IE54223B1 - Microbicidal compositions - Google Patents

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

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 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 OR, CH.

A, wherein R^ is 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl, 2-fluoro-4-chlorophenyl, 2-chloro-4-bromophenyl, 4-chloro15 phenyl cr 4-fluorophenyl, R2 is C3-Cg-cyclo-alkyl, or ciTC4-alkyl, R3 is benzyl, chlorobenzyl, di-chlorobenzyl, - C1-C4~alkyl or C3~C4-alkenyl. 3v ’alkyl’ is meant, depending on the given number of carbon atoms, for example the following groups: methyl, ethyl, propyl, butyl and isomers thereof, such as isopropyl, isobutyl· and tert-butyl. Alkenyl is for example: propenyl(1), allyl, butenyl-(1), butenyl-(2) or butenyl-(3). Cycloaikyl is, depending on the number of carbon atoms, fcr example: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. 4 2 2 3 The compounds of Che formula I at room temperature are stable oils, resins or solids, which are 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 active substances of the formula I accordina to the invention are characterised by very good microbicidal activity, and by their great ease of application.

Compounds cf importance among those of formula I are those wherein Rj is Cj-C^alkyl, while Rj and Rj are as defined above.

Furthermore, compounds of special importance are those wherein Rj is methyl, iso-CjH? or sec-C4Hg, while Rx and Rj are as defined above.

Individual compounds preferred in particular are for example: 1-(1H-1,2,4-triazol-l-yl)-2-benzyloxy-2-(2,4-dichlorophenyl)pentane, 1-(1H-1,2,4-triazol-l-yl)-2-methoxy-2-(2,4-dichlorophenyl)pentane, 1-(1H-1,2,4-triazol-l-yl)-2-methoxy-2-(4-fluorophenyl)-2cyclohexyl-ethane, 1-(1H-1,2,4-triazol-l-yl)-2-n-propoxy-2-(2,4-dichlorophenyl)pentane, 1-(lH-l,2,4-triazol-l-yl)-2-n-propoxy-2-(2-chloro-4-fluorophenyl) -pentane, 1-(1H-1,2,4-triazol-l-yl)-2-methoxy-2-(2,4-cichlorophenyl) 3-methylbutane, 1-(1H-1,2,4-triazol-1-yl) - 2-methor.y-2-(2-chloro-Λ-fluorophenyl) -pentane, and 1-(1H-1,2,4-triazol-1-yl)-2 - (p-chlorobenzyloxy)-2-(2,4dichlorophenyl) -propane.

Azolyl-ethane derivatives of the formula I can be produced according to the invention by reacting a compound of the formula II (II) with a compound of the formula III R3-W (III), wherein the substituents R^, R^ ar)<3 are 35 defined under the formula I, A and K are each -OH, -OM where M is an al-iali metal atom cr *ai ‘.sline-earr.-. retai atom, or one cf the removable groups, 15 halogen [for example: fluorine, chlorine, brcmine or iodine, preferably chlorine or bromine or iodine,«lore preferably chlorine or bromine]; -OSO2~R5; -OCO-R5; or -O-C=NRg, wherein Rg, Rg and R^ independently of cne another are each Cj-C3-alkyl or C^-Cj-haloalkyl, or phenyl 20 which is unsubstituted cr substituted by halogen, methyl, nitro, trifluoromethyl and/or methoxy, with the proviso that the choice of the reactants II and III is always such that either an MO or HO function reacts with a removable group or two hydroxyl functions react with each other.

In so far as alcohols, or alcoholates of the formula II 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 ff is a halide, preferably a chloride or bromide. The reaction is carried out in the temperature range of 0° to 150°C, either not in a solvent or, preferably, in aprotic solvents, such as aromatic and aliphatic hydrocarbons, ethers and ethereal compounds (diethyl ether, dioxane, tetrahydrofuran [THF], and so forth), acetonitrile, dimethylformamide [DMF], 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 II (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: l-phenyl-2-(lH-l,2,4-triazol-lyl)-ethanol derivatives in the German Offenlegungsschrift No. 3,042,302; ani 2-(lH-l,2,4-triazol-l-yl)-ethanol derivatives in the EP Offenlegungsschrift No. 0,015,756 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 R^ 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 centre (*) (I) and can therefore be present in two enantiomeric forms.

There is generally formed in the production of these substances a mixture of both enantiomeric 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 I a mixture of both enantiomeric forms.

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

The microorganisms occurring on plants cr 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 I, and also parts of plants subsequently growing remain preserved from such microorganisms. The active substances of the formula 1 are effective against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (for example Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomvcetes (for example the species: Hemileia, Rhizoctonia and Puccinia); in particular they are effective against the Ascomycetes class (for example: Venturia, Podosphaera, Erysiphe, Xonilinia and Uncinula). Furthermore, the compounds of the formula I have a systemic action. They can be used also as dressing 54233 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 I, and also to the use of these compositions, or of the active ingredients on 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); legumes: (beans, lentils, peas and soya-bean); oil plants: (rape, mustard, poppy, olives, sunflowers, coco, castor-oil plants, 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, 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 ir. the form cf compositions, and can be applied, simul5 4 2 2 3 taneously 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, nematicides 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 agencs, 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 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 12 2 3 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 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 Cg to C^j such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutylor 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, are as a rule natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite 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 ground plant residues.

Suitable surface-active compounds are, depending on the nature of the active substance cf the formula I to be formulated, nonionic, cationic and or anionic tensides 4 2 2 3 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 publications: Me 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 agrochemical preparations contain as a rule 0.1 to 99%, particularly 0.1 to 95%, of active substance of the formula I, 99.9 to 1%, especially 99.8 to 5%, of a solid or liquid additive, and 0 to 25%, 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 - Examples 1 and 2 illustrate the process steps used to produce the compounds of the invention.

Example 1: Production of NaH/CHjI II • · I il ii V ii 1- (lH-l,2,4-Triazol-l-yl)-2-phenyl-2-(2,4-dichlorophenyl)2- methoxy-ethane 1.8 g (0.041 mol) of sodium hydride dispersion (about 557. strength) in mineral oil are suspended, in a nitrogen atmosphere, twice with petroleum ether; and 50 ml of DMF are subsequently added. There is then added dropwise, with stirring, a solution cf 12.5 g (0.037 mol) of 1-(1H-1,2,4-triazol-l-yl)-2-phenyl-2-(2,4-dichlorophenyl)-ethanol in 70 ml of DMF; the reaction mixture is stirred at 40°C for 30 minutes, and 3.2 ml (0.052 mol) of methyl iodide are afterwards added dropwise, the temperature then rising to about 53°C. The mixture is stirred at RT for a 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 diechyl ether; it is finally cooled to RT and filtered; yield: 10.9 g of colourless crystals, m.p. 128-131^0.

Example 2: Production of NaH/BrCH,C,He 2 o 5 (KI) 1-(lH-l,2,4-Triazal-l-yl)-2-benzyloxy-2-(2,4-dichlorophenyl)-pentane To a suspension of 2.4 g of 557. sodium hydride in 100 ml of absolute DMF (adhering mineral oil is washed away beforehand wich hexane) is added dropwise, in a nitrogen atmosphere, a solution of 15 g of 1-(1H-1,2,4triazol-l-yl)-2-(2,4-dichlorophenyl)-pentan-2-ol in 40 ml of absolute DMF and 10 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 i.5 FT for L2 hours, and is afterwards 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 concen20 trated by evaporation. The residue is purified by columnchromatography (silica gel/dichloromethane). The first fraction yields 15 g of a yellowish oil.

Analysis : calculated: C * 61.557. H * 5.457. N - 10.777. Cl » 13.177. found : C « 61.67. H « 5.77. N =· 10.57. Cl = 13.07..

The following Table contains the aforementioned compounds and also further compounds which can be similarly produced by one of che precesses described in the foregoing. 54233 Table 1: Compounds of the formula OR, I * —CH I Canpound No.Ri .R2R3 X Physical const. [°C] 1 C6H3C12(2,4)C6H5CH3 N e.p. 128-131 2 C6H4C1(4)C6«5 ch3 N e.p. 126-127 3 W1(4) cyolohexyl CH3 H ».P. 118-119 4 C6H3C12(2,4) C3H7-n ch2-c6hs N oil 5 C6H4C1(4) cyolohexylCH2C6H5 H *.P. 116-118 C6H3C12(2,4) h.p. 170-175/ 6 C3H7-n ch3 N 0.01 ebar 7 C6V<4) cyolohexyl ch3 N e.p. 1OO-1O1 3 C6H4F(4) cyolohexylCVC6H5 N ».Ρ· 74-75 9 C6H3C12(2,4) cyclobexy1 c2h5 N 10C6H3C12(2’4) C3H7-n CH2CH-CH2 N oil 11 C6H3C12(2,4) C3H7-iCH3 N b.p. 158-162/ 0.03 h'»»· 12 C6H3C12<2,4) CH3 CH,-CH-CH, L i. N e.p. 58-70 13 C6H3CI2(2,4) ch3CH2-C6H4C1(4) N 14 C6H3Cl(2)Sr(4) ch3 ch3 N oil 15 C6H4C1(4) C3H7-n ch3 N b.p. 245-250/ 0.05 liar 16 C6H3C12(2,4) C4H9-n ch3 N h.p. 2*0-250/ 3 JJ* soar 17 CsH3C12(2,4) C4Hg-nCH2’C6H5 N 18 c6h3ci2(2,4) C4Hg-n CH2-C&H4C1(4) N ail S 4 3 3 3 Η Zoapound R R R X Physical const. [ C] No. 1 2 3 19 C6H4C1(4)C4H9-q ch3 H b.p. 185-195/ 0.01 «Par 20 C6H4C1(4>C4H9~nCH2_C6H5 ii oil 21 C6H3C12(2,4) oh3 ch3 S oil 22 C6H3C12(2,4) ch3 ch2-c6h5 s oil23 C.H3C12(2,4) CHj CH2-C6H4C1(4) s oil 24c6W2’4) ch3 C4Vn ?t oi- 25 C6H4C1(4) cyc’opentyl CH3 N 26 C6H3C12(2,4) cyclopentyl ch3 N oil 27 CbH3Cl2(2,4) cyclopentyl ch2-c6h5 Η 23 οΛα2(2,4) cyclopenty) CH2-C6H3C12(2,4 1 N 29 C6H3C12(2,4) CyclopentylC4Hg~n S 30 cydobi/yl ch3 N oil 31 C6H4C1(4) C3H7-n ch2c6h5 N b.p. 173-175/ 0,02 soar 32C6H3C12(2’4) cyclohexyl ch3 fi b.n. 230-2,0°/ 5.1 soar 33 0^01(2)7(4) ch3 N oil 34 C H_C1(2)F(4) 0 J CH,CH2C6H5 N b.p. 255/3.04 Par 135 JC6H3Cl(2)Br(4) CHj CH2C6Hj N b.p. 2'G/O -02 ’car Co·- pound No.R1R2R3 X Physical const. [ C] 36C6H3C12(2’4) οπ3C3B7-" N B.p. 52—54 37 C&H3C12(2,4) CH3 CH2-(f-CH2 ra3 N b.p. 165-175°/ 0.02 soar 38 C&H3C12(2,4) oh3 CH2CH*CHCH3 H , b.p. 190-200°/ 0.02 soar 39 C6H3C12(2,4)C3H7-° CH.-C-CH, 2 ι 2 ch3 N b.p. 170-180°/ 0.32 «tar 40 C6H3C12(2,4) C^^-n CH2CH»CHCH3 N b.p. 130-190 / 0.02 «bar 41 C&H3C12(2,4) C3H7-n H oil J 42 CfeH3Cl2(2,4)C4Hg-n N t.p. 159-195°/ 0.02 «bar 43 C6H3Cl(2)r(4) C.H.-n CH,-CH-CH, N b.p. 2,0/0.04 star 44 C6H3C1(2)F(4) C3H7-n K b.p. 208/0.04 ibar 45 C6H3C1(2)F(4) C,H--n CH- N b.p. 190/0.04 «bar 46 C&a3Cl(2)F(4) CA "3 N t.p. 148-153/0.02 ibar 47 C6H3C1(2)F(4)C2H5 CH,-CH-CH, N b.p. 130-,36/0:33 «bar 48 CaH,C1,(2,4) CA ch3 N o.p. I70-175/C.04 acar . 49 C6H3C12(2,4)C2H5 C3H7-a N b.p. 132-138/0.03 aaar 50 WC4)C2H5C4H9‘n H oil »4223 Comp.R.K2?‘3 Phvsical λ’ο. constants [°C] ...... 1 51 Cii.FW 0 *+CA -CH.)CII=CKCH3 N oil 52 C . FG) D ·* .y7-n y:7-n X oil ί - m Z7.5 C H.F(4) υ -4 ch3 CrU-Cjl Cx(A) - b m »T oil 54 CbH-F(4) c7h 1 " CH3 s I viscous oil Formulation examples for active substances of the formula I i'% = per cent by weight) (MG = molecular weight) Fmulsicn concentrates/wettable powders a) b) c) 5 active substance from Table 1 25% 4C% 50% calcium dodecylbenzenesulfonate 5% £ · ·. to 6% caster oil-polyethylene glycol ether (36 mols of ethylene oxide) 5% - tributylphenoyl-polyethylene glycol 1° ether (30 mols of ethylene oxide) • 12% 4% 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.

Solutions a) b) c) active substance from Table 1 S0% 10% ethylene glycol-monomethyl ether 20% polyethylene glycol MG 400 - 70% : -methyl-2-pyrrolidone - 20?= epoxidised coconut oil ligroin (boiling limits l60-lc0cC)The solutions crops. % 1% m4% itable for application i d) 95% :he form % Granulates a) b) active substance from Table 1 5% 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.

Dusts a) b) active substance from Table I 2% 5% highly dispersed silicic acid 1% 5% talcum 97% - kaolin - 90% Ready-for-use dusts are obtained by the intimate mixing together of the carriers with the active substance.

Biological Examples Example 2.1 Action against Ruccinia 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 20°C with 95-100% relative humidity, the infested plants were kept in a greenhouse at about 22°C.

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 . 000 67; of active substance, relative to the volume of soil) was poured onto the soil of wheat plants 5 days after sowing. After 43 hours, the treated plants were infested with a uredospore suspension of the fungus. After an incubation time of uS hours at about 20cC with 95-1007o relative humidity, the infested plants were kept in a greenhouse at about 22°C. An assessment of the development of rust pustules was mace 12 cays 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 cf 100%. Puccinia infection was reduced to 0 to 57; by, inter alia, the compounds Nos. 3-S, 10-16, 19, .21-24, 30, 31, 33-45 and 52-54, Example 2.2: Action against Cercospcra arachidicola on groundnut plants Residual protective action Groundnut plants 10-15 cm in height were sprayed with a spray liquor produced froa wettable powder of the active substance (0.0067. 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 21^0 with high relative humidity, and were subsequently kept in a greenhouse until the typical leaf spots had appeared. The assessment cf the fungicidal action was made 12 days after infestation, and was based on the number and size of the occurring sects.

Compared with untreated, but infested control plants (number and size of spots - 1007;), groundnut plants which hac been treated with active substances frcm Table 1 exhibited a greatly reduced level of Cercospora infection. Thus the compounds Vos. 3, 4, 6—8, 10—12. 14—16, 19-24, 33, 35 and 36-54 prevented tne occurrence of spots in the above test virtually completely 5 (0 to 10%).

Example 2.3: Action against Ervsiohe graminis on barley a) Residual protective action Barley plants about 3 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 coniciospores of the fungus. The infested barley plants were kept in a greenhouse at about 22°C, and the extent cf fungus infection was assessed after 10 days. b) Systemic action A spray liquor prepared froa wettable powder of che active substance (0.000670 of active substance, relative to the volume of soil) was poured onto che 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 che plants above the soil. After 48 hours, che treated plants were dusted with ccnidiospores of the fungus. The infested barley plants were kept in a greenhouse at about 22°C, 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. Uncreated but infested control plants showed a level of Erysiphe infection of lC0%.

Among other compounds from the Table I, compounds Nos. 3 16, 13-20, 21-24 , 26, 30, 31, 32-35 ar.d 26 — 54 reduced fungus infection or. oarley to 2 - :4. The compounds \'cs. , 5-3 , --/ rx Λ *) »> -I ~ 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, 10 and for a further 10 days they were kept at 20-24°C in a greenhouse. The extent of scab infection was assessed 15 days after infestation. Control plants were infected to the extent of 100%. Compounds Nos. 3, 4, 6, 7, 14-16, 19, 21-23, 30, 31, 33, 25-45 and 52 reduced infection to less 15 than 10%. Where treatment was carried out with the active substances Nos. 4,6, 7, 14, 16, 23, and 40-45 nc 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 cf the 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 Botrvtis cinerea, 25 and incubated for one week at about 20°C with high relative humidity. The presence and the size of the decayed areas on the fruit served as a basis for assessing the extent cf fungicidal activity. After treatment with the compounds Nos. 4, 5, 8, 10, 12, 14, 16, 19, 21, 23, 30 and 33 there were no, or virtually no, areas of decay to be observed (0-5% infection).

Claims (22)

1. Claims;

1. A compound of the general formula I, CH. wherein R^ is 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl, 5 2-fluoro-4-chlorophenyl, 2-chloro-4-bromophenyl, 4-chlorophenyl or 4-fluorophenyl, R 2 is C^-Cg-cyclo-alkyl, or Cj-C 4 -alkyl, R^ is benzyl, chlorobenzyl, di-chlorobenzyl, C 1 -C 4 ~alkyl or C 3 -C 4 -alkenyl.

2. A compound of the formula I according to Claim 1, 10 wherein R 3 is C 1 ~C 4 -alkyl, and R x and R 2 are as defined.

3. A compound of the formula I according to Claim 1, wherein R 2 is methyl, isopropyl or sec-butyl, and R^ and R 3 are as defined.

4. 1-{1H-1,2,4-triazol-1-yl)-2-me thoxy-2-(2,4-dichloro15 phenyl)-butane.

5. 1-llH-l, 2,4-triazol-l-yl)-2-n-propoxy-2-( 2,4-dichlorophenyl) -butane.

6. 1-(1H-1,2,4-triazol-l-yl)-2-allyloxy-2-(2,4-dichlorophenyl) -pentane. 20

7. l-(lH-l,2,4-triazol-l-yl)-2-methoxy-2-(2,4-dichlorophenyl)-pentane.

8. 1-(1H-1,2,4-triazol-l-yl)-2-methoxy-2-(2-chloro-4fluorophenyl)-pentane. m ο LC

9. 1-(1H-1,2,4-triazol-l-yl)-2-methoxv-2-(2,4-dichlorophenyl) -3-methylbutane.

10. 1-(1H-1,2,4-triazol-l-yl)-2-crotyloxy-2-(2,4-dichlorophenyl)-pentane.

11. A process for producing a compound of the formula I defined in claim 1, which comprises reacting a compound of the formula II: A S .!-CH,-/ | 2 *2 (II) with a compound of the formula III: r 3 -w (ITI) wherein R^, R, and R^ are as defined in claim 1, and A and W are each -OH, -OM where M is an alkali metal atom or alkaline earth metal atom, or one of the removable groups halogen, -OSO^R^, -OCO-R^ or -O-C=NRg NHR ? 15 wherein Rg, Rg and R, independently of one another are each C^-Cj-alkyl or C^-C 3 haloalkyl or phenyl which is unsubstituted or substituted by halogen, methyl, nitro, trifluoromethyl and/or methoxy, with the proviso that the choice of the reactants II and III is always such that either an MO or 20 HO function reacts with a removable group or two hydroxyl functions react with each other.

12. A microbicidal composition for controlling and/or preventing attack by phytcpathogenic microorcanisms, which composition contains, as at least one active ingredient, a 25 compound of the formula I as defined in Claim 1. 5 4 2 2 3 ??

13. A composition according to Claim 12, which contains, as active ingredient, the compound 1-(1H-1,2,4-triazol-lyl) -2-methoxy-2-(2,4-dichlorophenyl)-butane.

14. A composition according to Claim 12, which contains, as active ingredient, the compound 1-(1H-1,2,4-triazol1- yl) -2-n-propoxy-2-(2,4-dichlorophenyl)-butane.

15. A composition according to Claim 12, which contains, as active ingredient, the compound 1-(1H-1,2,4-triazol-lyl) -2-methoxv-2-(2,4-dichlorphenyl)-pentane.

16. A method of controlling or preventing attack by phytopathogenic microorganisms, which method comprises applying to plants, or to a locus susceptible to infection by microorganisms, a microbicidally effective amount of a compound of the formula I according to Claim 1.

17. A method according tc Claim 16, which method comprises applying the compound 1-(1H-1,2,4-triazol-l-yl)-2-methoxy2- (2,4-dichlorphenyl)-butane.

18. A method according to Claim 16, which method comprises applying the compound l-(lH-l,2,4-triazol-l-yl)2-n-propoxy-2-(2,4-dichlorophenyl)-butane.

19. A method according to claim 16, which method comprises applying the compound l-(lH-l,2,4-triazol-l-yl)2-methoxy-2-(2,4-dichlorcphenyl)-pentane.

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

21. A composition as claimed in claim 12 substantially as hereinbefore described with reference to any one of the Formulation Examples.

22. A method as claimed in claim 16 substantially as hereinbefore described with reference to any one of the Biological Examples.