GB2110684A

GB2110684A - Substituted azolyl-ethyl ethers and microbicidal compositions thereof

Info

Publication number: GB2110684A
Application number: GB08233499A
Authority: GB
Inventors: Robert Nyfeler; Alfred Meyer; Elmar Sturm
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1981-11-27
Filing date: 1982-11-24
Publication date: 1983-06-22
Also published as: KR880001812B1; NZ202629A; MY8700133A; AU9088282A; CA1195987A; ATE49200T1; EP0082340A1; ES8503644A1; BR8206872A; PT75902B; DK159774B; DK159774C; IE54223B1; PT75902A; AU567483B2; TR22376A; KR840002363A; GR77746B; JPS58103367A; DK528382A

Abstract

Novel substituted azolyl-ethyl ethers of the general formula I <IMAGE> wherein R1 is phenyl, phenyl mono- to trisubstituted by halogen, C1-C3- haloalkyl, nitro, C1-C3-alkoxy, C1-C8-alkyl and/or cyano, or phenyl substituted by phenyl or phenoxy, naphthyl, or naphthyl mono- or -disubstituted by halogen, nitro and/or C1-C3-alkyl, benzyl, or benzyl mono- or disubstituted by halogen, nitro and/or C1-C3-alkyl; R2 is phenyl, phenyl mono- to trisubstituted by halogen, C1-C3-haloalkyl, nitro, C1-C3-alkoxy, C1-C8-alkyl and/or cyano, or phenyl substituted by phenyl or phenoxy, or it is C1-C10-alkyl, C3-C8-cycloalkyl or C3-C8- cycloalkyl-(C1-C4-alkyl); R3 is C1-C12-alkyl, C2-C4-alkenyl, C3-C4-alkynyl, benzyl, or benzyl mono- or disubstituted by halogen, nitro and/or C1-C3-alkyl; and R4 is an azolyl group; including acid addition salts thereof, quaternary azolium salts and metal complexes, are used in agrochemical compositions for the preventive and curative combating of harmful microorganisms.

Description

1 GB 2 110 684 A 1

SPECIFICATION Microbicidal compositions

The present invention relates to novel substituted azolyl-ethyl ethers and acid addition salts thereof, to quaternary azolium salts and to metal complexes. The invention relates also to the production of these substances, as well as to microbicidal compositions which contain as active 5 ingredient at least one of these compounds. The invention moreover relates to the use of these active ingredients, or of the stated compositions, for combating harmful microorganisms.

There are embraced herein compounds of the general formula I OR3 1 IR,-CH2R4 1 R2 wherein R, is phenyl, phenyl mono- to trisubstituted by halogen, C,_C3-haloalkyl, nitro, Cl-C3-alkoxy, C,-C, alkyl and/or cyano, phenyl substituted by phenyl or phenoxy, naphthyl, naphthyl mono- or disubstituted by halogen, nitro and/or Cl-C.-alkyl, benzyl, or benzyl mono- or disubstituted by halogen, nitro and/or Cl-C3-alkyl; R2 is phenyl, phenyl mono- to trisubstituted by halogen, Cl- C3-haloalkyl, nitro, C1_C3_ alkoxy, C1_C8-aIkyI and/or cyano, phenyl substituted by phenyl or phenoxy, Cl-Clo-alkyl, C3_C13_ 15 cycloalkyl or C3_C,_CyCIoalkyI-(C,-C,-aIkyI); R3 is Cl-C127alkyl, C2--C, 7a[kenyl, C_CCalkynyl, benzyl, or benzyl mono- or disubstituted by halogen, nitro and/or Cl-C3- alkyl; and R4 is an azolyl group; including the acid addition salts thereof, quaternary azolium salts and metal complexes.

The term 'azolyl' denotes a five-membered, heterocyclic ring having nitrogen as the hetero atom and being of aromatic character. Typical representatives are 1 H-1,2,4,- triazole, 4H-1,2,4-triazole and 20 1 H-imidazole. By'alkyl' itself, or as a constituent of another substituent, are meant, depending on the given number of carbon atoms, for example the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and so forth, and isomers thereof, such as isopropyl, isobutyl, tert-butyl, isopentyl, and the like. Haloalkyl is a mono- to per-halogenated alkyl substituent, for example CHC'21 CHF2, CH2Cl1 CC'31 CH2F, CH2CH2Cl1 CHBr2, preferably CF3, and so forth. By halogen is meant here and in the following: fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Naphthyl is a- or A-naphthyl, preferably a-naphthyl. Alkenyl is for example: propenyl- (1), allyl, butenyl-(1), butenyl (2) or butenyl-(3); alkynyl is for example: propinyl-(l)- or propargyl. Cycloalkyl is, depending on the number of carbon atoms, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.

The present invention hence relates to the free organic molecules of the formula 1, to addition salts thereof, to quaternary azollum salts and to metal complexes. The free molecules are preferred, especially the (1 H) 1,2,4-triazolyl derivatives.

Examples of salt-forming acids are inorganic acids: hydrohalic acid, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid, as well as sulfuric acid, phosphoric acid, 35 phosphorous acid or nitric acid; and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p- toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2phenoxybenzoic acid or 2-acetoxybenzoic acid.

Metal complexes of the formula I consist of the basic organic molecule and an inorganic or organic metal salt, for example: the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates, and so forth; of the elements of the third and fourth main groups, such as aluminium, tin or lead, and also of the first to eighth subgroups, such as chromium, manganese, iron, zirconium, cobalt, nickel, copper, zinc, silver, mercury, and the like. The subgroup elements of the 4th period are preferred. The metals can be present here in the various valencies in which they occur. The metal complexes of the formula I can be mononuclear or polynuclear in form, that is to say, they can contain one or more organic molecule constituents as liqands. Complexes with the metals: copper, zinc, manganese, zirconium and tin are preferred.

The compounds of the formula I at room temperature are stable oils, resins or solids, which are 50 distinguished by very valuable microbicidal properties. They can be used in agriculture or in related fields in a preventive and curative manner for combating phytopathogenic microorganisms, the preferred compounds being the triazolyl derivatives embraced by the formula 1. The active substances of the formula I according to the invention are characterised by very good microbicidal activity, and by their great ease of application.

Within the scope of the present invention, the following substituent types and combinations of these substituents with one another are preferred by virtue of their pronounced microbicidal action:

2 GB 2 110 684 A - 2 for IR,: a) 2,4-dihalophenyi, 2,6-dihalophenyi, 2-halophenyl, 4- halopheny], phenyl, biphenyl, phenoxyphenyl, 2-haioa-naphthyi, 4-halo-cv-naphthyi, a-naphthy], 2- halobenzy], 4 halobenzy], 2,4-dihalobenzyi, 2,6-dih a lobe nzyi, 3,4-di ha lobe nzyi or benzy]; b) 2,4-dichlorophenyi, 2-chloro-4-bromophenyl, 2,6-dichlorophenyi, 4- chlorophenyl, 4 fluorophenyl, 2-chloro-a-naphthyi, 4-chloro-a-naphthyi, 2-chlorobenzyl, 4- chlorobenzy] or 5 2,4-dichlorobenzy]; for R2: a) phenyl, 2,4-dihalophenyi, 2,6-dihalopheny], 2-halophenyl, 4- halophenyl, biphenyl, phenoxyphenyl, Cl-CCalky], cyclopropyl, cyclopentyl or cyclohexy]; b) phenyl, 2,4-dichlorophenyi,2-chloro-4-bromophenyi,2,6-dichlorophenyi,4chiorophenyi, 4- fluorophenyl, Cl-CCalkyl or C3--C6-CYCloalkyl; for R3: a) Cl-C,-alkyl, C3-C4-alkenyl, propargyl, benzyi, or benzyl which is mono- or disubstituted by fluorine, chlorine and/or methyl; b) Cl-CCalky], allyl, propargyl, benzy], 2-halobenzyi, 4-halobenzyi, 2,4- dihalobenzyi, 2,6 dihalobenzyi or 3,4-dihalobenzy]; c) Cl-C,-alkyl, allyl, propargy], benzyl, 2,6-dichlorobenzy], 4- chlorobenzyl, 4-fluorobenzyl or 2,4-dichlorobenzyi; for R4: 1 H-1,2,4-triazoiyi, 1 H-imidazolyl or 4H-1,2,4-triazoiyi; and among these, the two first-named azoles, and more particularly 1 H-1,2,4-triazoly].

The term 'halo' denotes fluorine, chlorine, bromine and iodine.

There are thus given for example the following preferred substituent combinationj:

preferred compounds of the formula 1 are those wherein R, is phenyl, phenyl mono- to trisubstituted by fluorine, chlorine, bromine, CF3, Cl-C2-alkoXY, Cl-C3-alkyl and/or cyano, or biphenyi, phenoxyphenyl, naphthyl, or naphthyl mono- or disubstituted by fluorine, chlorine, bromine, nitro and/or C,-C,-alkyl, or benzy], or benzyl mono- or disubstituted by fluorine, chlorine, bromine, nitro and/or Cl-C3-alkyl; R, is phenyl, or phenyl mono- to trisubstituted by fluorine, chlorine, bromine, CF, Cl-C2-alkoxy, Cl-C3- 25 alkyl and/or cyano, or bipheny], phenoxyphenyl, C,-CCalkyl, C,7-C,- eycloalkyl or Cj-C,-cycloalkyl (C,-C2-alkyl); R3 is Cl-C,-alkyl, C,--C,-alkenyi, propargy], benzyi, or benzyl mono- or disubstituted by fluorine, chlorine, bromine, nitro and/or Cl-C,-alkyl; and R4'S 1 H-1,2,4- triazoiyi, 4H-1,2,4-triazoly] or 1 Wimidazolyl.

Preferred also are compounds of the formula 1 wherein R, is phenyl, biphenyl, phenoxyphenyl, a- 30 naphthy], benzyl, or a group from the series phenyl, cv-naphthyl and benzy], which group is mono- or disubstituted by fluorine, chlorine and/or methyl; R2 is phenyl, or phenyl mono-or disubstituted by fluorine, chlorine and/or methyl, or it is bipheny], phenoxyphenyl, Cl-C,- alkyl, cyclopropy], cyclopentyl or cyclohexyl; R. is Cl-C,-alkyl, allyl, propargy], benzy], 2-halobenzyi, 4-halobenzyl, 2,4-dihalobenzyi, 2,6-dihalobenzyi or 3,4-dihalobenzyl; and R, is 1 H-1,2,4-triazoiyi.

A further group is formed by the following preferred compounds of the formula 1 wherein R, is 24 dihalophenyl, 2,6-dihalophenyl, 2-halophenyl, 4-halophenyl, phenyl, biphenyl, phenoxyphenyi, 2-halo a-naphthyl, 4-halo-a-naphthyl, cv-naphthy], 2-halobenzyi, 4-halobenzyl, 2, 4-di ha lobe nzy], 2,6-dihalobenzyl, 3,4-dihalobenzy] or benzyl; R2 is phenyl, 2,4- dihalophenyl, 2,6-dihalopheny], 2-halopheny], 4-halophenyl, biphenyl, phenoxyphenyl, Cl-C6-alkyl, cyclopropyl, cyclopentyl or 40 cyclohexy]; R3 is Cl-C,-alky], allyl, propargyl, benzy], 2,6- dichlorobenzyl, 4-chlorobenzyi, 4-fluorobenzyl or 2,4-dichlorobenzyI; and R4'S 1 H-1,2,4-triazoiyl.

Particularly preferred are compounds of the formula 1 wherein R, is 2,4dichloropheny], 2-chloro-4-bromophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 4- fluorophenyl, 2-chloro-a-naphthy], 4-chloro-a-naphthyi, 2-chlorobenzyi, 4-chlorobenzyl or 2,4-dichlorobenzyi; R, is phenyl, 2,4-dichlorophenyi, 2-chloro-4-bromopheny], 2,6-dichlorophenyl, 4chlorophenyl, 4-fluoropheny], Cl-C,-alkyl or Cj-C,-eycloalkyl; R3'S Cl-C,-alkyl, allyl, propargy], benzyi, 2,6-dichlorobenzyi, 4-chlorobenzyi, 4-fluorobenzy] or 2,4-dichlorobenzyi; and R4'S 1 H-1,2,4- triazoly].

An especially preferred group is formed by those compounds wherein R, is 2,4-dichlorophenyi, 2 chloro-4-fluorophenyi,2-fluoro-4-chlorophenyi,2-chloro-4-bromophenyi,4chior o-or4-fluorophenyl; 50 R2 is C,--C,-cycloalkyl or Cl-C4-alkyl; and R, is benzyl, chlorobenzyi, dichlorobenzyi, C,-C47alkyl or C3-C4-alkenyl (= compound group T).

Compounds of importance among these are those wherein R, is Cl-C4-alkyl, while R, and R2 are as defined for group T.

Furthermore, compounds of special importance are those wherein R2 is methyi,'SO-C3H7 or sec- 55 C4H, while R, and R, are as defined for group T.

Individual compounds preferred in particular are for example:

1 -(1 H-1,2,4-triazol-1 -yi)-2-phenyi-2-(2,4-dichlorophenyi-2-methoxyethane, 1 -0 H-1,2,4-triazol-1 -yi)-2-phenyi-2-(4-chlorophenyi)-2-allyloxy-ethane, 1 -0 H-1,2,4-triazol-1 -yi)-2-phenyi-2-(4-chlorophenyi)-2-methoxy-ethane, 1 -0 H-1,2,4-triazol-1 -yi)-2-benzy[oxy-2-(2,4-dichlorophenyi)-pentane, 1 -0 H-1,2,4-triazol-1 -yi)-2-methoxy-2-(2,4-dichlorophenyi)-pentane, 1 -0 H-1,2,4-triazol-1 -yi)-2-methoxy-2-(4-fluorophenyi)-2-cyclohexyi- ethane, 1 -0 H-imidazol-1 -yi)-2-phenyl-2-(2,4-dichlorophenyi)-2-methoxy-ethane, 1-(1H-1,2,4-triazol-l-yi)-2-n-propoxy-2-(2,4-dichloropher,i)-pentane, 1 3 GB 2 110 684 A - 3 1 Al H-1,2,4-triazol-1 -yi)-2-n-propoxy-2-(2-chloro-4-fluorophenyi)- pentane, 1 -(1 H1,2,4-triazol-1 -yl)-2-methoxy-2-(2,4-dichlorophenyl)-3- methylbutane, 1 -(1 H- 1,2,4-triazol-1 -yi)-2-methoxy-2-(2-chloro-4-fluorophenyi)pentane, and 1 -(1 H-1,2,4-triazol-1 -yl)-2-(p-chlorobenzyloxy)-2-(2,4-dichlorophenyl)- propane.

Azolyi-ethane derivatives of the formula 1 can be produced according to the invention by reacting 5 a compound of the formula 11 with a compound of the formula Ill A 1 R,- -CH2R4 1 K2 R3-W (11) wherein the substituents R, R2, R3 and R4 are as defined under the formula 1, A and W are each -OH, 10 -OM or one of the customary removable groups, M is an alkali metal atom or alkaline-earth metal atom, with the proviso that the choice of the reactants H and Ill is always such that either an MO or HO function reacts with a removable group or two hydroxyl functions react with each other. A customary removable group is to be understood, here and in the following, as being substituents such as halogens (for example: fluorine, chlorine, bromine or iodine, preferably chlorine or bromine]; 15 sulfonyloxy groups, preferably -OSO,-R5; acyloxy groups, preferably -OCO- R,; and isourea groups, preferably -O-C=NRe, 1 NHIR7 wherein R., R6 and R7 independently of one another are each Cl-C.-alkyl or Cl-C3-haloalkyl, or phenyl which is unsubstituted or substituted by halogen, methyl, nitro, trifluoromethyl and/or methoxy. 20 In so far as alcohols or alcoholates of the formula 11 are concerned (A=OH or OM), compounds of the formula I will in practice be produced by customary etherification with a compound of the formula III wherein W is a halide, preferably a chloride or bromide. The reaction is carried out in the temperature range of 00 to 1 500C, either not in a solvent or, preferably, in atropic solvents, such as aromatic and aliphatic laydrocarbons, ethers and ethereal compounds (diethyl ether, dioxane, tetrahydrofuran [THF], 25 and so forth), acetonitrile, dimethylformamicle [DMF1, and others familiar to the expert in the case of etherification reactions. To be recommended also is the production in the phase-transfer process.

Alcohols of the formula 11 (A=OH) are for the most part known from the literature, or they can be produced by methods analogous to those described therein. There are thus described as fungicides: 1 - phenyl-2-(l H-1,2,4-triazol-1 -yl)-ethanol derivatives in the German Offenlegungsschrift No. 3,042,302; 30 2-(1 H-1,2,4-triazol-1 -yl)-ethanol derivatives in the EP Offenlegungsschrift No. 0,015,756; and 1 phenyl-2-(1 H-imidazol-1 -yl)-ethanol derivatives in the German Offenlegungsschrift No. 3,042,303. The compounds of the formula I according to the invention are superior to the cited substances.

In all cases in which the substituents R, and R2 in the compounds of the formula are different, the compounds of the formula I contain, in the position adjacent to the oxygen function, an asymmetric 35 centre N OR3 1 R,- CH2R4 1 R2 (1), and can therefore be present in two enantiomeric forms. There is generally formed in the production of these substances a mixture of both enentiomeric forms; and this can then be separated, by the customary methods of enantiomer separation, for example by fractional crystallisation of a diastereoisomeric salt mixture with an optically active strong acid, or by column-chromatography on an optically active carrier and with an optically active eluting agent, into the optical antipodes. The two antipodes exhibit a different microbicidal activity. Except where specially emphasised, there exists in all cases where reference is made to a compound of the formula 1 a mixture of both enantiomeric forms.

It has been shown that the active substances of the formula 1, and compositions containing them, 45 exhibit, for practical purposes, a very favourable microbicidal spectrum, in particular against phytopathogenic fungi. The compounds of the formula 1 thus have a very favourable curative, preventive 4 GB 2 110 684 A 4 and systemic action for the protection of plants, especially cultivated plants, without affecting these in a disadvantageous manner.

The microorganisms occurring on plants or on parts of plants (fruit, blossom, foliage, stalks, tubers or roots) of various cultivated crops can be inhibited or destroyed with the active substances of the formula 1, and also parts of plants subsequently growing remain preserved from such microorganisms. The active substances of the formula I are effective against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (for example Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidlomycetes (for example the species: Hemileia, Rhizoctonia and Puccinia); in particular they are effective against the Ascomycetes class (for example: Venturia, Podosphaera, Erysiphe, Monilinia and Uncinula). Furthermore, the compounds of the formula I have a 10 systemic action. They can be used also as dressing agents for the treatment of seed (fruits, tubers and grain), and of plant cuttings to protect them from fungus infections, and also against phytopathogenic fungi occurring in the soil.

The invention relates also to compositions which contain, as at least one active ingredient, a compound of the formula 1. and also to the use of these compositions, or of the active ingredients on 15 their own, for combating and/or preventing an infestation by microorganisms.

Within the scope of this invention, target crops with respect to the range of indications disclosed herein include for example the following species of cultivated plants: cereals: (wheat, barley, rye, oats, rice, sorghum and related cereals); beet: (sugar beet and fodder beet); pomaceous fruit, stone fruit and soft fruit: (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); 20 legumes: (beans, lentils, peas and soya-bean); oil plants: (rape, mustard, poppy, olives, sunflowers, coco, castor-oil plan - ts, cocoa and groundnuts)-; Cucurbitacea: (pumpkins, cucumbers and melons); fibre plants: (cotton, flax, hemp and jute); citrUs-fruits: (oranges, lemons, grapefruit and mandarins); varieties of vegetables: (spinach, lettuce, asparagus, varieties of cabbage, carrots, onions, tomatoes, potatoes and paprika); laurel plants: (avocado, cinnamon and camphor); or plants such as maize, tobacco, nuts, 25 coffee, sugar beet, tea, grapevines, hops, bananas and natural rubber plants. Plants within the scope of the present invention are however also all types of other green vegetation, whether it be in the form of ornamental plants (composites), areas of grass, embankments or general low cover crops.

Active substances of the formula I are customarily used in the form of compositions, and can be applied, simultaneously or successively, with further active substances to the area or plants to be treated. These further active substances can be fertilisers, trace- element agents or other preparations influencing plant growth. They can however also be selective herbicides, insecticides, fungicides, bactericides, nernaticides or molluscicides, or mixtures of several of these preparations, optionally together with carriers commonly used in formulation practice, tensides or other additives facilitating application.

Suitable carriers and additives can be solid or liquid and they correspond to the substances customarily employed in formulation practice, for example: natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders or fertilisers.

The compounds of the formula I are used either in an unmodified form or preferably together with auxiliaries customarily employed in formulation practice, and are thus processed in a known manner for 40 example into the form of emulsion concentrates, brushable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granulates, and also encapsulations in for example polymeric substances. The application processes, such as spraying, atomising, dusting, scattering, brushing or pouring, and likewise the type of composition, are selected to suit the objectives to be achieved and the given conditions. Favourable applied amounts are in general between 10 g and 5 kg of active substance (AS) per hectare, preferably between 100 g and 2 kg of AS per hectare, and in particular between 200 g and 600 g of AS per hectare.

The formulations, that is to say, the compositions or preparations containing the active substance of the formula I and optionally a solid or liquid additive, are produced in a known manner, for example by the intimate mixing and/or grinding of the active substances with extenders, such as with solvents, solid 50 carriers and optionally surface-active compounds (tensides). These measures are familiar to one skilled in the art.

Suitable solvents are: aromatic hydrocarbons, preferably the fractions C. to C121 such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl- or dioctylphthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, as well as ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or - ethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, and also optionally epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, for example for dusts and dispersible powders, areas a rule natural mineral 60 fillers, such as calcite, talcum, kaolin, monomorillonite or attapulgite. To improve the physical properties, it is also possible to use highly dispersed silicic acid or highly dispersed absorbent polymers.

Suitable granulated adsorptive carriers are porous types, for example: pumice, ground brick, sepiolite or bentonite; and suitable nonsorbent carriers are for example calcite or sand. In addition, a great number of pre-granulated materials of inorganic or organic nature can be used, such as in particular dolomite or 65 1 GB 2 110 684 A 5 ground plant residues.

Suitable surface-active compounds are, depending on the nature of the active substance of the formula I to be formulated, nonionic, cationic and/or anionic tensides having good emulsifying, dispersing and wetting properties. By'tensides' are also meant mixtures of tensides.

The tensides customarily used in formulation practice are described, inter alia, in the following 5 publications: "Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ringwood, New Jersey, 1980, and Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1980.

The agrochernical preparations contain as a rule 0.1 to 99%, particularly 0. 1 to 95%, of active substance of the formula 1, 99.9 to 1%, especially 99.8 to 5%, of a solid or liquid additive, and 0 to 25%, 10 in particular 0.1 to 25% of a tenside. Whereas commercial products are preferably in the form of concentrated compositions, the compositions employed by the end-user are as a rule diluted.

The following Examples serve to further illustrate the invention without limiting the scope thereof.

Temperature values are given in degrees Centigrade, and percentages and 'parts' relate to weight.

RT= room temperature and absolute= anhydrous.

PRODUCTION EXAMPLES EXAMPLE 1

Production of f \ OH CH2-N IN 0:o 1 Cl \--N 11 Cl NaH/CH31 O-CH3 N V f \ CH/ 1v 0: i Cl k1 Cl (1.1) 1(1H-1,2,4-Triazol-l-yi)-2-phenyi-2-(2,4-dichlorophenyi)-2-methoxy-ethane 1.8 g (0.041 mol) of sodium hydride dispersion (about 55% strength) in mineral oil are suspended, in a nitrogen atmosphere, twice with petroleum ether; and 50 mi of DIVIF are subsequently added. There is then added dropwise, with stirring, a solution of 12.5 g (0.037 mol) of 1 -(1 H-1,2,4-triazol-1 -yi)-2 phenyi-2-(2,4-dichlorophenyl)-ethanoI in 70 mi of DMF; the reaction mixture is stirred at 401C for 30 minutes, and 3.2 mi (0.052 mol) of methyl iodide are afterwards added dropwise, the temperature then rising to about 531C. The mixture is stirred at RT fora further 16 hours; it is subsequently poured into ice-water, and extracted twice with ethyl acetate. The combined extracts are washed four times with semi-saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated by evaporation. The residue is suspended at reflux temperature with diethyl ether; it is finally cooled to RT and filtered; yield: 10.9 9 of colourless crystals, m.p. 128-131 'C.

EXAMPLE 2

Production of Cl Cl OH v CH2-N / N NaH/BrCH.C^ C3H7 -"c- (K1) CH 2_ C1 Cl 1 \--i Cl CH2-NI N H7-n 1 -(1 H-1,2,4,-Triazol-1 -yl)-2-benzyloxy-2-(2,4-dichlorophenyl)-pentane To a suspension of 2.4 g of 55% sodium hydride in 100 ml of absolute DMF (adhering mineral oil 35 is washed away beforehand with hexane) is added dropwise, in a nitrogen atmosphere, a solution of g of 1 Al H-1,2,4-triazol-1 -yl)-2-(2,4-dichlorophenyl)-pentan-2-oI in 40 ml of absolute DMF and ml of absolute THF. After the exothermic reaction has subsided, stirring is maintained for 1 hour at 50'C, and 1 g of potassium iodide is subsequently added. There are then added dropwise 9.6 g of benzyl bromide in 10 ml of DMF; the reaction mixture is stirred at RT for 12 hours, and is afterwards 40 poured into ice-water. The cloudy emulsion is saturated with sodium chloride, and repeatedly extracted with ethyl acetate. The combined extracts are washed with semi-saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated by evaporation. The residue is purified by column chromatography (silica gel/dichloromethane). The first fraction yields 15 g of a yellowish oil.

6 GB 2 110 684 A 6 Analysis., calculated: C = 61.55% H = 5.45% N = 10.77% Cl = 18.17% found:C = 61.6% H = 5.7% N = 10.5% Cl = 18.0% The following Table contains the aforementioned compounds, and also further compounds which 5 can be similarly produced by one of the processes described in the foregoing.

TABLE 1

Compounds of the formula:

0 R3 X / X R1 CH2 -N -F \-IN R 2 Compound Physical No. R, R2 R, I x const. LOCI 1 C,,H,Cl,(2,4) CA CH, N M.P. 128-131 2 C,H,CI(4) C,H, CH, N M.P. 126-127 3 C,H,C 1(4) CA CH2CH=CH2 N oil 4 C,H3C'2(2,4) C6H, CH2-C,H, N M.P. 118-119 C6H,C 1(4) CH, CH2-C,H, N M.P. 116-119 6 C6H3C'2(2,4) CA CH2CH=CH2 N M.P. 130-132 7 C6H,CI(4) cyclohexyl CH, N M.P. 118-119 8 C,,H,C 12(2,4) C3H,-n CH2-C6H, N oil 9 C61-14CI(4) cyclohexyl C1-12-C61715 N M.P. 116-118 C6H,C'2(2,4) C,H,-n CH3 N b.p. 170-175/ 0.04 mbar 11 C6H,F(4) cyclohexyl CH3 N M.P. 100-101 12 C6H,F(4) cyclohexyl CH2-C6H, N M.P. 74-75 13 C6Hs-CH2 C,H,-n CH3 N oil 14 C6Hs-CH2 C3H,,-n CH2-C,,H5 N oil C61-1, cyclopropyl CH3 N oil 16 C,H,C'2(2,4) cyclohexyl C21-15 N 17 C6H3C'2(2,4) C3H,-n C.H2CH=CH2 N oil 18 C6H3C'2(2,4) C3H,-i CH3 N b.p. 158-162/ 0.03 mbar 19 C6H,C'2(2,4) CH3 CH2-CH=CH2 N M.P. 68-70 C6H3C'2(2,4) CH3 CH2-C,H4C 1(4) N 21 C6H3C'(2)Br(4) CH3 CH3 N oil 22 CAC 1(4) C3H,-n CH3 N b.p. 245-2501 0.05 mbar a 7 GB 2 110 684 A. 7 TABLE 1 (Continued) Compound Physical No. R, R2 R, X const. PC1 23 CH3C 12 (2,4) C^-n CH3 N b.p 240-250/ 0.04 mbar 24 C^Cl,(2,4) C4H.-n CH2-CH, N C6H3C12(2j4) C4H.-n CH2-C.1rl N 4C1(4) oil 26 C^ C411,-n CH3 N oil 27 C6H, C41-1,-n CH2-C^ N 28 C6H4C1(4) C^-n CH3 N b.p. 185-195/ 0.01 mbar 29 C,H4C1(4) C4119-n CH2-C^ N oil C6H, t-butyl CH, N b.p. 150-160/ 0.1 mbar 31 C6H, CH(CH,), CH, N b.p. 25010.04 mbar 32 C6H, CH(CH,), CH,-C^ N b.p. 25010.04 mbar 33 C61-14CH3(4) C^-n CH, N b.p. 170-1801 0.5 mbar 34 C6114CH,(4) C^,-n CH2-C^ N C^C 1,(2,4) CH, CH, N oil 36 C6H3C12(214) CH3 CH2-C61-15 N oil 37 C6H3C12(2,4) CH3 CH2-CAC1(4) N oil 38 C61-13C12(2,4) CH3 C4Hg-n N oil 39 C,H3C12(2,4) CH3 C6H5 N C6HIC12(2,4) CH3 C61-1,1\102(4) N 41 CMC12(2,6) CH3 CH3 N 42 C6H3CM3,4) CH3 CH2-Ms N 43 C6H4C 1(4) CH23-n CH, N oil 44 M4C1(4) C,,H23-n CH2C61-1, N b.p. 25010.04 mbar C6H3C1,(2,4) C,H 1 1-ri CH3 N b.p. 25510.04 mbar 46 C6H3C12(2,4) C^,-n C'4Hg-n N 47 C^ C 1,(2,4) 1 C^,-n CH,-C61-1, N 8.

GB 2 110 684 A 8 TABLE 1 (Continued) Compound Physical No. R, R2 R, const. PCl X 48 C61-1, cyclopentyl CH, N m.p. 91-92 49 CH, cyclopentyl C1-12-C61-14C1(4) N C61-114C1(4) cyclopentyl CH, N 51 CAC 1,(2,4) cyclopentyl CH, N oil 52 C^CM2,4) cyclopentyl CH2-C6H5 N 53 C^C12(2,4) cyclopentyl CH2-C61-11,C12(2,4) N 54 C^CM2,4) cyclopentyl C^-n N C61-1, C1-12-CYClohexyl CH, N 56 C61-11, (CH2)3-CYC'ohexyl CH, N 57 CH,-C,^C 1(2) t-butyl CH3 N 58 CH2-CAF(2) t-b uty 1 CH3 N 59 CH4C1(4). CH,-C61-1,1F(2) CH, N C6H, C61-1,C 1(4) CH, CH visc. oil 61 C6H5 C6H, CH2CEECH CH 62 C6H5 C^C 12(3,4) CH(CH3), CH 63 C^ CMOCH,(4) CH, CH 64 a-naphthy 1 CH, CH3 N m.p. 100-102 a-naphthyl CH, CH, CH 66 P-naphthyl CH, CH, N b.p. 195-2001 0.01 mbar 67 P-naphthyl CH, CH3 CH 68 a-naphthyl CH3 CH2-C6H5 N 69 a-naphthyl CH3 CH2-C6H5 CH CH40CK, CH3 CH3 N oil 71 C^OC^ CH3 CH CH oil 72 C^C61-1, CH, CH3 CH 73 C,1-14-C,H, CH, CH3 N 74 C,H2C1,(2,4,6) CH3 CH, N C^Cl,(2,4) C^ CH, CH oil 9 GB 2 110 684 A. 9 TABLE 1 (Continued) Compound Physical No. R, R2 R, X const. [Cl 7F3 C^C 1(4) C6H5 CH2CH=CH, CEI 77 C^C 12(2,4) C,H,-n CH2-CH, CH 78 C^C12(2,4) C,H,-n CH, CH 79 CM,F(4) cyclohexyl CH, CH C^ C^-n CH, N oil 81 C6H5 C^-n CH2C6H5 N oil 82 C^ cyclohexyl CH, N b.p. 190-200'/ 0.01 mbar 83 C^17(4) cyclobutyl CH, N oil 84 C 6H4C 1(4) C^-n CH2C6H5 N b.p. 170-176/ 0.02 mbar C^CH, C^C 1 (4) CH, N m.p. 88-90 86 C^Cl,(2,4) cyclohexyl CH, N b. p. 200-210 1 / 0.1 mbar 87 C,,HC 1(2) F(4) CH, CH, N oil 88 CH, C 1(2) F(4) CH3 CHAH, N b.p. 250/0.04 mbar 89 CAC 1(2)Br(4) CH, CHAH5 N b.p. 21910.02 mbar F(2)C61-13CH2 C^,-t CH3 N oil 91 C^C 1(4) C6% CH.C=CH CH oil 92 C^C 12(2,4) CH3 C^-n N m.p. 62-64 93 C^C 1,(2,4) CH3 C1-12-C=CH, N b.p. 165-17501 1 0.02 mbar Uti, 94C 6H, C 1, (2,4) CH, CH,Cl-l=CHCH, N b.p. 190-200' 0.02 mbar CACI,(2,4) C^-n C1-12-C=CH2 N b. p. 170-1803/ 1 0.02 mbar 6H3 96 061-1,C12(2,4) C^,-n CH,.CH=CHCH, N b.p. 180-190/ 0.02 mbar 97 C6H3C 12(2,4) C^-n C^-n N oil 98 C,^C12(2,4) C^-n C^-n N b.p. 189-1950/ 0.02 mbar GB 2 110 684 A 10 TABLE 1 (Continued) Compound Physical 99 C^CI(2)17(4) C^-n CH,.-CH=CH2 N b.p. 21010.04 mbar C,^C 1(2) F(4) C^-n C^-n N b.p. 20810.04 mbar 101 C^CI(2)F(4) C^-n CH, N b.p. 190/0.04 mbar 102 C^CI(2)F(4) C^ CH, N b.p. 148-153/" 0.02 mbar 103 C^CI(2)F(4) C^ CH,.-CH=CH, N b.p. 180-186/ 0.03 mbar 104 C,H 3C 12(2,4) C2H, CH, N b.p. 170-1751 0.04 mbar C,H3C12(2,4) G2H, C^-n N b.p. 192-1981 0.03 mbar 106 C^F(4) C^ C^,-n N oil 107 C^F(4) C21-1, -CH2CH=CHCH, N oil 108 C^C 1(2,4) C^-n -CH2-C=_CH N b.p. 178-185C/ 0.04 mbar 109 C^F(4) C31-1,-n C^ -n N oil CH4F(4) CH, C H2-CM4C 1 (4) N oil ill. CH41F(4) C^ CH3 N 1 viscous oil Formulation examples for active substances of the formula 1 (% = per cent by weight) (MG = molecular weight) Emulsion concentrates/wettable powders a) b) C) active substance from Table 1 25% 40% 50% Calcium dodecylbenzenesulfonate 5% 8% 6% caster oil-polyethylene glycol ether (36 mols of ethylene oxide) 5% tributylphenoyi-poiyethylene glycol ether (30 mols of ethylene oxide) 12% 4% 10 cyclohexanone - 15% 20% xylene mixture 65% 25% 20% Emulsions of any required concentration can be produced from concentrates of this type by dilution with water. () Wettable powders are produced when xylene is replaced with silicic acid and/or kaolin.

11 GB 2 110 684 A 11 Solutions active substances from Table 1 ethylene glycol-monomethyl ether polyethylene glycol MG 400 N-methyl-2-pyrrolidone epoxidised coconut oil ligroin (boiling limits 160-1900C) The solutions are suitable for application in the form of very small drops.

a) b) 80% 10% 20% c) d) 5% 95% 70% 20% - - 5 1 % 5% 94% Granulates a) b) active substances from Table 1 5% 10% 10 kaolin 94% highly dispersed silicic acid 1 % - attapulgite - 90% The active substance is dissolved in methylene chloride; the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. 15 Dusts a) b) active substance from Table 1 2% 5% highly dispersed silicic acid 1 % 5% talcum 97% - kaolin - 90% 20 Ready-for-use dusts are obtained by the intimate mixing together of the carriers with the active substance.

BIOLOGICAL EXAMPLES EXAMPLE 2.1 26 Action against Puccinia graminis on wheat a) Residual protective action Six days after being sown, wheat plants were sprayed with a spray liquor prepared from wettable powder of the active substance (0.002% of active substance). After 24 hours, the treated plants were infested with a uredospore suspension of the fungus. After an incubation time of 48 hours at about 201C with 95-100% relative humidity, the infested plants were kept in a greenhouse at about 221C. 30 An assessment of the development of rust pustules was made 12 days after infestation.

b) Systemic action A spray liquor prepared from wettable powder of the active substance (0. 0006% of active substance, relative to the volume of soil) was poured onto the soil of wheat plants 5 days after sowing.

After 48 hours, the treated plants were infested with a ureclospore suspension of the fungus. After an 35 incubation time of 48 hours at about 20'C with 95-100% relative humidity, the infested plants were kept in a greenhouse at about 221C. An assessment of the development of rust pustules was made 12 days after infestation.

Compounds from the Table I exhibited against Puccinia fungi a good action. Untreated but infested control plants displayed a level of Puccinia infection of 100%. Puccinia infection was reduced to 0 to 5% 40 by, inter alia, the compounds Nos. 1- 4, 5-12, 15, 17-23, 26, 28, 33-38, 45, 48, 60, 80, 81, 83, 84, 87-90, 92- 101 and 108-111.

12 -- GB 2 110 684 A 12 EXAM P LE 2.2 Action against Cercospora arachidicola on groundnut plants Residual protective action Groundnut plants 10-15 cm in height were sprayed with a spray liquor produced from wettable powder of the active substance (0.006% of active substance); and 48 hours later they were infested with a conidiospore suspension of the fungus. The infested plants were incubated for 72 hours at about 21 C with high relative humidity, and were subsequently kept in a greenhouse until the typical leaf spots had appeared. The assessment of the fungicidal action was made 12 days after infestation, and was based on the number and size of the occurring spots.

Compared with untreated, but infested control plants (number and size of spots = 100%), groundnut plants which had been treated with active substances from Table 1 exhibited a greatly reduced level of Cercospora infection. Thus the compounds Nos. 1-3, 5-8, 10-12, 15, 17-19, 21-23, 28, 29, 35-38, 87, 89 and 92-111 prevented the occurrence of spots in the above test virtually completely (0 to 10%).

EXAMPLE 2.3 Action against Erysiphe graminis on barley a) Residual protective action Barley plants about 8 cm in height were sprayed with a spray liquor prepared from wettable powder of the active substance (0.002% of active substance). After 3-4 hours, the treated plants were dusted with conidiospores of the fungus. The infested barley plants were kept in a greenhouse at about 20 220C, and the extent of fungus infection was assessed after 10 days.

b) Systemic action A spray liquor prepared from wettable powder of the active substance (0. 0006% of active substance, relative to the volume of soil) was poured onto the soil of barley plants about 8 cm in height.

Care was taken to ensure that the spray liquor did not come into contact with the parts of the plants 25 above the soil. After 48 hours, the treated plants were dusted with conidiospores of the fungus. The infested barley plants were kept in a greenhouse at about 221C, and an assessment of the extent of fungus infection was made after 10 days.

Compounds of the formula I exhibited a good action against Erysiphe fungi. Untreated but infested control plants showed a level of Erysiphe infection of 100%. Among other compounds from the Table 1, 30 compounds Nos. 1-23,25, 26,28-32, 35-38,43,45,48, 51, 63,70, 71,75, 80-84, 87-89 and 91-111 reduced fungus infection on barleyto Oto 5%.The compounds Nos. 1-8, 10-13, 15, 17-19, 21-23, 28, 35-37,45, 84, 88, 89, 92-101, 108 and 109 were particularly effective (no infection).

EXAMPLE 2.4

Residual protective action against Venturia inaequalis on apple shoots Apple seedlings having 10-20 cm long fresh shoots were sprayed with a spray liquor prepared from wettable powder of the active substance (0.006% of active substance). The treated plants were sprayed after 24 hours with a conidiospore suspension of the fungus. The plants were then incubated for 5 days with 90-100% relative humidity, and for a further 10 days they were kept at 20-241C in a 40 greenhouse. The extent of scab infection was assessed 15 days after infestation. Control plants were infected to the extent of 100%. Compounds Nos. 1-3, 6-8, 10,11, 15, 21-23, 28,35-37, 45, 83, 84, 87, 89, 92-101, 108 and 109 reduced infection to less than 10%. Where treatment was carried out with the active substances Nos. 8, 10, 11, 21, 23, 45 and 96-101 no infection at all occurred.

EXAMPLE 2.5 Action against Botrytis on apples Residual protective action Artificially damaged apples were treated by applying drops of spray liquor, prepared from wettable powder of the active substance (0.02% of active substance), to the damaged areas on the apples. The treated fruit was then inoculated with a spore suspension of Botrytis cinerea, and incubated for one 50 week at about 200C with high relative humidity. The presence and the size of the decayed areas on the fruit served as a basis for assessing the extent of fungicidal activity. After treatment with the compounds Nos. 1, 8, 10, 12, 13, 17, 19, 21, 23, 28, 35, 37, 83, 87 and 90, there were no, or virtually no, areas of decay to be observed (0-5% infection).

1 15. 1 13 GB 2 110 684 A - 13 c AIMS 1. A compound of the general formula 1 OR3 1 IR,- -CH2R4 i M2 (1) wherein R, is phenyl, phenyl mono- to trisubstituted by halogen, Cl-C3-haloalkyl, nitro, C,-C,-alkoxy, C,-C.alkyl and/or cyano, or phenyl substituted by phenyl or phenoxy, naphthyl, or naphthyl mono- or disubstituted by halogen, nitro and/or C 1-C3-alkyl, benzyl, or benzyl mono- or disubstituted by halogen, nitro and/or Cl-C.-alkyl; R2 is phenyl, phenyl mono- or trisubstituted by halogen, C 1-C3-haloalkyl, nitro, Cl-C.-alkoxy, Ci-C.-alkyl and/or cyano, or phenyl substituted by phenyl or phenoxy, or it is C,-Cl.-alkyl, C3-C8-cycloalkyl or C3-C,-Cycloalkyl-(Cl-C4-alkyl); R3'S Cl- C,2-alkyl, C2--CC alkenyl, C3-C4-alkynyl, benzyl, or benzyl mono- or disubstituted by halogen, nitro and/or Cl-C3-alkyl; and R4 is an azolyl group; including the acid addition salts thereof, quaternary azollum salts and metal complexes.

Claims

2. A compound of the formula I according to Claim 1, wherein R, is phenyl,

or phenyl mono- to trisubstituted by fluorine, chlorine, bromine, CF31 C,-C,-alkoxy, Cl-C3- alkyl and/or cyano, or it is biphenyl, phenoxyphenyl, naphthyl, or naphthyl mono- or disubstituted by fluorine, chlorine, bromine, nitro and/or Cl-C,-alkyl, or benzyl, or benzyl mono- or disubstituted by fluorine, chlorine, bromine, nitro and/or Cl-C3-alkyl; R2 is phenyl, or phenyl mono- to trisubstituted by fluorine, chlorine, bromine, CF 31 Cl-C2-alkoxy, Cl-C.-alkyl and/or cyano, or biphenyl, phenoxyphenyl, C,-C.- alkyl, C3-C,7CYCloalkyl or C3-C6-CYC'oalkyl-(Cl-C2-alkyl); R3'S Cl-C,-alkyl, C27-C,-alkenyl, propargyl, benzyl, or benzyl 20 mono- or disubstituted by fluorine, chlorine, bromine, nitro and/or Cl-C3- alkyl; and R4 is 1 H-1,2,4 triazolyl, 4H-1,2,4-triazolyl or 1 H-imidazolyl.

3. A compound of the formula I according to Claim 1, wherein R, is 2,4dihalophenyl, 2,6 dihalophenyl, 2-halophenyl, 4-halophenyl, phenyl, biphenyl, phenoxyphenyl, 2-halo-ce-naphthyl, 4-halo cv-naphthyl, a-naphthyl, 2-halobenzyl, 4-halobenzyl, 2,4-dihalobenzyl, 2, 6-dihalobenzyl, 3,4 dihalobenzyl or benzyl; R2 is phenyl, 2,4-dihalophenyl, 2,6-dihalophenyl, 2-halophenyl, 4-halophenyl, biptienyi;. phenoxyphenyl, C,,-C,7alkyl, cyclopropyl, cyclopentyl or cyclohexyl; R3 is C,-C,-alkyl, allyl, propargyll benzyl, 2,6-dichlorobenzyl, 4-chlorobenzyl, 4-fluorobenzyl or 2,4-dichlorobenzyl; and R4'S 1 H-1,2,4-triazolyl.

4. A compound of the formula I according to Claim 1, wherein R, is 2,4dichlorophenyl, 2-chloro- 30 4-bromophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 4-fluorophenyl, 2- chloro-a-naphthyl, 4-chloro-a naphthyl, 2-chlorobenzyl, 4-chlorobenzyl or 2,4-dichlorobenzyl; R2 is phenyl, 2,4-dichlorophenyl, 2 chloro-4-bromophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 4-fluorophenyl, C,-C,-alkyl or C,-C, cycloalkyl; R. is Cl-C.-alkyl, ally[, propargyl, benzyl, 2,6- dichlorobenzyl, 4-chlorobenzyl, 4-fluorobenzyl or2,4-dichlorobenzyl; and R4'S 1H-1,2,4-triazolyl.

5. A compound of the formula I according to Claim 1, wherein R, is 2,4dichlorophenyl, 2-chloro 4-fluorophenyl, 2-fluoro-4-chlorophenyl, 2-chloro-4-bromophenyl, 4- chlorophenyl or 4-fluorophenyl; R2 is C,-C,-cycloalkyl or C,-C4-alkyl; and R3 is benzyl, chlorobenzyl, dichlorobenzyl, C,-C4-alkyl or C3-C4-alkenyl.

6. A compound of the formula 1 according to Claim 5, wherein R3'S Cl-C4alkyl, and R, and R2 are 40 as defined.

7. A compound of the formula 1 according to Claim 5, wherein R2 is methyl, isopropyl or see-butyl, and R, and R3 are as defined.

8. A compound of the formula 1 according to Claim 1, selected from the series comprising:

1 -0 H1,2,4-triazol-1 -yi)-2-phenyi-2-(2,4-dichlorophenyi)-2-methoxyethane, 1 -0 H-1,2,4-triazol-1 -yl)-2-phenyi-2-(4-chlorophenyi)-2-allyloxy-ethane, 1 -(1 H-1,2,4-triazol-1 -yl)-2-phenyl-2-(4-chlorophenyi)-2-methoxy-ethane, 1 -0 H-1,2,4-triazol-1 -yi)-2-benzyioxy-2-(2,4-dichlorophenyl)-pentane, 1 -0 H-1,2,4-triazol-1 -yi)-2-methoxy-2-(2,4-dichlorophenyl)-pentane, 1 -0 H-1,2,4-triazol-1 -yi)-2-methoxy-2-(4-fluorophenyl)-2-cyclohexyi- ethane, 1 -(1 H-imidazol-1 -yi)-2-pheny]-2(2,4-dichlorophenyi)-2-methoxy-ethane, and 1 -0 H-1,2,4-triazol-1 -yi)-2-methoxy-2-(2,4-dichlorophenyi)-3methyibutane.

9. A process for producing a compound of the formula 1 defined in Claim 1, which process comprises reacting a compound of the formula 11 A so IR,- 1 -CH2R, (11) 55 1 R2 14 GB 2 110 684 A 14 with a compound of the formula Ill Rj-W (111), wherein the substituents IR,, IR, IR,, and R4 are as defined in claim 1, A and W are each -OH, -OM or one of the customary removable groups, M is an alkali metal atom or alkaline-earth metal atom, with the proviso that the choice of the reactants Hand Ill is always such that either an MO or HO function 5 reacts with a removable group or two hydroxyl functions react with each other.

10. A process according to Claim 9, wherein A or W as a removable group is halogen, -OSO2R., -OCO-R, or -O-C=NIR, 1 NI-1R7 wherein R5, R. and R7 independently of one another are each Cl-C3-alkyl or Cl-C3-haloalkyl, or phenyl which is unsubstituted or substituted by halogen, methyl, nitro, trifluoomethyl and/or methoxy. 10 11. A microbicidal composition for controlling and/or preventing attack by phytopathogenic microorganisms, which composition contains, as at least one active ingredient, a compound of the formula 1 as defined in Claim 1.

12. A composition according to Claim 11, which contains, as active ingredient, at least one compound as defined in anyone of Claims 2 to 4 orin Claim 8.

13. A composition according to Claim 11, which contains, as active ingredient, at least one compound as defined in Claims 5, 6 or 7.

14. A method of controlling or preventing attack by phytopathogenic microorganisms, which method comprises applying to plants, or to a locus likely to be infected by microorganisms, a microbicidally effective amount of a compound of the formula 1 according to Claim 1.

15. A method according to Claim 14, which method comprises applying a compound of the formula 1 according to any one of Claims 2 to 4 or 8.

16. A method according to Claim 14, which method comprises applying a compound of the formula 1 according to any one of Claims 5, 6 or 7.

17. A compound of the formula 1, defined in claim 1 substantially as hereinbefore described with 25 reference to any one of the foregoing Examples.

18. A composition as claimed in claim 11 substantially as hereinbefore described with reference to any one of the Formulation Examples.

19. A method as claimed in claim 14 substantially as hereinbefore described with reference to any one of the Biological Examples.

Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1983. Published by the Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.

1 1 i