NZ208847A - Fungicidal compositions containing diazole and triazole derivatives - Google Patents

Abstract

1. Use of substituted diazolyalkyl carbinols of the formula see diagramm : EP0131845,P16,F1 in which A represents a nitrogen atom or the CH group ; B represents a nitrogen atom or the CH group ; X represents hydrogen and straight-chain or branched alkyl with 1 to 4 carbon atoms ; Y represents straight-chain or branched alkyl with 1 to 4 carbon atoms ; and, if X represents hydrogen, also represents allyl, methylallyl, propargyl, methylpropargyl or benzyl which is optionally substituted in the phenyl part by flourine, chlorine, bromine, methyl, isopropyl, tert.-butyl, methoxy, methylthio, triflouoromethyl, trifluoromethoxy, triflouromethylthio, nitro and cyano ; R represents phenyl which is mono- or disubstituted by identical or different substituents from the group comprising methylthio, triflouromethoxy, trifluoromethylthio, nitro, cyano, hydroxyl, hydroxycarbonyl, methoxycarbonyl, ethoxycarbonyl, hydroximinomethyl, 1-hydroximinoethyl, methoximinomethyl and 1-methoximinoethyl, and also comprising phenyl, phenoxy, benzyl or benzyloxy, each of which is optionally substituted by flourine, chlorine or methyl, and R furthermore represents the grouping see diagramm : EP0131845,P16,F2 wherein Alk**1 represents methyl or ethyl, Alak**2 represents methyl or ethyl ; Alk**1 and Alk**2 , together with the carbon atom to which they are bonded, represent cyclobutyl, cyclopentyl or cyclohexyl ; and R**1 represents methyl, ethyl, n-propyl, i-propyl, n-butyl, neopentyl, and phenyl, benzyl, phenethyl, phenoxy, phenylthio, pnenoxymethyl, phenoxyethyl, phenylthiomethyl, phenylthioethyl, benzyloxy or benzylthio, it being possible for each of the eleven aforementioned radicals to be substituted in the phenyl part by fluorine, chlorine, bromine, methyl, isopropyl, tert.-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, nitro, cyano, hydroxyl, hydroxycarbonyl, hydroximinomethyl, 1-hydroximinoethyl, methoximinomethyl or 1-methoximinoethyl, and by phenyl, phenoxy, benzyl and/or benzyloxy, each of which is optionally substituted by fluorine, chlorine or methyl, and acid addition salts and metal salt complexes thereof for combating fungi in plant protection.

Description

New Zealand Paient Spedficaiion for Paient Number £08847 20884 Priority Date(s): '.T!. ". & y Complete Specification Filed: Class: [faj.VAZ/f.ZJSZ* Publication Date: .... ^ .991 J?8$ J2 &<£ P.O. Journal, No: • '• • ■ AMENDED under Section 1.^ of the Patents' Act j 953 frirfm l.fe. ck K R NEW ZEALAND ASS COMMISSIONER OF PATENTS Patents Act 1953 COMPLETE SPECIFICATION M 7 PATENT OFFlpjL t0 JUL 1984 received.

"FUNGICIDAL AGENTS AND THEIR PREPARATION AND USE" We, BAYER AKTIENGESELLSCHAFT, a Company registered under the laws of the Federal Republic of Germany, of Leverkusen, Germany do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement : - - 1 - (followed by 1A) - 1A- 208847 The present Invention relates to the use of substituted dlazolylalkyl-carb1nols as fungicidal agents.

It has already been disclosed that certain diazolyl derivatives, such as, for example, 1,3-di-(1,2,4-triazol-5 1-yI)-2-(2-chlorophenyD- or -(3-chlorophenyl)- or -<4-chlorophenyD- or -phenyl-2-propano I, have fungicidal properties (compare New Zealand Patent Specification No 191,136. However, the action of these compounds is not always completely satisfactory, especially when low 10 amounts and concentrations are applied.

It has been found that the substituted diazolyl-aIky l-carbino Is of the general formula i ? ,-B R - C C-N Y i \=- N (I) N ii in which A represents a nitrogen atom or the CH group, B represents a nitrogen atom or the CH group, X represents hydrogen or alkyl, Y represents alkyl, or, if X represents hydrogen, also alkenyl, alkinyl or optionally substituted benzyl, and R represents optionally substituted phenyl or the grouping Alk1 i wherein Alk^ represents alkyl and ALk^ represents alkyl, or Alk^ and Alk^ together represent a cycboali- ■ t"' phatic ring, and represents alkyl, aLkenyl or in each case op-tionally substituted phenyl, phenylalkyl, phenoxy, phenylthio, phenoxyaIkyI, pheny11hioaIky I , ben-zyloxy or benzylthio, and acid addition salts and metal salt complexes thereof, have good fungicidal properties.

Where relevant, the compounds of the formula (I) possess two asymmetric carbon atoms; they can then exist in the two geometric isomer forms.

Surprisingly, the substituted diazolyI alky I-car- binols of the formula (I) to be used according to the invention have a better fungicidal activity than the diazolyl derivatives which are already known from the prior art, such as, for example, 1,3-di-(1,2,4-triazol-1-yl)-2-(2-15 ch lorophenyI)- or -(3-chlorophenyl)- or -(4-ch loropheny I)-or -pheny l-2-propanoI, and which are closely related compounds structurally and from the point of view of their action. The use, according to the invention, of the substances of the formula (I) thus represents an enrichment 20 of the art.

Formula (I) provides a general definition of the substituted diazolylalky I-carbino Is to be used according to the invention. Preferably, in this formula A represents a nitrogen atom or the CH group; 25 B represents a nitrogen atom or the CH group; X represents hydrogen or straight-chain or branched alkyl with 1 to 6 carbon atoms; Y represents straight-chain or branched alkyl with 1 to 6 carbon atoms; or, if X represents hyd-30 rogen, also straight-chain or branched alkenyl or alkinyl with in each case 3 to 6 carbon atoms, or benzyl which is optionally mono-, di- or tri-sub-stituted in the phenyl part by identical or different substituents, substituents which may be 35 mentioned being: halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 to 4 carbon atoms, halogenoalkyI, halogeno-alkoxy and ha logenoa I ky Ithio with in each case 1 or 2 carbon atoms and 1 to 5 identicaL or different haLogen atoms, such as, preferably, fluo-5 rine and chlorine atoms, nitro and cyano; and R represents phenyl which is optionally mono-, di-or tri-substituted by identical or different sub-stituents, preferred substituents which may be mentioned being: halogen, alkyl with 1 to 4 car-10 bon atoms, alkoxy and alkylthio with in each case 1 to 4 carbon atoms, haLogenoa lkyI, ha Iogenoa I koxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as, preferably, fluorine and 15 chlorine atoms, nitro, cyano, hydroxyl, hydroxy- carbonyl, aLkoxycarbonyL with 1 to 4 carbon atoms in the alkyl part, hydroximinoalkyl with 1 to 4 carbon atoms, alkoximinoalkyl with 1 to 4 carbon atoms in each alkyl part, and phenyl, phenoxy, 20 benzyl and benzyloxy, each of which is optionally substituted by halogen and/or alkyl with 1 or 2 carbon atoms; or R furthermore preferably represents the grouping AI k 1 R^-C- Alk2 ' wherei n A I k^ represents straight-chain or branched alkyl with 1 to 4 carbon atoms; and Alk^ represents straight-chain or branched alkyl with 1 to 4 carbon atoms; or 30 Alk^ and Alk^, together with the carbon atom to which they are bonded, represent a 3-membered to 7-membered cycLoaLiphatic ring; and r1 represents straight-chain or branched alkyl with 1 to 6 carbon atoms, alkenyl with 2 to 4 car- bon atoms, or phenyl, phenylalkyl with 1 to 4 cat— bon atoms in the alkyl part, phenoxy, phenylthio, phenoxyalkyl with 1 to 4 carbon atoms in the alkyl part, phenylthioalkyl with 1 to 4 carbon atoms 5 in the alkyl part, benzyloxy or benzylthio, each of which is optionally mono-, di or tri-substi-tuted in the phenyl part by identical or different substituents, preferred possible substituents being the phenyl substituents already mentioned 10 for R.

Particularly preferred compounds of the formula (I) are those in which A represents a nitrogen atom or the CH group; 15 B represents a nitrogen atom or the CH group; X represents hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms; Y represents straight-chain or branched alkyl with 1 to 4 carbon atoms; or, if X represents 20 hydrogen, also allyl, methyI a 11 y I, propargyl, methy Ipropargy I, or benzyl which is optionally mono-or di-substituted in the phenyl part by identical or different substituents, substituents which may be mentioned being: fluorine, chlorine, bromine, 25 methyl, isopropyl, tert.-butyl, methoxy, methyl- thio, trifluoromethyl, trif luoromethoxy, trifluoromethylthio, nitro and cyano; and R represents phenyl which is optionally mono- or di-substituted by identical or different substi-30 tuents, substituents which may be mentioned being: fluorine, chlorine, bromine, methyl, isopropyl, tert.-butyl, methoxy, methylthio, trif luoromethy I, trif I uoromethoxy, trifluoromethylthio, nitro, cyano, hydroxyl, hydroxycarbonyI, methoxycarbony I, 35 ethoxycarbonyl, hydroximinomethyl, 1-hydroximino- ethyl, methoximinomethyl, 1-methoximinoethyI and phenyl, phenoxy, benzyl and benzyloxy, each of which is optionally substituted by fluorine, chlorine or methyl; or R furthermore represents the grouping A I k 1 R1-!:- Alk 2 whe rei n Alk^ represents methyl or ethyl; and Alk^ represents methyl or ethyl; or Alk^ and Alk^, together with the carbon atom 10 to which they are bonded, represent cyclobutyl, cyclopentyl or cyctohexyl; and r1 represents methyl, ethyl, n-propyl, i-propyl, n-butyl, neopentyl or phenyl, benzyl, phenethyl, phenoxy, phenylthio, phenoxymethyI, phenoxyethy I, 15 phenyIthiomethyl, phenyIthioethyI, benzyloxy or benzylthio, each of which is optionally mono- or di-substituted in the phenyl part by identical or different substituents, possible substituents being the substituents on phenyl which have already 20 been mentioned for R.

Addition products of acids and those substituted diazo ly I alkyI-carbino Is of the formula (I) in which the substituents A, B, X, Y and R have the meanings which have already been mentioned as preferred for these substi-25 tuents are also preferred compounds according to the invention.

Preferred acids which can be added on include hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, 30 and furthermore phosphoric acid, nitric acid, monofunc-tional and bifunctional carboxylic acids and hydroxycarb-oxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and 6 <308847 sulphonic acids, such as p-toluenesulphonic add and 1,5-naphthalenedlsuIphonlc acid.

II to IV and of sub-groups I and II and IV to VIII and 5 those substituted diazolylalkyl-carbinols of the formula (I) 1n which the substituents A, B, X, Y and R have the meanings which have already been mentioned as preferred for these substituents are also preferred compounds according to the Invention.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred here. Possible anions of these salts are those which are derived from acids leading to physiologically acceptable addition products. In this connection, particularly preferred acids 15 of this type are the hydrogenha 11de acids, such as, for example, hydrochloric acid and hydrobromic acid, nitric acid and sulphuric acid.

Addition products of salts of metals of main groups The active compounds to be used according to the invention are described in EP 0120126, 2 and are obtained by reacting azolyl-oxiranes of the formula X I CH2— 0 Y 'B^l J ' (II) in which B, R, X and Y have the abovementioned meaning, with azoles of the formula (III) in which A has the abovement1oned meaning. i 208647 in the presence of an Inert organic solvent, such as, for example, alcohols, and, if appropriate, in the presence of a base, such as, for example, alkali metal alcoholates, at temperatures between 60 and 150°C. 5 If appropriate, an acid or a metal salt can then be added onto the compound of the formula (I) thus obtained.

The azo lyl-oxiranes of the formula (II) are described in EP 0120126, and can be obtained by reacting azolyl-ketones of the formula I ,B=j r co c - <1V) in which B, R, X and Y have the abovementioned meaning, either o< ) with dimethyloxosulphonium methylide of the formula & (V) <ch3)2soch2 in the presence of a diluent, such as, for example, di-20 methyIsuIphoxide, at temperatures between 20°C and 80°C in a manner which is known per se (in this context, compare the statements in J.Am. Chem.Soc. 87, 1363-1364 (1965), or JB) with trimethyIsuIphonium methyl-sulphate of the 25 formula C(CH3)3S+D ch3so4" (VI) in the presence of an inert organic solvent, such as aceto-nitrile, and in the presence of a base, such as, for example, sodium methylate, at temperatures between o°C and 30 60°C, preferably at room temperature, in a manner which is known per se (compare also the statements in Hetero-cycles 8, 397 (1977)). 208W7 If appropriate, the oxiranes of the formula (II) thus obtained can be further reacted directly, without being isolated.

The azolyl-ketones of the formula (IV) are known (compare, for example, GB 1,464,224, GB 1,533,706, NZ 201,828 and can be obtained by the processes mentioned therein, for example, by reacting halogenoketones of the formula X I R - CO - C - Hal * ' (VII) in which R, X and Y have the abovementioned meaning and Hal represents chlorine or bromine with azoles of the formula o— (VIII) ' i H -N^ I in which B has the abovementioned meaning, in the customary manner in the presence of an inert organic solvent, such as, for example, acetone, and in the presence of an acid-binding agent, such as, for example, 25 potassium carbonate, at temperatures between 40 and 100°C, The halogenoketones of the formula (VIII) can be obtained in a generally known manner, by reacting corresponding ketones of the formula X R - CO - C - H (IX> I Y in which R, X and Y have the abovementioned meaning, 2 088 47 with chlorine or bromine in the presence of an inert organic solvent, such as, for example, chlorinated hydrocarbons, at room temperature; or with customary chlorinating agents, such as, for example, sulphuryl chloride, at 5 temperatures between 20 and 60°C.

The compounds of the formula (I) according to the invention can also be obtained by reacting diazolyl-ke-tones of the formula — A * , B ~ | VN - CH2 - CO - C - N j (X) N —^ Vr N i n wh i ch A, B, X and Y have the abovementioned meaning, with a Grignard reagent of the formula R - Hg - Hal' (XI) i n wh i ch R has the abovementioned meaning and Hal' represents halogen, in the customary manner under the conditions of a Grignard reaction; or by reacting dihalogenoalkanols of the formula OH X I l R - C - C - Hal CH2 Y (XII) Hal in which R, Hal, X and Y have the abovementioned meaning, with azoles of the formula (III) in the customary manner.

The acid addition salts of the compounds of the 25 formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be isolated in a known manner, for example by f i L — 30 tration, and if appropriate purified by washing with an inert organic solvent. 2088 47 The metal salt -complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding the solu-5 tion to the compound of the formula (I). The metal salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystalli-sat ion.

The active compounds to be used according to the 10 invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired microorganisms. The active compounds are suitable for use as plant protection agents.

Fungicidal agents in plant protection are employed 15 for combating Plasmodiophoromycetes, Oomycetes, Chytridio-mycetes. Zygomycetes, Ascomycetes, Basidiomycetes and Deu-t eromycet es.

The good toleration, by plants, of the active compounds, at the concentrations required for combating plant 20 diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.

As plant protection agents, the active compounds according to the invention can be used with particularly 25 good success for combating cereal diseases, such as Ery-siphe graminis, Cochliobolus sativus, rust and Pyrenophora teres; Uromyces species, such as against the bean rust causative organism (Uromyces appendicu latus); Venturia species, such as against the apple scab causative organism 30 (Venturia inaequalis); and rice diseases, such as Pyri-cularia oryzae and Pellicularia sasakii. The substances according to the invention also exhibit a broad and good fungicidal in vitro action spectrum.

It should be emphasised that the substances accor-35 ding to the invention not only display a protective action but in some cases are also systemic. Thus, it is possible 208847 to protect plants from fungal attack if the active compounds are fed to the above-ground parts of the plant via the soil and the root or via the seed.

The active compounds can be converted to the cus-5 tomary formulations, such as solutions, emulsions, wet-table powders, suspensions, powders, dusting agents, foams pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed treatment powders, natural and synthetic materials impregnated with active compound, 10 very fine capsules in polymeric substances and in coating compositions for seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist formulations.

These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or disper-20 sing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated 25 aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as buta-nol or glycol as well as their ethers and esters, ketones, 30 such as acetone, methyl ethyl ketone, methyl isobutyl ketone or eyelohexanone, strong polar solvents, such as di-methylformamide and dimethylsulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under 35 normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitro 208847 H # # gen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, mont-morillonite or diatomaceous earth, and ground synthetic 5 minerals, such as highly-dispersed silicic acid, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and or-10 ganic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethy-15 lene-fatty alcohol ethers, for example alkylaryl poly-glycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydro lysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcel lulose. 20 Adhesives such as carboxymethyIce11ulose and natu ral and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

It is possible to use colorants such as inorganic 25 pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs and azo metal phtha locyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. 30 The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in the formulations or in the various use 35 forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.

The active compounds can be used as such or in the form of their formulations or the use forms prepared there-5 from by further dilution, such as ready-to-use solutions, emu Is ions, suspensions, powders, pastes and granules.

They are used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, injecting, forming a slurry, brushing on, dusting, 10 scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 15 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concen-20 trations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight are required at the place of action. Preparation examples; Example 1 oh ch3 ch2 ch3 n [j 3.6 g (0.052 mol) of 1,2,4-triazole are added to a solution of 0.11 g (0.047 mol) of sodium in 30 ml of n-propanol at room temperature, with stirring. The mixture is heated to reflux temperature and a solution of 2-(4-chlorophenyl)-2-C2-(1,2,4-triazol-1-yl)-prop-2-ylI]-30 oxirane in 20 ml of n-propanol is added. The reaction mixture is heated under reflux for 15 hours and then 14 cooled and poured onto water. The mixture is extracted with methylene chloride and the organic phase is dried over sodium sulphate and concentrated. The residue is purified by column chromatography (silica gel; chloroform: 5 methanol = 9:1). 3.7 g (24.2% of theory) of 2-(4-chloro-phenyl)-1,3-di-(1,2,4-triazol-1-yl)-3-methyl-2-butanol of melting point 114°C are obtained.

Preparation of the starting substance are dissolved in 9.6 g (0.118 mol) of dimethyl sulphate under a nitrogen atmosphere. 5.2 g (0.044 mol) of potassium tert,-butylate are added at room temperature and the mixture is subsequently stirred at room temperature for 15 6 hours. A solution of 9.9 g (0.0397 mol) of 4-chloro-phenyl 2-(1,2,4-triazol-1-yl)-prop-2-yl ketone in 16 ml of tetrahydrofuran is then added dropwise at room temperature. The reaction mixture is subsequently stirred at room temperature for 15 hours and under reflux for 4 hours, 20 cooled and filtered. The filtrate is concentrated in vacuo, the residue is poured onto water and the mixture is extracted with methylene chloride. The organic phase is dried over sodium sulphate and concentrated in vacuo. .4 g (100% of theory) of 2-(4-ch lorophenyI)-2-C2-(1,2,4- 9.6 g (0.044 mol) of trimethylsulphonium iodide triazo 1-1-yI)-prop-2-yID-oxirane of refractive index N^0 1.5388 are obtained.

(IVa-I) 80 g (0.31 mol) of 2-bromo-prop-2-yI 4-chloro- 208847 phenyl ketone, 26.9 g (0.39 mol) of 1,2,4-triazo le and 53.8 g (0.39 mol) of potassium carbonate are heated under reflux in 350 ml of acetone for 6 hours. The mixture is allowed to cool and is filtered and the filtrate is 5 concentrated in vacuo. The residue is taken up in methylene chloride and the mixture is washed with water, dried over sodium sulphate and concentrated in vacuo. The residue is recrystat lised from diisopropyl ether. 19.9 g (25.7% of theory) of 4-chlorophenyl 2-(1,2,4-triazol-10 1-yl)-prop-2-yl ketone of melting point 111°C are obtained. ch3 CL~<^)- CO - C - Br CH3 65.5 g (0.36 mol) of 4-chlorophenyl isopropyl ketone are dissolved in 200 ml of chloroform, and 1 ml of hydrogen bromide/glacial acetic acid is added. 57.5 g 15 (0.36 mol) of bromine are then slowly added dropwise at 30°C and the mixture is subsequently stirred at room temperature for 30 minutes. The mixture is concentrated in vacuo to give 86.6 g (92% of theory) of crude 2-bromo-prop-2-yl 4-chlorophenyl ketone as an oil, which can be 20 further reacted directly.

Example 2 ch3 oh ch3 — f — c — ch3 ch2 iT'-N N U 3.6 g (0.052 mol) of 1,2,4-triazoIe are added to a solution of 0.1 g (0.043 mol) of sodium in 30 ml of 25 n-propanol at room temperature, while stirring. a solution of 13.2 g (0.043 mol) of 2-(4-chlorophenyl-tert.-butyI)-2-C1-(1,2,4-triazo 1-1-yI)-ethy13-oxirane in 20 ml of n-propanol is then added. The reaction mixture is 208847 16 heated under reflux for 20 hours and is then cooled and poured onto 300 ml of water. The mixture is extracted with methylene chloride and the methylene chloride phase is washed with water, dried over sodium sulphate and concentrated in vacuo. The residue is purified by column chromatography (silica gel; ethyl acetate: ether = 3:1). 4 g (24.8% of theory) of 1-(4-ch lorophenyl)-2,2-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-4-(1,2,4-triazol-1-yl)-3-pentanol of melting point 59°C are obtained.

Preparation of the starting substance A solution of 9.8 g (0.077 mol) of dimethyl sulphate and 5.3 g (0.085 mol) of dimethyl sulphide in 50 ml of acetonitrile is stirred at room temperature for 5 days. 15 A solution of 13 g (0.044 mol) of 4-ch lorophenyl-tert.-butyl 1 — (1,2,4-triazol-1-y l)-ethyl ketone in 20 ml of acetonitrile is then added dropwise at room temperature. 4.8 g (0.088 mol) of sodium methylate are introduced at the same temperature and the mixture is subsequently 20 stirred for 20 hours and then concentrated in vacuo. The residue is stirred overnight with a mixture of 35 ml of ethyl acetate and 25 ml of water. The organic phase is separated off, dried over sodium sulphate and concentrated in vacuo. 13.2 g (98.2% of theory) of 2-(4-chloro-25 phenyl-tert.-butyl)-2-C1-(1,2,4-triazol-1-yl)-ethyl3-oxi-rane of refractive index n^0 1.5431 are obtained.

CI The following compounds of the general formula OH X CH2 Y (I) are obtained in a corresponding manner: 208847 -^ch2-ccch3)2 tX^*C(CH3>2- L-®-c(CH3)2- X Y A B Melting pgjnt ( C) or n^ chj ch3 N N 56 ch J ch3 N N 156 CHj « ch3 N N 202 ch3 ch3 N N 185-90 ch3 ch3 ch N 196 CHj ch3 ch N 90-100 ch 3 ch3 ch N 100-10 H ch3 N N glasslike H ch3 N N 143-145 H ch3 N h 110 H ch3 N h 96-99 h ch3 n n 478 H ch3 N N 36 H ch3 N n 52 (Form a) H ch3 n N 60 (Form B) Forms A and B: The two possible geometric isomers Ex ample No. 18 19 21 22 23 24 ZOf - continued.: A B Melting ( C) or n^ /CL CI / .CI H -C4H9n CL^^" H C2H5 C1'(P)- CH3 CH3 CH3 CH3 CI CH, Va 1 -<g>-CH2-C- H CH, CH.

N N H -CH2-CH=CH2 N N N N N N N N N N N N 126 144 154 110 N N 90 78 138 64-67 208847 Use examples: The compounds given below are used as comparison substances in the use examples which follow: —N 0H N — (a) i vch2-c-ch2-n' i n-si/ i v=n CI — N 0H W — N j ,N —| (b) | n-ch2-c-ch2-n | N=/ I ^=N <8 I Cl — N OH N_ l~\ I /n— (c) | n-ch2-c-ch2-n N-=^ 1 — m 0H w — i —Nv , /N —| (0) i n-ch2-c-ch2-n i | n=-N Cl 208®47 Example A Erysiphe test (barley)/protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol 5 ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concen-10 tration.

To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. 15 hordei.

The plants are placed in a greenhouse at a temperature of about 20°C and a relative atmospheric humidity of about 80X, in order to promote the development of powdery mildew pustules.

Evaluation is carried out 7 days after the inocu lation.

In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 3, 4, 6, 9, 25 10, 11, 12, 13, 15 and 16. ✓ 208847 Table: A Erysiphe test (barIey)/protective/ Active compound Active compound concentration in the spray liquor in % by weight Disease infestation in % of the untreated control — n 0h w — i-nv | /n=r, 6s n-ch2-c-ch2-n . N —/ \=.N 0.0025 100 Cl (A) (known) F"^3"i~\""NV ' (3) °*0025 25,0 N—' I V„ \=-n ch2 ch3 ,rvH ?H!'N=i C>?-rN 1 ch2 ch3 ^Nxn n' (4) 0-0025 50,0 __ oh ch3 /^V1 1 /N I (' >c c—n | | ch2 ch3 rrNi nLJj (6) 0-0025 .0 20884? Table: A (continued) Erysiphe test (barley)/protective/ Active compound Active compound concentration in the spray liquor in X by weight Disease infestation in % of the untreated control oh CH3 w_ CL^W-i-N7 ch? I r*s nM) i CH3 — N (9) 0.0025 50*0 oh ch3 w__ ch2 r^N nI u — N (1 0) 0.0025 .0 oh ch3 I I / (ch3)3c-c—ch-n i ch? I N"=r (12) 0.0025 .0 f. nv Cl /cl oh ch3 •TV- X=/ ' ^=-N ch? rf^ N_U (11) 0*0025 12.5 01 Table: A (continued) Erysiphe test (barley)/protective/ Active compound Active compound concentration in the spray liquor in X by weight Disease infestation in % of the untreated control oh ch3 /T\ 1 17 F\ 7"c~~ch~n (13) 0.0025 12*5 ch? I ALJ? =-n ch3 oh ch3 „ jT\ f I I /N=^ f-c >ch2-c c—ch-n \=i/ £ i I \=N ch3 ch2 f^NxN $ 1? (15) 0.0025 12.5 ch3 oh ch3 /t-\ I I I /nr^ cih' vc c—ch-n \=/ I ch3 ch2 (Form-A) (16) 0.0025 .0 Example B Cochliobolus sativus test (barley) / protective Solvent: 100 parts by weight of dimethyIformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol 5 ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired con-10 centration.

To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are sprayed with a conidia suspension of 15 Cochliobolus sativus. The plants remain in an incubation cabinet for 48 hours at 20°C and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 20°C and a relative atmospheric 20 humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, a clearly superior activity compared with the prior art is shown, for example, by the 25 compounds according to the following preparation examples 6, 9, 10, 11, 13, 15 and 16. 208847 Table B Cochliobolus sativus test (barley)/protective Active compound Active compound concentration in the spray liquor in % by weight Disease infestation in X of the untreated control r=N. oh i n-ch2-c-ch2-n Cl 0.025 100 (b) (known) Cl oh ch3 u \-=/ | | \=.N ch2 chj r]N|N n: (6) 0.025 21.2 oh ch3 .. ch2 ch3 n n I !i i % (9) 0.025 12. 5 oh ch3 m_ I I /n~| c—ch-n ^=-N (10) 0.025 12.5 208847 Table B (continued) Cochliobolus sativus test (barley)/protective Active compound Active compound concentration in the spray liquor in % by weight Disease infestation in % of the untreated control /cl oh ch3 n_ cl-^7— c—ch-n | J.. VrN (11 ) 0.025 21.2 CH? I ') I.

N J oh ch* I I / f \ )"c"~ch~n ch2 N=r, (13) 0.025 21. 2 — N fx * ^=.N ch3 oh ch3 m \ • I I /N=*l f-t_y-ch2-c c—ch-n ch3 ch2 I n (15) 0-025 0.0 •n=" ch3 oh ch3 JT~\ I l I ci-^ y-c c—ch-n ch3 ch2 ff'si (Form a) n (16) 0.025 33. 3 f Example C Uromyces test (dwarf bean)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol 5 ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired 10 concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous uredospore 15 suspension of the bean rust causative organism (Uromyces appendiculatus) and remain in a dark humidity chamber at 20 to 22°C and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse under 20 intensive illumination at 20 to 22°C and a relative atmospheric humidity of 70 to 80% for 9 days.

Evaluation is carried out 10 days after the inoculation.

In this test, a clearly superior activity com-25 pared with the prior art is shown, for example, by the compounds according to the following preparation examples: 3 and 1 208847 Table C Uromyces test (dwarf bean)/protective Active compound Infestation in X at an active compound concentration of 1 ppm Cl r=Nv i /N=i I N-CH2-C-CH2-N J 100 N=/ Jh (B) (known) CH3 OH m_ |-\ » I /N-| I N-C C-CH2-N I (3) 27 N=-/ I | ^=-N CH3 1 — w CH3 OH m — .-N , , /N — j N-C C-CH2-N I N=/ I | V=s. N CH3 1 ( 1 ) E xamp Le D Venturia test (apple)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol 5 ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired 10 concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous conidia 15 suspension of the apple scab causative organism (Venturia inaequalis) and then remain in an incubation cabin at 20°C and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse 20 at 20°C and a relative atmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, a clearly superior activity 25 compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 3, 1 and 4.

Table D Ventur i a test - 30 -(apple)/protective/ Active compound Infestation in % at an active compound concentration of 25 ppm 0 >r /N-i -c-ch2-n ah v-n n-ch2-c-ch2-n i 23 (C) (known) — m ch3 oh -Nv I I /N=-| n-c c-ch2-n | (3) I ch3 — M CH3 OH |-NX , 3 , I f1. n-c c-chp-n ( ' > N-=/ • | ^=-N ch3 m ch3 oh |-N\ I I /N_l | n-c c-ch2-n i (4) Nj-/ i I V=_(vj C!% ' 208847 Example E Pyricularia test (rice)/protective Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol 5 ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, 10 to the desired concentration.

To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension 15 of Pyricularia oryzae. The plants are then placed in a greenhouse at 100% relative atmospheric humidity and 25°C.

Evaluation of the disease infestation is carried out 4 days after the inoculation.

In this test a clearly superior activity compared 20 with the prior art is shown, for example, by the compounds according to the following preparation examples: 3, 1, 4 and 11 . 208847 Table E Pyricularia test (rice)/protective Active compounds Active compound concentration in % Disease infestation in % of the untreated control r->, y n-ch2-c-ch2-n N zsJ I oh 0-025 75 (c) (known) rss N Cl ci ,n=-, I / n-ch?-c-ch2-n h=/ I oh (D) (known) 0.025 100 —m ch3 oh . I s I I /N=l ' n-c f-ch2-f( i CH3 1 (3) 0.025 FN n-c c-ch2-n HM/ JH3, Wn Cl (1) 0.025 Table E (continued) Pyricularia test (rice)/protective Active compounds Active compound Disease infes- concentration tation in % of in % the untreated control CH3 OH ■ _ N , * , /N—.

| Vc C-CH2-N I ( 4 ) N=y I I \=-N N=/ <!H3 Cl a. 025 / OH CH3 m__ c^Hh-C3 (11) 0.025 CH? A 2088 47 Example F Pyricularia test (rice)/systemic Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol 5 ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent, and the concentrate is diluted with water and the stated amount of emulsi-10 fier, to the desired concentration.

To test for systemic properties, standard soil in which young rice plants have been grown is watered with 40 ml of the preparation of active compound. '7 days after the treatment, the plants are inoculated with an 15 aqueous spore suspension of Pyricularia oryzae. Thereafter, the plants remain in a greenhouse at a temperature of 25°C and a relative atmospheric humidity of 100% until they are evaluated.

Evaluation of the disease infestation is carried 20 out 4 days after the inoculation.

In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 3, 1, 4 and 11. s

Claims (7)

- 35 - Table F Pyricularia test (rice)/ systemic 208847 Active compounds Amount applied in mg of active compound per 100 cm Disease infestation in % of the untreated control O /»=! ,-n i F*\ I;i n-ch2-c-ch2-;in ^;(C) (known);?H3 ?H;1 00;75;\ I " I /N";n-c c-ch?-n n=/ i.. jl \=-n o;(3);100;20;—m ch3 oh r\ i i /Nn n-c c - c h 2" n;W I;(1);100;Cl w ch3 oh rN^, 1 1;Na/;\ T J I /N=1;n-c c-ch?-n i ch3;Cl oh c h 3;I I;c —ch-n ' SN-';ch2;•uT;N1 M;(4);(11 );100;100;22;30;20884?;- 36 - I NOW AMENDED |;WHAT WE CLAIM IS:;1) Fungicidal agents, characterised in that/they con tain at least one substituted diazolylalkyl-carbinol of the general fornula;R -;in which;(I);A represent^a nitrogen atom or the CH group,;B represents a nitrogen atom or the CH groups X repr/e/sents hydrogen or alkyl,;Y represents alkyl, or, if X represents/hydrogen,;a^fso alkenyl, alkinyl or optionally s'ubstituted benzyl, and;R represents optionally substituted phenyl or the g roup ing wherein;Alk;1;C -;Alk';Alk^ represents aUcyi and Alk2 represents a^lkyl, or;Alk^ and A Ik2 t'ogether represent a cycloali-phatic ring^/and;R1 represents alkyl, alkenyl or op tion a ILy substituted phenyl, phenylalkyl, phenoxy, pheny'lthio, phenoxya lky I, pheny Ithioa lky I, ben-zyA'oxy or benzylthio;;or acidl/addi11 on salts and metal salt complexes thereof. 2) / Fungicidal agents according to Claim 1,;wherein, 1n formula (I),;A represents a nitrogen atom or the CH group; B represents a nitrogen atom or the CH group;;/F;;fAS AM ENDED;2;- 36 -;WHAT WE CLAIM IS:;1) Fungicidal agents, characterised in that they con tain at least one substituted diazolylalkyl-carbinol of the general formula;R -;OH I;C —;I;C"2;rfNv;X;I /B C-N J, \=.N;(
1. I);i n whi ch;A represents a nitrogen atom or the CH group, B represents a nitrogen atom or the CH group, X represents hydrogen or alkyl,;Y represents alkyl, or, if X represents hydrogen, also alkenyl, alkinyl or optionally substituted benzyl, and;R represents ^the grouping Alk1;wherein |;Alk^ represents alkyl and Alk^;Alk2 represents alkyl, or;Alk^ and Alk2 together represent a cycloali-phatic ring, and r1 represents \ alkenyl or :op tionally substituted jphenoxy,;phenylthio, phenoxyalkyl, phenylthioalkyI, ben-zytoxy or benzylthio;;or acid addition salts and metal salt complexes thereof.
2. 2) Fungicidal agents according to Claim 1,;wherein, in formula (I),;A represents a nitrogen atom or the CH group; B represents a nitrogen atom or the CH group;;208847;NOW AMENDED [;- 37 -;X represents hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms;;Y represents straight-chain or branched alkyl with 1 to 4 carbon atoms; or, if X represents^ hydrogen, also allyl, methy la I ly I, propargyl or methyIpropargyI, or benzyl which is optionally substituted in the phenyl part by fUiorine, chlorine, bromine, methyl, isopropyl,/tert.-butyl, methoxy, methylthio, trifluoromethyI, trifluoro-methoxy, trifluoromethylthio, nitro or cyano; R represents phenyl which is optionally substituted by fluorine, cholerine, bromine, methyl, isopropyl, tert.-but^,f, methoxy, methylthio, tri-fluoromethy I, tfi fluoromethoxy, trifluoromethylthio, nit ro^/cyano, hydroxy I, hydroxyca rbony L, methoxyca^rbony I, ethoxycarbony I, hydroximicornethyI 1-hydro'ximinoethy I, methoximi nomethy I, l^methox-imin'oethyl or phenyl, phenoxy, benzyl/or benzyloxy ^each of which is optionally substituted by fluorine, chlorine or methyl; or, furthermore, the;.1;grouping;Alk;R - C -;Alk.';wherei n;Alk^ represent^ methyl or ethyl; and Alk^ represents methyl or ethyl; or AIk^ a ndy A^k2 , together with the carbon atom to whiten they are bonded, represent cyclobutyl, cyc^fopentyI or cyclohexyl; and;R/* represents methyl, ethyl, n-propyl, i-propyl, n-butyl, neopentyl or phenyl, benzyl, phenethyl, phenoxy, phenylthio, phenoxymethyI, phenoxyethy I, phenylthiomethyl, pheny I th i oet hy I, benzylo/xy or benzylthio, each of which is optionally substi- AS AMENDED 208847 - 37 - X represents hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms; Y represents straight-chain or branched alkyl with 1 to 4 carbon atoms; or, if X represents hydrogen, also allyl, methyI a I lyI, propargyl or methyIpropargyI, or benzyl which is optionally substituted in the phenyl part by fluorine, chlorine, bromine, methyl, isopropyl, tert.-butyl, methoxy, methylthio, trifluoromethy I, trifluoro-methoxy, trifluoromethylthio, nitro or cyano; R represents \ / _ jphenoxy, benzyl or benzyloxy, each of which is optionally substituted by fluorine, chlorine or methyl; or, furthermore, the grouping Alk1 I R1- C -Alk2 wherei n Alk^ represents methyl or ethyl; and Alk^ represents methyl or ethyl; or Alk^ and Alk^, together with the carbon atom to which they are bonded, represent cyclobutyl, cyclopentyl or cyclohexyl; and (^represents / \neopentyl or phenoxy, phenylthio, phenoxymethyl, phenoxyethyI, phenylthiomethyl, phenylthioethyl, benzyloxy or benzylthio, each of which is optionally substi- 2088 47 - 38 - tuted in the phenyl part by the substituents on phenyl which have already been mentioned for R.
3. 3) Method of combating fungi, characterised in that substituted diazolylalkyl-carbinols of the formula (I) are allowed to act on fungi or their environment.
4. 4) Use of substituted diazo lyI a IkyI-carbino Is of the formula (I) for combating fungi.
5. 5) Use of substituted diazolylalkyl-carbinols of the formula (I) as plant protection agents.
6. 6) Process for the preparation of fungicidal agents, characterised in that substituted diazolylalkyl-carbinols of the formula (I) are mixed with extenders and/or surface-active agents.
7. 7) An agent according to claim 1 substantially as herein described or exemplified. BAYER AKTIENGESELLSCHAFT By Theyr Attorneys n.z. patent office 10 JUL 1984 RECEIVE