moreover, they also have a growth-regulating action, in particular a growth-inhibiting action, especially on tropical cover crops.
The following groups of substances are preferred, because of their marked microbicidal action, in particular their phytofungicldal action: compounds of the formula X in which Az Is 1H-1,2,4-trlazole or 1H-lmidazole; Ar is an unsubstituted or substituted aromatic radical from the aeries comprising phenyl, biphenyl and phenoxyphenyl, Rj Is hydrogen; Rj 1» hydrogen, fluorine or Cj-Cj-alkyl; and R3 is hydrogen, fluorine, Cj-C^alkyl, C^-Cj-haloalkyl, Cj-c^-elkoxy, C^-Cj-alkyIthio, phenyl, phenyloxy or phenylthio, each phenyl moiety being unsubstituted or substituted by fluorine, chlorine, bromine, methyl, methoxy, Cfj, N02 and/or cyano; Including the acid addition salts, quaternary azolium salts and metal complexes* provided that R^ and R^ are not simultaneously fluorine.
Particularly preferred compounds of the formula X within this group are those In which Az is 1tt-1,2,4-triazole; Ar is phenyl or phenoxyphenyl which Is unsubstituted or, pror I ferably, substituted in the 2- and/or 4-position by eethyl or halogen, preferably fluorine or chlorine; Rf ii hydrogen; Rj Is hydrogen, fluorine or nethyl; and Rj Is hydrogen, fluorine, Cf-C^-alkyl or a radical fro· the series com5 prising phenyl, phenoxy and phenylthio which is substituted by fluorine, chlorine and/or bromine; provided' that Rj and R3 are not simultaneously fluorine· Examples' of specific particularly preferred substances from a fungicidal point of View are: l-OH-1,2,4-triaxoL-1-yl)-2-<2,4-dichlorophenyL)-3-fluorobutan-2-ol, 1-GH10 1,2,4-triazol-1-yl)-Z-(2-chloro-4-fluorophenyl>-3-fluorobutan-2-ol, 1-11H-1 ,-2,4-t ri azo 1*1 -yl>-2-12,4-d1 chlorophenyO3-fluoropcntan-2-ol, 1-(1H-1,2,4-triazol-l-yl)-2-(2,4-dichloropheny0-3-fluoro-4-methylpentan-2-ol, 1-(1H-1,2,4tr1azol-1-yl)-2-(2-chloro-4-fluorophenyl>-3-fluoropentan15 2-01, 1-(1H-1,2,4-tr1aiol-1-yO-2-(2,4-dichlorophenyl)-3(4-chlorophenoxy)-3-fluoropropan-2-ol, 1-(1H-1,2,4-triazolo 1- yO-2-Cp-(4-chlorophanoxy)pheny13-3*fluoropropan-2-oI, i-<1H-1,2,4-triazol-l-yl)-2-(4ch loropheny I) -3-f luorohexan-2-ol/ 1-(1 H-1,2,4-triazol-1-yO2- (2,4-dichlorophenyO-3-fluorohexan-2-ol, 1-ClH-1,2,4-triazol-1-yI)-2-(2,4-dichlorophenyl-3,3-dlfluoropentan-2-ol, 1- (1H-1,2,4-tr1azo1-1-yO-2-(2,4-dichlorophenyl)-3-fluoro-425 methy lpentan-2-ol, 1-(1 H-1,2,4-triazol-1-yO-2-Cp-(4-bromophenoxy)pheny0-3,3-d1fluoropropan-2-ol, 1-(1H-1,2,4-tri0201*1-y O-2-Cp-(4«f luorophenoxy) pheny 0-3,3-di f luor o-propan2- 0 L, 1-(1H-1,2,4-triazo1-1-yO-2-Cp-(4-chLorophanoxy)phony133,3-di fjluoropropan-2-ol and 1-(1H-1,2,4-tr1azol-1-yl)-2-Cp30 (4-chlorophanoxy)-2-methylpheny0-2-hydroxy-3-fluoropropane.
The compounds of the formula X are prepared by a process which comprises first reacting an oxlrane of the formula XX t with an azole of the fornula XII M—Ax (III) to give a compound of the formula la OH I Ar-C-CB^-Ax (Ia) I 2 I and, if required, converting the alcohol la into an ether of the fornula X in the conventional nanner, for example by re- ί action with a conpound of the fornula IV R1 - U (IV) In which formulae Ia, XI, III and IV, the substituents R^, 4 R2, Rj, Ar and Az are as defined under formula I, N 1s hydrogen or, preferably, a metal atom, in particular an ♦ alkali metal atom, such as Ll, Na or K, and V Is OH or a conventional leaving group. Conventional leaving groups are known from the literature.
If appropriate, the reaction of II u1th III to give la Is carried out 1n the presence of condensing agents or acid-binding agents. Suitable egents are organic end Inorganic bases, for example tertiary amines, such as trlalkylamlnes (trlmethylamlne, triethylamine, trlpropylamlne and the like), pyridine and pyridine bases (A-d1methylaminopyr1d1ne, A-pyrrolldylemlnopyrldlne and the like), oxides, hydrides snd hydroxides, carbonates and bicarbonates of alkali metals end alkaline earth metals CCaO, BaO, NaOH, KOH, NaH, Ca(0H)2, KHCOj, NaHCOj, Ca(HC03)2, KgCO^ and Na2C(f3) and alkali metal acetates, such as CH3C90Na or, CH3C00K. Moreover, alkali metal alcoholates, such es C2H3ONa, CjHj-nONa and the like, are also suitable.
In some cease. It may be advantageous If the free azole XXX CM · hydrogen) Is first converted Into the corresponding salt, for exaaple 1n situ with ah alcoholate, end then to react the salt with the oxlrane of the fornula XI. Xn the preparation of the 1,2,4-trlazole derivatives, 1,3,4-trlazolyl isomers are generally also formed in e parallel reaction, and these can be separated free one another in a conventional aanner, for exaaple with different solvents.
The reaction (XX with XXX to give la) 1« preferably carried out In an organic solvent which Is relatively polar but Inert in the reaction, for exaeple M,M-d1aethyIforeanlde, N,Ν-dlnethylacetaelde, dleethyIsulfoxlde, acetonitrile, benzo nitrile and the like· Such solvents can be used In conblna__-Ί tion with other solvents which are Inert in the reaction, for exaeple benzene, toluene, xylene, hexane, petroleue * 10 ether, chlorobenzene, nitrobenzene and the like. The reaction teeperatures are In a teeperature range froe 0° to 150°C, preferably 20° to 100°C.
This reaction (XX with XIX to give Xa) can furthermore be carried out analogously to reactions which are al15 ready known for other oxlranes with azoles (cf· Seraan Offenlegungsachrlft 2,912,288).
Xn the part reactions Mentioned, the Interaedlatea can be Isolated froe the reaction aedlua and, If desired, purified by one of the generally conventional aethods, for exaaple by washing, digestion, extraction, crystallisation, chroaatography, distillation and the tike, before the further reaction.
Xn cases where W In foraula XV Is a conventional leaving group, the further reaction of Xa to give X la car25 rled out In the absence or, preferably, in the presence of a solvent which 1s Inert In the reaction· Exanples of suitable solvents are the following: Ν,Ν-dlaethylforaaslde, N,N-d1aethylacetaelde, hexaaethylphosphoric acid trlaalde, dleethylauIfoxide, 2-oethyl-2-pen30 tanone and the like. Mixtures of these solvents with one another or with other conventional Inert organic solvents, « for exaaple with aroaatlc hydrocarbons, such as -benzene, toluene, the xylenes and the like, can also be used· Xn sone esses It nay prove advantageous to carry out the reaction In " 35 the presence of a base, for exaaple an alkali aptal hydride, hydroxide or carbonate. In order to accelerate the rate of reaction· However, 1t aay also be advantageous first to convert the alcohol of the formula Ia (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 2 and the like) and alkali natal-organic 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 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 tho formula IV (In which U *1s a leaving group), the reaction advantageously being carried out 1n the presence of a crown ether.
If N K, 18-crown-6, 1n particular. Is present; and if- N » Na, 15-erown-5, In particular, Is present. The reaction Is advantageously carried out In a medium which 1s Inert 1n 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 hydro25 carbons, such as benxene, toluene or the xylenes.
The following solvents are examples of the organic water-lmmladble phases aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, the xylenes and the like,1 halogcnatcd hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, 1,2-d1chloroethane, 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 arts tetraaIkylammonlum halides, bisulfates or hydroxides, such as tetrabutylammonium chloride, bromide or Iodide; trlethyIbenzylammonlum chloride or bromide; tetrapropylammenlum ι chloride, bromide or Iodide; and the like. Possible phase transfer catalysts include phosphonium salts· The reaction temperatures Ore in general between 30° and 130°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 advantageously 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 III itself can be used as the solvent. This condensation reaction is advantageously carried out in the preaence of a strong acid, for example paratoluenesulfonlc acid, at the boiling point of the azeotropic 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 M and then to react the product with a compound of the formula IV (where H » OH).
The starting substances of the formula III are generally known, or they can be prepared by methods which are known per ae· The oxiranes of the formula II are novel and are the subject of Divisional Patent Specification No. Ihey 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 ta in a simple manner, and, moreover, some of the compounds of the formula II have a fun35 glcidal activity towards harmful fungi from the families'of Ascomycetes, BaaIdiomycetes or Fungi imperfecti.
Epoxides of the formula II can be prepared from to ketones of the foraula V h Ar-C-C-F <▼) II I °*3 in a manner which is known per ae by reaction with dlnethylsulfoniun aethylide or dinethyloxosulfonium aethylide (Corey and Chaykovsky, JACS, 1962, 84^ 3782).
The ketones of the foraula V are accessible by methods which are known per se fron the literature (ef· J. Le- * roy, J. Org. Chen· 46, 206 (1981) or Houben-Weyl, volume V/3, page 211), fron the corresponding known tt-bromo-ketones by conventional replacenent 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 parti15 eular case, one or more solvents or diluents which are Inert 1ri the reaction can be present 1n 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 end petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetraehloroethylene; 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 proplonltrlle; M,M-d1alkyl«ted amides, such as dimethylformamide; dimethylsulfoxide; ketones, such as acetone, diethyl ketone and aethyl ethyl ketone, and mixtures of these solvents with one another. In t 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 ef the formula I A«— CBj- Ar (I) always have an asymmetric C atom C* In the position adjacent to the substituents Ar and OR-j and can therefore exist in two enantiomeric forms. Xn general, a mixture of the two enantiomers Is formed In the preparation of these substances, and this can be split Into the pure optical antipodes In a conventional manner, for example by fractional crystallisation of salts with strong optically active adds. 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 1n activity may also occur in the same action spectrum· Xf the radicals R2and R3 are different, the molecule contains a further centre of asymmetry (*), which leads to the existence of diastereomeric mixtures (three- and erythro-forma), 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 steps1 Is an Important component of the present invention.
Xt has been found, surprisingly, that compounds of the formula X have a microbicidal spectrum against phytopathogenic fungi and bacteria which 1s 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 •4 Ο .4 W of the formula X, the additional future growth of parts of plants also remaining protected from such microorganisms.
The active substances of the formula X are effective against phytopathogenlc fungi belonging to the following classes: Fungi imperfectl (for example, Botrytls, Helminthosporlum, Fusarlum, Septorla, Cercospora and Alternaria); and Basldlomycetes (for example the genera Hemilela, Rhizocotonia and Puccinia); and they are particularly active against the class of Ascomycetes (for example Venturia, Podosphaera, Eryslphe, Monilinia and Unclnula). Moreover, the compounds of the formula X 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 phytopathogenlc fungi which occur In the soil.
The invention thus also relates to microbicidal compositions and to the use of the compounds of the formula X for the control of phytopathogenlc microorganisms. In particular fungi which are harmful to plants, and for preventative prophylaxis of an attaefc 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 carriers and adjuvants described In this Application. The present Invention also includes a method of treating plants which comprises application of the compounds of the formula X 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 end 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 menderin); vegetable varieties: (spinach, lettuce, asparagus, cabbage varieties, carrot, onion, tooato, 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 X are usually employed In the form of formulations and can be applied to the area or plant to be treated et 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, 1$ nematlddes, mollusclcldee or mixtures of several of these products. If necesssry 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 1120 quid and correspond to the substances appropriate In the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackl* flora, thickeners, binders or fertilisers.
A preferred method of application of an active Bub25 stance of tha formula X or of an agrochemical composition containing at least one of these active substances Is application to tha foliage (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 X cen also enter the plants through the root via the sell (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 1n the form of granules (soil application). The compounds of the formiila I can, however, also be applied to seed (costing), by s method in which the seed Is either soaked In a liquid formulation of tha id active substance or coated with a solid formulation. Moreover, other types of applleitlon are possible in particular cases, thus, for exanple, controlled treatment of the plant stems or the buds.
The compounds of the formula X 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 known manner to, for example, emulsion concentrates, brushable pastes, directly sprayable or dilu10 table solutions, dilute eaulsions, wetteble 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 dr15 cumstances, as Is the type of composition. Favourable application amounts are generally 50 g to 5 kg of active substance IAS) per hectare; preferably 100 g to 2 kg of AS/hectare, and In particular 200 g to 600 g of AS/hectare.
The formulations, 1.e. the compositions, preparations or mixtures, containing the active substance* of the formula X and, If appropriate, a solid or liquid adjuvant are prepared In a known nanner, for example by Intimate mixing and/ or grinding of the active substances with extenders, for example with solvents, solid carriers snd. If necessary, sur25 face-active compounds (surfactants).
Suitable solvents ares aromatic hydrocarbons, preferably Cg to C^g fractions, for example xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dlbutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such os 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-methyl2-pyrrol1done, 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 exaaple for dust and λ 35 dispersible powders, ere ss a rule ground natural minerals, such as calclte, talc, kaolin, aontmorlLlonlte 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, sepiollte or bentonite, 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, dolomite or comminuted plant residues, can moreover be used. Further particularly advantageous adjuvants which promote application and can lead to a large reduction 1n the amount applied are natural (animal or vegetable) or synthetic phospholipids of the cephalln and lecithin series, for exsmple phosphat1dylothanolamlne, phosphatldyIserlne, phosphatidylcholine, sphingomyelin, phosphatidylinositol, phosphatidylglycerol, Lysoleclthln, plasmalogens or card1ol1p1n, which can be Isolated, for example, from animal or vegetable cells. In particular from the brain, heart or Uver or froa egg yolks or soya bean· Examples of commercial mixtures which can be used are phosphatidylcholine mixtures. Examples of synthetic phospholipids are dloctanoylphosphatldylchollne and d1paIm1toyLphosphatIdylcholine.
Suitable surface-active compounds, depending on the nature of the active substance of the formula X to be formulated, are non-1on1c, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood ss 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 <£io~c22)' *or example the Na or K salts of oleic add or stearic add, or of naturally occurring fatty add mixtures, which can be obtained, for example, from coconut IG oil or tallow oil. The fatty acid methyl-laurin salt* are ; also suitable.
However, so-called synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated bonzlmi5 dazole 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 acyl radicals, for example the Na or Ca salt of ligninsulfonlc acid, dodecyIsulfurlc acid ester or a fatty alcohol sulfate mixture prepared from naturally occurring fatty acids. These compounds also include the salts of sulfuric acid es15 ters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benximidaxole 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 triethanolamine salts of dodecylbensenesulfonic acid, dibutyInaphthaleneeulfonic add or a naphthalenesulfonic ae.id/formaIdehyde condensate.
Corresponding phosphates, for example salts of the phosphoric add ester of a p-nonylphenol-(4-14)-ethylone 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 18 carbon atoms In the olkyl radical of.the alkylphenols.
Other suitablE non-ionic surfactants are the watersoluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide and polypropylene glycol, ethylenediamlnopoly35 propylene 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 nonylphenoLpolyethexyethenols, castor oil polyglycol ethers, polypropylene polyethylene oxide adducts, trlbutylphenoxypolyethylene5 ethanol, polyethylene glycol end oetyIphenoxypolyethoxyethenol.
Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.
The cationic surfactants are. In particular, quater10 nary eaMoniun salts which contain at least one alkyl radical having a to 22 C atons as N-substltuent and lower alkyl er benzyl radicals, which aay or aay not be halogenated, or lower hydroxyalkyl radicals, as further substituents. The salts are preferably 1n the fora of halides, aethylsulfates or ethyIsulfates, and are, for exaaple, stearyltrlaethylamaonium chloride or benzyldl(2-chloroethyl)ethylemmon1ua bromide.
The surfactants conventionally used In the art of foraulatlon are described, Inter alia, 1n the following publications: He Cutcheon'a Detergents and Eaulslflers Annual gc Publishing Corp·, Ridgewood New Jersey., 1981 and Helaut Stache Tensld-Taschenbuch (Surfactant Handbook), Carl Hauser-Verlag Munich/Vlenna 1981.
The agrochenlcel formulations aa a rule contain 0.1 to 992, 1n particular 0.1 to 95Z, of active substance of the foraula Z, 99.9 to IS, 1n particular 99.8 to SS, of a solid er liquid adjuvant and 0 to 25S, 1n particular 0.1 to 25S, of a surfactant.
. Whilst concentrated compositions are rather preferred as commercial products, the final user as a rule eaploys dilute compositions.
The compositions can also contain other adjuvants, such as stabilisers, entlfoams, viscosity regulators, binders, tacklflerS’and fertilisers, or other active substances, in order to achieve special affects.
Such agrochemical compositions are s component of the present Invention· The exanples which follow serve to illustrate the Invention In nore detail without restricting 1t. Teaporatures are In degrees centigrade. Percentages and parts sre by weight. In addition, the following symbols are used: h » hour; d a day; nin. " nlnute; RT roon teeperature; N " normality; abs absolute, anhydrous; DMSO " dlnethylsulfoxlde; and DMF ® dinethylfornanlde. Pressures are given In aillibar mb or bar b.
Preparation examples Exanple H1s Preparation of zC1 / OB CBP-CjHj ’ F*2 Λ U II 1-C1H-1,2,4-Tr1axol-1 -yl)-2-(2,4-dichlorophenyl)-3-fluoropentan-2-ol a) Preparation of the Intornedlate /1 Cl—p—C-CHF-CjBj — o 1-(2.4-01chlorophenyI)-2-fluorobutanone g of dry potasslun fluoride were added to a o1xture of 77 g of 1-(2,4-d1chlorophenyl)-2-bronobutanone and 500 ng of 18-crown-6 In 750 al of absolute acetonitrile and the.mixture was slowly hosted to 100° to 110°C, while stirring. After ebout 48 hours, the reaction had ended (checked by ges chromatography or by NMR). The reaction solution was then poured onto 2 litres of ice-water and extracted several tines with diethyl ether. The coablned extracts were washed with water, dried over eodlua sulfate and evaporated· Yield: 57 g of the oily product· (H-F coupling constant 50 Mx> Bolling point: 77-78°/0.008 nbar. b> Preparation of another Intermediate Ζ1 cx- 2-(2ζ4-Ρichlorophenyl)-2-(1-fluoropropyl)-oxirane g of SOX sodiue hydride were suspended in 300 el of absolute OMSO. 68 g of trlnethyloxosulfoniue iodide were S introduced into this suspension in portions under a nitrogen ataosphere, while stirring, when 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-d1chlorophenyl)-2-fluorobutanone in 100 al of tetrahydrofuran was then added dropwise in the course of 30 minutes, snd the resulting mixture was stirred for 3 hours and then diluted to five times Its volume with Icewater 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. Yields 55 g in the form of a brown oil. c) Preparation of the end product: A mixture of 55 g of 2-(2,4-dichloropheny1)-2-(1fluoropropyI)-oxirane, 30 g of 1,2,4-trlazole and 3.5 g of potassium tert.-butylate In 500 ml of PHF waa stirred at 80°C for 20 hours. The reaction solution was then cooled to RT, poured onto 2 litres of Ice-water snd extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and concentra25 ted. Yield of 1-(1H-1,2,4-tr1azol-1-yl)-2-(2,4-d1chlorophenyl)-3-fluoropentan-2-ols 26 g In the form of colourless crystals. Halting points 204-206°C.
Example H2: Preparation of ii n ao 1-(1H-1,2,4-Triazole-1 -y1)-2-(2,4-d1chlorophenyl)-3-(4-chlero phenoxy) -3-fluoropropan-2-ol e) Preparation of the Intermediate: 1-(2,4-01chlorophenyI)-2-broao-2-fLuoroethanone A solution of 16 g of bromine in 100 ml of carbon tetrachloride was added to a solution of 20.7 g of «-fluoro2,4-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: 17 g. Bolling point: 89-92°C/0.02 mbar. b) Preparation of another Intermediate: 1-(2.,4-PichlorophonyI)-2-<4-chlorqphcqoxy)-2-fluoroethanone 12.8 g of chlorophenol and 13.8 g of potassium carbonate were stirred 1n 200 ml of acetone for 1 hour. 28 g of 1-(2,4-diehlorophenyl)-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 flLtered and the filtrate was concsntratsd. The oily crude product crystallises after digestion with n*hexane. 4 Yield: 21.5 g in the form of yellowish crystals. Melting point: 85-87°C.
¢) Preparation of another Intermediate: 2-(2^4-0ichlorophenyl)-2-(4-chlorophenoxyfluorooethy1)oxlrane 1 g of 80% sodiua hydride was stirred in 80 ml of DMSO under a nitrogen atmosphere and 10.3 g of trlaethyloxosulfonlum Iodide were added In portions· After the exothermic reaction had subsided, the mixture was stirred at RT for a further hour> a solution of 2-(2,4-41ehlorophenyl)-210 (4-chlorophenoxy)-2-fluoroethanone In 30 ml.of tetrahydrofuran waa then added dropwlse and the reaulting mixture waa stirred at 25° 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 wers washed with water, dried over sodium 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-d1chloropheny1)-2-(4chlorophenoxyf LuoroaethyU-oxIrane, 4 g of 1,2,4-triazole and 0.5 g of potassium tert.-butylate 1n 100 ml of DRF was stirred at 80° to 100°C for 15 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 ex25 tracts were washed with water, dried over sodium sulfate and filtered end the filtrate waa 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.
The substances shown below can also be prepared 1n an analogous manner: Tabla 1 Compounds of the formula °*i *s Ar 1«.
Compound No. Ar »1 *1 s X Physical constant 1 C6H3C12<2,4) U a 0—* Cl a melting point 155-157* 2 C,.H,C1,(2,4) a a C2H5 a meIting point 204-206· 3 C.H,C1,<2,4) a a a N melting point 142-143 4 C£H4C1(4> a aC3Hl· N melting point 14&Ϊ51· 5 C6H3C1(2)F(4) a H a a melting point 132-133* 6 ci—f >-o-< >- a a a a melting point iw-i2o· 7 ·· ·· ·«·· ·—·* Cl—f 0—( a a a cu melting point 156-157* β ·«· ’···' C6H3C1(2,4) a a «2 a melting point 202-20«· Table 1 Continuation) Compound No. Ar «I "2 *3 X Physical constant 9 - ·· ·*· It H II H melting point 87-100* 10 r—f o—f 11 H H Cll melt ing point 100-105* ·· ··· 11c,,3 11C2U5 N 12 C6H3C12(2,4) Bensyl II H N melting point 13 C6ll3Cl(2)F(4) II IIC2U5 N ιπ-ιη* U /1 Cl-.( )-0--( )- II II H N melting point 160-163* INI |OS /1 15 Cl./ ).-0-/ ).- U U It Cll ·· ·· 16 C6U3C1(2)T(«) ClljCH-CII? HC2H5 N Resin Table 1 (fontinuation) Compound NO. Ar *1 *2 »3 X Physical constant 17 C6H3C12<2,4> 11 II Cllj-CUtCU,), II 10 CjUjCijtM) II H CM(CII3)2 N me. ynq point. 1’ . C6H4F(4) z~\ C«2" \ Z01 *»· 1 U 11 N Resin 20 W‘*> ·—· C,,2-‘C z"C1 ·*· H II CII 21 W<«> 11 II C1I2CII2 N 22 wu> 11 ii Z‘\ °\ Z "Cl ·· N 23 C6II3«2<2.«) H CH3 ·*· /'~CI ··· N 24 C6H3cl2tf,4) C..3 11 Cll3 N Resin 25 c6ii4Br<4) II II c2h5 N 26 C&H4Br(4) C3 uC2H5 « Table 1 (Continuation) Conpound NO. Ar *1 *2 s X Physical constant 27 B^phenyl-4-yl II 11c«3 H 2A ¢^01,(2,4) II u "2Η5 H 29 Ce»3Cl2(2.) u H SC3«l7-n H 30 c6h4ci(2) II H OC1I3 H 31 C6U}C1(2)F(4) II U s-·^ ^«-Cl • \ z • a* N 32 C6U}C1(2)F(4) II ll Cll 3 N netting point 163-165· 33 ·«·· ·· · <Ε?ί-·ζ ^<-0-·^ ✓»- •a· ·· II U · CM. 3 CH netting point 146-142* 34 •a* ·· 11 K CU 3 N netting point 173-174· Table 1 (fontInuation) Compound No· Ar l 2 »3 X Physical constant 35 II H W» N 36 CjH^ClC*) II II C^CIM) N· 37 C6H4Cl(2)F(4) tt Hc>.3 K melt ing point 186-198* 38 C6U3C1(2)F(4) C«3 H CU3 N 39 C6H3C1(2)F(4> H cn3 ο-«ζ ^.-Cl Ii ·· 40 C6H4c12<2,4) II F c2H5 N melting point 141-143° Table 1 (Cent inuat ion) Cooound NO. Ar l *2 s X Physical constant 41 Wl2U-*) li uC2H5 CH W melting point 42 43 C6M3CI2<2,4) C61I3C12<2,4) H II u II SV* c4H9-n H N 141-1«· "1ιΜ· ·—· .·*"·» melting point 44 b f Ifc Βΐ-·Γ / /" 11 11 H N 118-119· ··· ·*· ·—· ·—·. melting point 45 »r- ·( )-°··( 11 II 11 Cll 120-125* ··· ·«· meltinq point 46 47ctU4 i4) CJI.M2.4) 4 3 2 251½ 11 11 It »C2U5 C25 N N 141-1«· melting point . 154-156· 4ft \ . z‘\ Cl-ζ >-o-\ /- ·». ·—· H 11 11 Ν , viscous oil Table 1 (Cmtinuat ion> Coapounc No. Ar lR2 *3 X Physical constant 49 Br- ·Γ H r u N melt ng^po int 50 •99 ·* U F H N aeltinq point ?O-72‘ 51 y*\ Ci-< >-O-< > H r H N melting point 125-122· 52 „0*0 •a· ·· «*3 F U N viscous oil z"3 53 «-< >- «*3 11 0*3 N Resin 54 ci—ς ✓ °"λ a ClijCH-CII? H «3 N ">3 55 • a· ··· 11 U Vs N Table 1 (Cort inuation) ι Coapound I NO . Ar •l >2 «3 X Physical constant ' ' 56 C6U3C|2<2,4) II H Vs N 57 C.H.CK4) " /·> II II Vs N 58 «-< ;·-<>-< \-Z 11 11 m3 N 59 \ Z~\ H H Vs N •a·, ·· 60 ‘VVs 11 «*3 N •a· ·· /«3 61 Z\ z \ ci-< >- «Ws II Vs N •a· «a· /1 62 Z\ z \ Cl-< >-o-< >- ll il "3 N •a. ·· Formulation example» for liquid active substances of the formula I (X * per cent by weight) F1. Emulsion concentrates a) b) C) Active substance from the table 25X 40X 50X Ca Dodecylbenzenesulfonate 5X ax 6X Castor oil polyethylene glycoL ether <36 mol of ethylene oxide) 5X - - TributyIphenol polyethylene glycol ether (30 mol of ethylene oxide) - 12Z 4Z CycLohexanone wa 15X 20X Xylene mixture 65Z 25X 20X Emulsions of any desired concentration can be prepared from such concentrates by dilution with water· * F2. Solutions e) b) c) d) Active substance from the table BOX 10X 5X 95X Ethylene glycoL monomethyl ether 20X - - Polyethylene glycol HU 400 - 70X - - N-Methyl-2-pyrrotidone em 2QX - - Epoxidised coconut oil aa 1X 5X Benzine (boiling range 160-190°C) - - 94Z - (HU e nolecular weight) The solutions are suitable for application in the form of very small drops. F3. Granules a) b) Active substance from the table 5X 10X Kaolin 94X - Highly disperse silica IX - Attapulglte .- 90X The active substance Is dissolved 1n methylene chlo- ride, the solution 1s sprayed onto the carrier and the sol- vent Is then evaporated off In vacuo.
F4. Busts a)- b) Active substance from the table 2X 5X Highly disperse silica 1X SX Talc 97X Kaolin - 90X Ready-to-use dusts are obtained by Intimate mixing s of tho carriers with the active substance· Formulation exanples for solid active substances of the formula I (% a per cent by weight) F5. Wettable powders a) b) c) Active substance fron the table 25% 50% 75% Na Llgnlnsulfonete 5% 5% - Na Laurylsulfate 3% w 5% Na OilsobutyInaphthalenesulfonate vs 6% 10% Octylphenol polyethylene glycol ether (7-8 nol of ethylene oxide) 2% Highly disperse silica 5% 10% 10% Kaolin 62% 27% - The active substance 1s mixed thoroughly with the adjuvants and tha 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· Emulsion concentrate Active substance from the table Octylphenol polyethylene glycol ether ¢4-5 mol of ethylene oxide) Ca DodecyIbenzenesulfonate Castor oil polyglycol ether <35 mol of ethylene oxide Cyclohexanone Xylene mixture Emulsions of any desired concentration can be pre pared from this concentrate by dilution with water. % 3% 3% % 50% F7.
Active substance from the table Talc Kaolin Ready-to-uss duets are obtained substance with the carrier and grinding suitable mill.
F8. Extruded granules Active substance from the table Ns Llgnlnsulfonete a) % 95% b) 8% 92% by mixing the active the mixture on e % 2% Carboxymethylcellulose 1X Kaolin IX The active substance 1s mixed with the adjuvants and the mixture 1s ground and moistened with water. This mix5 ture Is extruded and subsequently dried in a stream of air. F9, Coated granules Active substance from the table 3X Polyethylene glycol (MU 200) 3% Kaolin 94X (MU ’ molecular weight) The finely ground active substance is uniformly applied, In e mixer, to the kaolin, which has been moistened with polyethylene glycol. Dust-free coated granules are obtained In this manner.
F1Q, Suspension concentrate Active substance from the table 40X Ethylene glycol 10X Monylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6X Na Ligninsulfonate 10X Carboxymethylcellulose IX 37X Aqueous formaldehyde solution 0.2X Silicone oil In the fora of a 75X aqueous emulsion 0.8X 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.
Biological examples: Example 81: Action against Puccinla greminis on wheat a) Residual-protective action days after sowing, wheat plants were sprayed with a spray liquor (0.02X ef active subatence) prepared from a wattable powder of the active substance. After 24 hours, the treated plants were infected with e uredospore suspension of the fungus. After incubation at 95-100X relative atmos33 pherlc humidity and 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. b) Systemic action 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 95-100X relative atmospheric humidity at about 20°C for 48 hours, the infected plants were placed in a green* house at about 22°C. The development of rust pustules was evaluated 12 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 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 SX.
Example B2: Action against Cercospora-arachldlcola on groundnut plants Residual-protective action Groundnut plants 10 - 15 co high were sprayed with a spray liquor (0.006Z 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 fun30 glcldal.. action was evaluated, on the basis of the number and size of the spots which had appeared, 12 days after the infection.
* In comparison with untreated but infected control plants (number and size of spots 100X), groundnut plants which had been treated with active substances from the table * showed a greatly reduced Cercospora attack. Thus, compounds 1 to 9, 13, 18z 19, 24, 32, 37, 40-46 and 49-53 almost completely prevented the occurrence of spot* in the above experiments CO-1OX).
Example S3: Action against Ery_»1phc graminis on barley a) Residual-protective action Barley plants about 8 cm high were sprayed with a 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 coni dia 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 abn-t.8 cm high were watered with a spray liquor (Q.006X of active substance, based on the volume of soil) prepared from a wettable powder of the active substance. Cere 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 conldla of the fungus.. The Infected barley plants were placed 1n e 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 100X. Amongst other compounds from the table, compounds 1 to 10, 13, 14, 16,18 , 19,24 , 32 χ 34 r 37 ,40 -46 end 48"53 Inhibited the fungal attack on barley to 0 to 5X, end, 1n particular, compound No. 2 effected complete reduction of attack.
Example B4t Residual-protective action against Venturia inacqualis on apple shoots Apple seedlings with fresh shoots IQ - 2Q cm long were sprayed with a spray liquor C0.006X of 'active substance) <· prepared from a wettable powder of the active substance.
After 24 hours, the treated plants were infected with a conldla suspension of the fungus. The plants were then Incu- * bated at 90 - 100X relative atmospheric humidity- for 5 days end placed in a greenhouse at 20-24°C for a further 10 days.
The scab attack was evaluated 15 days after the infection. Compounds 1 to 6, 8, 9, 13/16 / 18, 19/ 32, 40, 42, 44 - 46 and 48 - 52 Inhibited the disease infestation to less than 10X. Xn contrast, untreated but infected control shoots showed 100X attack.
Example B5s Action against Botrytis cinerea on beans Residual-protective action Bean plants about 10 cm high were sprayed with a spray liquor (0.02X of active substance) prepared from a wettable powder of the active substance. After 48 hours, the treated plants were infected with a conldia suspension of the fungus. After incubation of the Infected plants at 95-100X 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 0.02X, compounds 1 to 6, 8, 9, 13/ 14, 19, 24, 32, 34, 40, 42, 44, 45, 46 and .48-52, for example, proved to be completely effective. The disease infestation was 0 to 8X.
The Botrytis attack of untreated but Infected bean plants was 1Q0X.
Example B6s Action against Piricularia oryzae on rice plants Residual-protective action After being grown for two weeks, rice plants were sprayed with a spray liquor C0.002X of active substance) prepared from a wettable powder of the active substance.
After 48 hours, the treated plants were infected with a conldia suspension of the fungus. After incubation at 95100X 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. 13 or 32, as the active substance, showed a fungal attack of less than 10X, In comparison with the untreated control plants C100X attack).
Claims (18)
1. A compound of the general formula X Ar C-F (I) in which Az is 1H-1,2,4-triazole, 4H-1 z 2,4-triazole or 1Himidazole; Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl, phenoxyphenyl and naphthyl; R^ is hydrogen, Cj-C^alkyI, C3-C5alkenyl or benzyl; R 2 hydrogen, fluorine or C^-C^alkyl and R3 is hydrogen, fluorine, Cj-C^-alkyl, C^-C^haloalkyl, C-j-C 6 -a Ikoxy, C^-C^-alkylthi0, phenyl, phenoxy., phenylthlo or Cj-Cy-cycloalkyl, and each aromatic substituent or aromatic moiety of a substituent Is unsubstituted or mono* or poly-substituted by halogen, C^-C^-alkyl, C-j-C^-atkoxy, C 1 -C^-haloaIkyl z nitro and/or cyano; including the acid addition salts, quaternary azolium salts and metal complexes; provided that R^ and R^ cannot each simultaneously be fluorine.
2. A compound of the formula X according to claim 1, in which Az is 1H-1,2,4-tr1az.ole or ίΗ-lmidazole; Ar is an unsubstltuted or substituted aromatic radical from the series comprising phenyl, biphenyl and phenoxyphenyl; R^ is hydrogen; R 2 Is hydrogen, fluorine or C^-Cj-alkyl; and Rj is hydrogen, fluorine, C^-C^-alkyl, C^-C^-haloalkyl, C^-Cj-aIkoxy, C^-Cj-alkylthio, phenyl, phenoxy or phenylthlo, each phenyl moiety being unsubstituted or substituted by fluorine, chlorine, bromine, methyl, methoxy, CF3, N0 2 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 1H-1,2,4-triazol<; Ar is phenyl or phenoxyphenyl which Is unsubstituted or substituted In the 2- and/or 4-posltlon by methyl or halogen; R^ Is hydrogen; R 2 1s hydrogen, fluorine or methyl; and R3 la hydrogen, fluorine, C^-C^-alkyl or a radical from the series comprising * 10 phenyl, phenoxy and phenylthio which Is substituted by fluorine, chlorine and/or bromine.
4. A compound of the formula X according to claim 1, selected from the group comprising: 1-dH-1,2,4-tr1azol-1-y l> 2-(2,4-d1chlorophenyl)-3-fluorobutan-2-οI, 1-(1H-1,2,4trlazol-1-yl)*2-(2-ehloro-4-fluorophenyl)-3-fluorobutan-2-ol, 1-(lH-1,2,4-tr1azol“1-yl)-2-(2,4-dichlorophenyL)-3-fluoropentan-2-ol, 1-(1H-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyI)-3-fLuoro-4-methylpentan-2-ol, 1-(1H-1,2,4-triazol1 -yl)-Z-(2-chloro-4-fluorophenyl)-3-f Luoropentan-2-oI, 1- (1H-1,2,4-t riazo1-1-yI)-2-Cp-(4-chlorophenoxy)pheny13-3fluoropropan-2-olor1-(1H-1,2,4-tr1azol-1-yl)-2-(2,4-d1chLorophenyI)-3-(4-chtorophenoxy )-3-fluoropropan-2-ol·
5. A compound of the formula X according to claim 1, chosen from the series: 1-(1H-1,2,4-tr1azol-1-y1)-2-(4chLorophenyl)-3-fluorohexan-2-ol, 1-(1H-1,2,4-triazol-1-yl)2- (2,4-d1chlorophenyI)-3-fluorohexan-2-ol, 1-(lH-1,2,4-triazo1-1-yl)-2-(2,4-diehloropheny1-3,3-di fluoropentan-2-ol, 1-(1H-1,2,4-tr1azol-1-yI)-2-(2,4-d1chlorophenyl)-3-fluoro4-aethylpentan-2-oI, 1-(1H-1,2,4-triazol-1*yl)-2-Cp-C4-bromophenoxy)pheny13-3,3-dlfluoropropan-2-ol, 1-(1H-1,2,4-trlazol1-yl)-2-Cp-(4-fLuorophenoxy)phenyl3-3,3-d1fLuoropropan-2-ol, 1-(1 H-1,2,4-t ri azo 1-1-y I)-2.-Cp* (4-ch lorophenoxy)pheny 13-3,3dl fluoropropan-2-ol and 1-dH-1,2,4-triazol-1-yl)-2-Cp-(4chlorophenoxy)-2-methylphenyl3*2-hydroxy-3-fLuoropropane·
6. A process for the preparation of a compound of the formula I as defined in claim 1, which comprises first reacting an oxlrane of the formula XX F (XI) 3 8 with' an azole of the formula XXX tt—Ax (XXI) to give, a compound of the formula Xa OH I Ar-OCK -Az (ia) I 2 V c-R 3 F 5 and,, if required, converting the alcohol Xa into an ether of the formula I in the conventional manner, for example by re- * action with a compound of the formula XV - V (IV) in which formulae Xa, 11, III and IV, the substituents R-j, Λ 10 Rj, R^, Ar and Az are as defined under formula X, H is hydrogen or a metal atom and U is OH or a conventional leaving group.
7. A composition for controlling or preventing attack by microorganisms, which contains, in addition to conven* 15 tional carriers, a compound of the formula X according to claim 1 as at least one active component.
8. A composition according to claim 7, which contains 0.1 to 99X of an active substance of the formula X, 99.9 to 1X of a solid or liquid adjuvant and 0 to 25X of a surfac20 tant.
9. A method of controlling or preventing attack on crop plants by phytopathogenic mieroorganisms, which comprises applying a compound of the formula X as defined in claim 1 to the plants or their location.
10. Compounds of foraula I substantially as described uith reference to any of the preparation Examples.
11. · Process for producing coapounds of foraula I substantially as described with 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-c hlorophenoxy)-3-fluoropropan-2-ol.
14. 1-OH-1 ,2,4-tr iazol-1-y l)-2-C4-chlaropheny 1)3-fluorohexan-2-ol.
15. 1-I1H-1,2,4-t riazo 1-1-yl)-2-Cp-(4-c h lorophenoxy) 15 pheny l3-3-*f luoropropan-2-ol.
16. 1-<1H-1, 2,4-triazo I-1-y 0-2-<2-chloro*4-f luorophenyl) 2-propenyIoxy-3-ftuoropentane.
17. 1-OH-1,2,4-triazol-1-yO-2-(4-fluorophenyl)-2<4-chlorobentyloxy)-3-fLuoropropane.
18. 20 18. 1-(1H-1 / 2,4-triazol-1-yO-2-(2,4-dichlorophenyl)2-methoxy-3-fluorobutane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IE2419/88A IE56379B1 (en) | 1982-12-14 | 1983-12-13 | Fluorine-containing aryl oxirane compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH726982 | 1982-12-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE832933L IE832933L (en) | 1984-06-14 |
| IE56378B1 true IE56378B1 (en) | 1991-07-17 |
Family
ID=4322494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE2933/83A IE56378B1 (en) | 1982-12-14 | 1983-12-13 | 1-azolyl-2-aryl-3-fluoroalkan-2-ols as microbicides |
Country Status (29)
| Country | Link |
|---|---|
| EP (1) | EP0113640B1 (en) |
| JP (1) | JPS59118771A (en) |
| KR (1) | KR910002541B1 (en) |
| AR (1) | AR240810A1 (en) |
| AT (1) | ATE53027T1 (en) |
| AU (2) | AU570659B2 (en) |
| BG (1) | BG48681A3 (en) |
| BR (1) | BR8306860A (en) |
| CA (1) | CA1209152A (en) |
| CS (1) | CS250237B2 (en) |
| DD (1) | DD215930A5 (en) |
| DE (1) | DE3381589D1 (en) |
| DK (1) | DK161199C (en) |
| ES (1) | ES8504151A1 (en) |
| FI (1) | FI83776C (en) |
| GB (2) | GB2132195B (en) |
| GR (1) | GR81348B (en) |
| HU (2) | HU196891B (en) |
| IE (1) | IE56378B1 (en) |
| IL (1) | IL70422A (en) |
| MA (1) | MA19972A1 (en) |
| NO (1) | NO161256C (en) |
| NZ (1) | NZ206562A (en) |
| PH (1) | PH22949A (en) |
| PL (1) | PL139146B1 (en) |
| PT (1) | PT77797B (en) |
| SU (1) | SU1326194A3 (en) |
| TR (1) | TR22109A (en) |
| ZA (1) | ZA839259B (en) |
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| GB8520027D0 (en) * | 1985-08-09 | 1985-09-18 | Ici Plc | Insecticidal ethers |
| US4935436A (en) * | 1989-01-23 | 1990-06-19 | The Dow Chemical Company | Substituted triazoles and their use as fungicides |
| US5140023A (en) * | 1990-04-27 | 1992-08-18 | G. D. Searle & Co. | Azatetracycle compounds |
| JP3471831B2 (en) * | 1991-12-09 | 2003-12-02 | 富山化学工業株式会社 | Novel triazole derivatives and their salts |
| HU212424B (en) * | 1993-09-23 | 1996-06-28 | Richter Gedeon Vegyeszet | New propan-2-ol derivatives substituted with triazole or imidazole and process for producing them |
| ES2159676T3 (en) * | 1995-12-22 | 2001-10-16 | Ss Pharmaceutical Co | TRIAZOL DERIVATIVES WITH ANTIMICOTIC AND INTERMEDIATE ACTIVITY. |
| US6002028A (en) * | 1995-12-22 | 1999-12-14 | Ss Pharmaceutical Co., Ltd. | Triazole derivative, preparation process thereof and pharmaceutical comprising the same as an effective ingredient |
| US5939448A (en) * | 1996-06-21 | 1999-08-17 | Ss Pharmaceutical Co., Ltd. | Triazole derivative or salt thereof |
| TW438784B (en) * | 1997-08-29 | 2001-06-07 | Ssp Co Ltd | Triazole derivative or salt thereof and pharmaceutical composition for treating mycosis containing the same |
| JP3638438B2 (en) | 1997-12-26 | 2005-04-13 | エスエス製薬株式会社 | Triazole derivative or salt thereof, process for producing the same, and medicament containing the compound as an active ingredient |
| JP2004359646A (en) * | 2003-06-09 | 2004-12-24 | Ss Pharmaceut Co Ltd | New azole derivative with antimycotic activity |
| EP2731935B1 (en) | 2011-07-13 | 2016-03-09 | BASF Agro B.V. | Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds |
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| WO2013010885A1 (en) | 2011-07-15 | 2013-01-24 | Basf Se | Fungicidal alkyl- and aryl-substituted 2-[2-chloro-4-(dihalo-phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds |
| EP2744792B1 (en) | 2011-08-15 | 2016-10-12 | Basf Se | Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkynyloxy-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 |
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| EP2744791B1 (en) | 2011-08-15 | 2015-10-28 | Basf Se | Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-3-methyl-butyl}-1h-[1,2,4]triazole compounds |
| CN103827096A (en) | 2011-08-15 | 2014-05-28 | 巴斯夫欧洲公司 | Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-hexyl}-1h [1,2,4]triazole compounds |
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| EP2735563A1 (en) * | 2012-11-27 | 2014-05-28 | Basf Se | Meta substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides |
| CN104955813A (en) | 2012-11-27 | 2015-09-30 | 巴斯夫欧洲公司 | Substituted [1, 2, 4] triazole compounds |
| WO2014082879A1 (en) | 2012-11-27 | 2014-06-05 | Basf Se | Substituted [1,2,4]triazole compounds |
| BR112015012003A2 (en) * | 2012-11-27 | 2018-05-15 | Basf Se | compounds of formula I, composition, use of a compound, method for combating harmful fungi, seed, process for preparing the compounds and intermediate compounds |
| WO2014082881A1 (en) | 2012-11-27 | 2014-06-05 | Basf Se | Substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides |
| WO2014082871A1 (en) | 2012-11-27 | 2014-06-05 | Basf Se | Substituted 2-[phenoxy-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds and their use as fungicides |
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| 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 |
| BR122019013926B1 (en) * | 2013-01-09 | 2019-10-29 | Basf Agro Bv | process for preparing a triazole compound of formula i |
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| EA037646B1 (en) * | 2013-12-12 | 2021-04-27 | Басф Агро Б.В. | Process for the preparation of substituted triazoles |
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-
1983
- 1983-12-06 BG BG63332A patent/BG48681A3/en unknown
- 1983-12-07 GB GB08332617A patent/GB2132195B/en not_active Expired
- 1983-12-08 DE DE8383810576T patent/DE3381589D1/en not_active Expired - Lifetime
- 1983-12-08 AT AT83810576T patent/ATE53027T1/en not_active IP Right Cessation
- 1983-12-08 EP EP83810576A patent/EP0113640B1/en not_active Expired - Lifetime
- 1983-12-09 MA MA20193A patent/MA19972A1/en unknown
- 1983-12-09 FI FI834522A patent/FI83776C/en not_active IP Right Cessation
- 1983-12-09 PT PT77797A patent/PT77797B/en not_active IP Right Cessation
- 1983-12-12 CS CS839326A patent/CS250237B2/en unknown
- 1983-12-12 SU SU833675009A patent/SU1326194A3/en active
- 1983-12-12 TR TR22109A patent/TR22109A/en unknown
- 1983-12-12 CA CA000443044A patent/CA1209152A/en not_active Expired
- 1983-12-12 PL PL1983245063A patent/PL139146B1/en unknown
- 1983-12-12 DD DD83257812A patent/DD215930A5/en not_active IP Right Cessation
- 1983-12-12 GR GR73213A patent/GR81348B/el unknown
- 1983-12-12 AR AR295072A patent/AR240810A1/en active
- 1983-12-12 IL IL70422A patent/IL70422A/en unknown
- 1983-12-13 BR BR8306860A patent/BR8306860A/en unknown
- 1983-12-13 NO NO834592A patent/NO161256C/en unknown
- 1983-12-13 HU HU834246A patent/HU196891B/en not_active IP Right Cessation
- 1983-12-13 DK DK573883A patent/DK161199C/en not_active IP Right Cessation
- 1983-12-13 IE IE2933/83A patent/IE56378B1/en not_active IP Right Cessation
- 1983-12-13 NZ NZ206562A patent/NZ206562A/en unknown
- 1983-12-13 ZA ZA839259A patent/ZA839259B/en unknown
- 1983-12-13 HU HU834334A patent/HU196978B/en not_active IP Right Cessation
- 1983-12-13 AU AU22345/83A patent/AU570659B2/en not_active Ceased
- 1983-12-13 ES ES527986A patent/ES8504151A1/en not_active Expired
- 1983-12-14 KR KR1019830005924A patent/KR910002541B1/en not_active IP Right Cessation
- 1983-12-14 PH PH29977A patent/PH22949A/en unknown
- 1983-12-14 JP JP58236016A patent/JPS59118771A/en active Pending
-
1985
- 1985-09-04 GB GB08522010A patent/GB2166729B/en not_active Expired
-
1988
- 1988-01-22 AU AU10752/88A patent/AU603417B2/en not_active Ceased
Also Published As
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Patent lapsed |