NZ202629A

NZ202629A - 1,2,4-triazolylethyl ethers and microbicidal compositions

Info

Publication number: NZ202629A
Application number: NZ202629A
Authority: NZ
Inventors: R Nyfeler; A Meyer; E Sturm
Original assignee: Ciba Geigy Ag
Priority date: 1981-11-27
Filing date: 1982-11-26
Publication date: 1986-06-11
Also published as: BR8206872A; JPS58103367A; MY8700133A; AU9088282A; DK159774C; IE54223B1; PT75902A; ES8503644A1; ATE49200T1; IE822820L; PH20349A; GB2110684B; IL67339A0; JPH0463071B2; DK159774B; EP0082340A1; GB2110684A; GR77746B; KR840002363A; 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

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £02629 202629 Priority Date(s); Q.lr..I /. Complete Specification Filed: Class: CP7.QcP.Q 9i .j. A 01 jiU&J&(/., Publication Dote-: .. .ft I JUN Patents Form No.5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION "MICROBICIDAL COMPOSITIONS" -I-,WE CIBA-GEIGY AG, a Swiss Corporation, of Klybeckstrasse 141, 4002 Basle, Switzerland, hereby declare the invention, for which iVwe pray that a patent may be granted to me/us, and the method by which it is to be performed, to be particularly described in and by the following statement - 1 - (followed by page I A.) -1A- 202620 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 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-. N=- 1 / R.— CH — N wherein R^ is 2,4-dichlorophenyl, 2-chloro-4-fluoro-phenyl, 2-fluoro-4-chlorophenyl, 2-chloro-4-bromophenyl, 4-chlorophenyl or 4-fluorophenyl; R£ is C^-Cg-cyclo-alkyl or C^-C^-alkyl; R^ is benzyl, chlorobenzyl, di-chlorobenzyl, C^-C^-alkyl or C^-C^-alkenyl; and the acid addition salts, quaternary azolium salts and metal complexes thereof. By alkyl is meant, the following groups: methyl, ethyl, propyl, butyl, and isomers thereof, such as isopropyl, isobutyl, tert-butyl, and the like. Alkenyl is for example: propenyl-(1), allyl, butenyl-(l), butenyl-(2) or butenyl-(3). Cycloalkyl is, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. The present invention hence relates to the free organic molecules of the formula I, and to addition salts, quaternary azolium salts and metal complexes. N^ jty z 22 JAN W86 202629 -2- The free molecules are preferred. Examples of salt-forming acids are inorganic acids: hydrohalic acid, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, as well as sulfuric acid, phosphoric acid, phosphorous acid or nitric acid; and organic acids, such as acetic acid, trifluoro-acetic acid, trichloroacetic acid, 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, methane-sulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic 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 ligands. 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 distinguished by very valuable microbicidal properties. They can be used in agriculture or in related fields in a preventive and 202629 -3- 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: for R-^ : 2,4-dichlorophenyl, 2-chloro-4-bromophenyl, 4-chlorophenyl, 4-fluorophenyl; for R2 : methyl, iso-C^H^ or sec-C^Hg; for : C^-C^-alkyl, allyl, proparyl, benzyl, 2,6- Individual compounds preferred in particular are for example: 1-(IH-1,2,4-triazol-l-yl)-2-benzyloxy-2-(2,4-dichlorophenyl)-pentane, 1-(IH-1,2,4-triazol-l-yl)-2-methoxy-2-(2,4-chlorophenyl)-pentane, 1-(IH-1,2,4-triazol-l-yl)-2-methoxy-2-(4-fluorophenyl)-2-cyclohexy1-ethane, 1-(IH-1,2,4-triazol-l-yl)-2-n-propoxy-2-(2,4-dichlorophenyl)- non +- an o phenyl)-pentane, and 1-(IH-1,2,4-triazol-l-yl)-2-(p-chlorobenzyloxy)-2-(2 ,4-dichlorophenyl)-propane. The compounds of the formula I can be produced according to the invention by reacting a compound of the formula II dichlorobenzyl, 4-chlorobenzyl, or 2,4-dichlorobenzyl. A Ri * CH0R. 1 i 2 4 (II) R, '2 20Z629 -4- with a compound of the formula III Vw (III), wherein the substituents R^, are as defined under the formula I, R^ is the IH-1,2,4-triazol-l-yl group, A and W are each -OH, -0M 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 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. 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]; sulfonyloxy groups, preferably -0S02~R^; acyloxy groups, preferably -OCO-R,.; and isourea groups, preferably -0-C=NR^, wherein R.., R,. , o Ob NHR? and Rj independently of one another are each C^-C^-alkyl or C-^-C^-haloalkyl, or phenyl which is unsubstituted or substituted by halogen, methyl, nitro, trifluoromethyl and/or methoxy. 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 W 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 atropic 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 productic in the phase-transfer process. 22 JAM 1986 -5- 202625 Alcohols of the formula II (A=0H) are for the most part known from the literature, or they can be produced by methods analogous to those described therein. The compounds of the formula I contain, in the position adjacent to the oxygen function, an asymmetric centre (*) 0R3 Rj }* CH2R4 (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 5 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 10 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 15 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 or on parts of 20 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 I 25 are effective against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (for example Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (for example the species: Hemileia, Rhizoctonia and Puccinia); in particular they 30 are effective against the Ascomycetes class (for example: Venturia, Podosphaera, Erysiphe, Monilinia and Uncinula). Furthermore, the compounds of the formula I have a systemic action. They can be used also as dressing 202 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 soilc 5 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. 10 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); 15 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); 20 Cucurbitacea: (pumpkins, cucumbers and melons); fibre plants: (cotton, flax, hemp and jute); citrus fruits: (orangesj lemons, grapefruit and mandarins); varieties of vegetables: (spinach, lettuce, asparagus, varieties of cabbage, carrots, onions, tomatoes, potatoes and paprika); 25 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 30 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, simul- 2026 2 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 5 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 10 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 15 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 example into the form 20 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, 25 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 ar.e in general between 10 g and 5 kg of active substance (AS) per hectare, preferably between 100 g and 30 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 2026 2 -x? 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 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, 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 of the formula I to be formulated, nonionic, cationic and/or anionic tensides 202629 - 10 - 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: 5 "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 agrochem'ical preparations contain as a rule 0.1 to 10 99%, particularly 0.1 to 9570, 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 15 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 20 and 'parts' relate to weight, RT = room temperature and absolute = anhydrous, Example I is included to illustrate the process of production. 2026 2 - >5 - Production Examples Example 1: Production of NaH/CH3J II V ii ii ^ / ii 1-(IH-1,2,4-Triazol-l-yl)-2-phenyl-2-(2,4-dichlorophenyl)-5 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 ml of DMF are subsequently added. There is then added 10 dropwise, with stirring, a solution of 12.5 g (0.037 mol) of 1-(IH-1j 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 tempera-15 ture 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, 20 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 g of colourless crystals, m.p. 128-131°C. I§ 202^2 Example 2: Production of NaH/BrCH0CcHr Z O D (KJ) 1-(IH-1,2,4-Triazol-l-yl)-2-benzyloxy-2-(2,4-dichloro phenyl) -pentane 5 To a suspension of 2.4 g of 55% sodium hydride in 100 ml of absolute DMF (adhering mineral oil is washed away beforehand with hexane) is added dropwise, in a nitrogen atmosphere, a solution of 15 g of 1-(1H-1,2,4-triazol-l-yl)-2-(2,4-dichlorophenyl)-pentan-2-ol in 40 ml 10 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 15 RT for 12. 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 concen-20 trated by evaporation. The residue is purified by column-chromatography (silica gel/dichloromethane). The first fraction yields 15 g of a yellowish oil. Analysis: calculated: C = 61.55% H = 5.45% N = 10.77% Cl = 18.17% The following Table contains the aforementioned compounds, and also further compounds which can be similarly produced by one of the processes described in the foregoing. 25 found : C = 61.6% H = 5.7% N = 10.5% Cl = 18.0%. 202629 - 13 - The following Table contains the aforementioned compounds, and also further compounds which can he similarly produced by one of the processes described in the foregoing. Table 1: Compounds of the formula Compound No. RI R2 R3 X Physical ! const. ( C) 1 C6H4C1(4) cyclohexyl ais N m.p.118-119 2 c6n5ci2(2.4) C3H7.n C,,2-C6,,S N oil 5 C6H4C1C4) cyclohexyl a,2-C6HS H ii. p. 116-118 4 C6HjCI2(2.4) SV" a,3 S b.p.170-175/ 0.04 mbar 5 Wf4> cyclohexyl a,3 N m.p.100-101 6 W(4) cyclohexyl a,2-C6»5 N B.p. 74-75 7 C6H3C12C.4) cyclohexyl C2Hs N 8 WV2.-0 cjh,-n CH2CH=CH2 N oil 9 C6H3C12(2'4) C^-i C"3 N b.p.158-162/ 0.03 mbar 10 C6H3C12(2,4) a,3 CH2-Cfi«ai2 N n.p. 68-70 11 C6i,3CI2(2.4) ai5 a!2-Wi(4) N 12 C6ll3Cl(2)Br(4) <*3 ch3 N oil 13 :6H4C1(4) a,3 N b.p.245-250/ 0.05 mbar '22 JAN»86 202629 - 14 - Compound No. 14 15 16 17 IS 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 C6I!3C12(2,4) C6II.C1,(2,4) C6H3C12(2,4) C6II4C1(4) C6H4C1(4) C6H3C12(2,4) C6H3Cl2(2.4) C6H3C|2C2.4) C6H3C12C2,4) C6H4C1(4) C6H3C12C2,4) C6H3C12C2.4) C6H3C12(2,4) C6H3C12(2,4) C6H4F(4) C6H4C1(4) Wl2{2'4) C6H5C1(2)F(4) C6HSC1C2)F{4) C6HsCl(2)Br(4) C4Hp-n. C4H9-n fc4»9-n fc4Hg-n C4»9-n a,3 ch3 ai$ ai3 cyclopentyl cyclopentyl cyclopentyl cyclopentyl cyclopentyl cyclobutyl C3«7-n cyclohexyl C«s CHS ch, ai3 ai2"C6nS CH2"C6H4C1(4) C1I, ch,-c,il 2 o o ai, ch2-c6h5 ai2-c6«4cK4) C4"9"n CH, CH, a,2-C6"5 CH,C6H3C12C2,4^ W ch, m2'6llS ch, ch, ch2c6h5 "Ws n n n Physical _ron£s.tJ__Cj_- b.p.240-250; 0.04 mbar oil b.p.185-195/ 0.01 mbar oil oil oil oil oil oil oil b.p.170-176/ 0.02 nbar b.p.200-210? 0.1 abar oil .p.250/0.04 mbar b.p.219/0.02 mbar |Z22 JANI986 202629 - 15 - Compound Nrt. R1 R2 R3 X Physica^ const.( C] 1 1 34 35 C6,1SC12(2.4) C6II3C12(2.4) ai3 aij c3ii7-n ch,-c-ch, 2 i - a,3 N N n.p.62-64 b.p.165-175$ 0.02 mbar 36 C6,.3GI2(2,4) a,3 CH2CH"C!ICH3 N b.p.190-200? 0.02 nbar 37 38 C6H3C1,(2,4) C6»«3C12(2,4) C_H„-:» 5 / C3"7-n ch.-c-ch, 2 J 2 ai3 ai,awaicn. 2 o N N b.p.170-180/ 0.02 nbar b.p.180-190? 0.02 nbar 39 40 C6,I3C12(2.4) c6n3ci2(2.4) C3Vn c3H7-n C3H7-n C4»9-n N N oil b.p.189-195? 0.02 mbar 41 C6H3C1(2)F(4) c3h7-n CII2-CII-CII2 N b.p "J10/0.04 mbar 42 C6!I3C1C2)F(4) c3h7-n c3h7-n N b.p.208/0.04 mbar 43 C6II3C1(2)F(4) c3h?-n □!3 N b.p.190/0.04 mbar 44 C,H.C1(2)F(4) o ^ c2hs a,3 N b.p.148-153/ 0.02 mbar 45 C6H3C1(2)F(4) C2H5 CH2-CH»a«2 S b.p.180-186/ O.OS nbar 46 C6H3C12C2.4) c2h5 a,3 N b.p.170-175/ 0.04 nbar 47 C6H3C12(2.4) C2H5 C3f,7"n N b.p.192-198/ 0.03 mbar 48 C6H4F(4) C2H5 C4H9-" N oil 202629 - 16 - Compound No- *1 R2 R3 X Physical j const.[°CJ | 49 W(J) C2!,5 -CH^CH-CHCHj X oi 1 50 C6H4F(4) CjM7-n C.H,-n J 7 N oil 51 C6H4F(4) CHj CH2"C6H4C1(4) N oil 52 C6H4F(4) C2H5 CH3 1 N viscous oil Formulation examples for active substances of the formula I (% = per cent by weight) (MG = molecular weight) Emulsion concentrates/wettable powder s 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% - - tributylphenoyl-polyethylene glycol 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.(*) Solutions a) b) c) d) active substance from Table 1 80% 10% 5% 95% ethylene glycol-monomethyl ether 20% - - - polyethylene glycol MG 400 - 70% - - N-methyl-2-pyrrolidone - 20% epoxidised coconut oil - - 1% 5% ligroin (boiling limits 160-190°C)- - 94% * Wettable powders are produced when xylene is replaced with silicic acid and/or kaolin. The solutions are suitable for application in of very small drops. 2026 n* Granulates a) b) active substance from Table 1 5% 10% kaolin 94% -highly dispersed silicic acid 1% 5 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) 10 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 15 together of the carriers with the active substance. Biological Examples Example 2.1 Action against Puccinia graminis on wheat a) Residual protective action Six days after being sown, wheat plants were sprayed 20 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 25 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 202629 '<6 - yt - 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 uredospore suspension of the 5 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. 10 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% by, inter alia, the compounds Nos . 1-6, 8-14, 17, 19-22, 28, 29, 31-33, 15 34-43 and 50-52. Example 2.2: Action against Cercospora arachidicola on groundnut plants Residual protective action 20 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 25 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. Groundnut plants 10-15 cm in height were sprayed with Compared with untreated, but infested control plants 30 (number and size of spots = 100%), groundnut had been treated with active substances from ' 202629 - & - exhibited a greatly reduced level of Cercospora infection. Thus the compounds Nos. 1, 2, 4-6, 8-10, 12-14, 17, 18, 19-22, 31, 33 and 34-52 prevented the . occurrence of spots in the above test virtually completely 5 (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 10 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 22°C, and the extent of fungus infection was assessed after 10 days. 15 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 20 the spray liquor did not come into contact with the parts of the plants 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 22°Cj and an assessment of the extent of fungus infection 25 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 l00?o. Among other compounds from the Table I, compounds Nos. 30 1-4, 16, 17,.18, 19-22, 24/ 28, 29, 31-33 and"34-52 reduced 0^\\ funcrus infection on barley to 0 to 5%. The compounds /A A //; Nos. 1, 2, 4-6, 8-10, 12t14, 17, 19-21, 29, 22, 33, 34-43, t . - -. flrtOA '! 2 2 J' -\ * V- </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 202629 and 50 were particularly effective (no infection). Example 2.4: Residual protective action against Venturia inaequalis on apple shoots 5 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 10 then incubated for 5 days with 90-100%, relative humidity, 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 ext^Qt of 100%. Compounds Nos. i, 2, 4,.5, 12-14, 17, 19-21, 28, 29, 31, 33, 34-43 and.50 reduced infection to less than 10%. Where treatment was carried out with the active substances Nos. 2>, .4, 5, 12, 14 and 38-43 no infection at all occurred. 20 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 the active substance (0.02% of active substance), to the 25 damaged areas on the apples. The treated fruit was then inoculated with a spore suspension of Botrytis cinerea, 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 30 of fungicidal activity. After treatment with the compounds Nos. 2, 4, 6, 8, 10, 12, 14, 17, 19, 21, 28 and 31 there were no, or virtually no, areas of decay to be observed (0-5% infection). - 21 - ZQZ629 WHAT WE CLAIM IS:

1. A compound of the general formula I,

0R3 N=«

I /

R, A CHt— N

1 I V

R2 • =N

wherein R.|^ is 2,4-dichlorophenyl, 2-chloro-4-fluoro-

phenyl, 2-fluoro-4-chlorophenyl, 2-chloro-4-bromophenyl,

4-chlorophenyl or 4-fluorophenyl; R„ is C-,-C,--cyclo-

Zoo alkyl or Cj-Cj-alkyl; R^ is benzyl, chlorobenzyl, di-chlorobenzyl, C^-C^-alkyl or C^-C^-alkenyl; and the acid addition salts, quaternary azolium salts and metal complexes thereof.

2. A compound of the formula I according to Claim 1,

wherein is C-^-C^-alkyl, and R^ and R2 are as defined in claim 1.

3. A compound of the formula I according to Claim 1,

wherein R2 is methyl, isopropyl or sec-butyl, and R1 and R^ are as defined in claim 1.

4. 1-(IH-1,2,4-triazol-l-yl)-2-methoxy-2-(2,4-dichlorophenyl) -butane.

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

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

7. 1-(IH-1,2,4-triazol-l-yl)-2-methoxy-2-(2,4-dichlorophenyl) -pentane.

8. 1-(IH-1,2,4-triazol-l-yl)-2-methoxy-2-(2-chloro-4-fluorophenyl)-pentane.

9 . 1-(IH-1,2,4-triazol-l-yl)-2-methoxy-2-(2,4-dichlorophenyl)-3-methylbutane.

10. A process for producing a compound of the formula I as defined in Claim 1, which process comprises reacting a

202639

- 22 -

compound of the formula II

R'

CH0R. 2 4

with a compound of the formula III

(II)

r3-w

(III) ,

N r o

wherein the substituents R^, R2 and R3 are as defined in Claim 1 and R^ is the IH-1,2,4-triazol-l-yl group, A and W are each -OH, -OM or one of the customary removable groups selected from halogen, -0S02R,., -OCO-R^, -OCO R,- and -0-C=NR6, wherein R NHR_

5,

Rg and R7 independently of one another

4F EB1986

are each Cj-C^-alkyl or C^-C3~haloalkyl, or phenyl which is unsubstituted or substituted by halogen, methyl, nitro, trifluoromethyl and/or methoxy.

11. 1-(IH-1,2,4-triazol-l-yl)-2-crotyloxy-2-(2,4-dichloro-phenyl)-pentane.

12. 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 I as defined in Claim 1.

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

15. A composition according to Claim 12, which contains, as active ingredient, the compound 1-(IH-1,2,4-triazol-l-yl) -2-methoxy-2-(2,4-dichlorophenyl)-pentane.

16. A composition according to Claim 12, which contains, as active ingredient, the compound 1-(1H-1,2,4-triazol-l-yl) -2-allyloxy-2- (2,4-dichlorophenyl)-butane.

17. A method of controlling or preventing attack by

202629

yk\\

- 23

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 I according to Claim 1.

18. A method according to Claim 17, which method comprises applying the compound 1-(IH-1,2,4-triazol-l-yl)-2-methoxy-2-(2,4-dichlorophenyl)-butane.

19. A method according to Claim 17, which method comprises applying the compound 1-(IH-1,2,4-triazol-l-yl)-2-n-propoxy-2-(2,4-dichlorophenyl)-butane.

20. A method according to claim 17, which method comprises applying the compound 1-(IH-1,2,4-triazol-l-yl)-2-methoxy-2-(2,4-dichlorophenyl)-pentane.

21. A method according to Claim 17, which method comprises applying the compound 1-(IH-1,2,4-triazol-l-yl)-2-allyloxy-2-(2,4-dichlorophenyl)-butane.

CIBA-GEIGY AG By its attorneys

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