GB2103210A - Microbiodical and growth regulating substituted 2-hydroxy-3- azolyl-propane derivatives - Google Patents

Abstract

Novel 2-hydroxy-3-azolylpropane derivatives of the general formula I <IMAGE> wherein R1 is an azolyl group, R2 is C1-C4alkyl or an aryl group which is unsubstituted or substituted by halogen, cyano, C1-C3alkyl, C1-C3alkoxy, nitro, thiocyano, C1-C3alkylthio and/or C1-C3haloalkyl, R3 and R4, each independently of the other, are hydrogen or C1-C4alkyl, R5 is an unsubstituted or mono- or polysubstituted radical selected from C1-C8alkyl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C6alkynyl and aralkyl, said substituents being selected from the group consisting of halogen, cyano, C1-C3alkyl, C1-C5alkoxy, C1-C5haloalkoxy, C1-C3alkylthio, C1-C3haloalkyl, C1-C3haloalkylthio, nitro and/or thiocyano; and X is oxygen or sulfur, and the acid addition salts, quaternary azolium salts and metal complexes thereof, are useful in controlling phytopathogenic microorganisms and/or of regulating plant growth.

Description

SPECIFICATION Microbicidal and growth regulating compositions The present invention relates to novel substituted 2-hydroxy-3-azolylpropane derivatives and to the acid addition salts, quaternary azolium salts and metal complexes thereof. The invention relates further to the preparation of these compounds and to microbicidal and growth regulating compositions which contain at least one of these compounds as active ingredient. The invention also relates to the preparation of said compositions and to the use of the active ingredients or compositions for regulating plant growth and for controlling harmful organisms.

Comprised herein are compounds of the general formula I

wherein R, is an azolyl group, R2 is C1-C4alkyl or an aryl group which is unsubstituted or substituted by halogen, cyano, C1-C3alkyl, C1-C3alkoxy, nitro, thiocyano, C1-C3alkylthio and/or C1-C3haloalkyl, R3 and R4, each independently of the other, are hydrogen or C1-C4alkyl, R5 is an unsubstituted or mono- or polysubstituted radical selected from the group consisting of C,--C,all < yl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C6alkynyl and aralkyl, said substituents being selected from the group consisting of halogen, cyano, C1-C3alkyl, C1-C5alkoxy, C1-C5haloalkoxy, C1-C3alkylthio, C1-C3haloalkyl, C1-C3haloalkylthio, nitro and/or thiocyano; and X is oxygen or sulfur, and the acid addition salts, quaternary azolium salts and metal complexes thereof.

The term azolyl denotes a 5-membered heterocyclic ring containing nitrogen as heteroatom and having aromatic character. Typical representatives are 1 H-1,2,4-triazolyl, 4H-1 ,2,4-triazolyl and 1 Himidazole.

Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substituent comprises e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl etc. and the isomers thereof, e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc. Haloalkyl is a mono- to perhalogenated alkyl substituent, e.g. CHCl2, CHF2, CH2CI, CCl3, CH2F, CH2CH2Cl, CHBr2, CF3 etc.

Throughout this specification, halogen denotes fluorine, chlorine, bromine or iodine, with fluorine, chlorine or bromine being preferred. Naphthyl is or- or p-naphthyl, with a-naphthyl being preferred.

Alkylene denotes an unbranched or branched alkylene bridge, e.g. methylene, ethylene, propylene etc., and is preferably a bridge member containing 4 to 6 carbon atoms. Alkenyl is e.g. propen-l-yl, allyl, buten-l -yl, buten-2-yl or buten-3-yl. Alkynyl is e.g. propion-l-yl orpropargyl. Aryl is e.g. naphthyl, especially phenyl; and aralkyl is a lower alkyl radical which is substituted by an aromatic group.

Depending on the indicated number of carbon atoms, cycloaikyl is e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl etc.

Accordingly, the present invention relates to the free compounds of the formula I and to the acid addition salts, quaternary azolium salts and metal complexes thereof. The free compounds are preferred.

Examples of salt-forming acids are inorganic acids, e.g. hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid, phosphorous acid, nitric acid; and organic acids such as acetic acid, trifluoroacetic 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, methanesulfonic 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 etc. of the elements of the third and fourth main group of the Periodic Table such as aluminium, tin or lead, and of the first to eight auxiliary group such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, mercury etc.

Preferred elements are those of the auxiliary groups of the fourth period. The metals may exist in different valency states. The metal complexes of the formula I may be mononuclear or polynuclear, i.e.

they can contain one or more parts of the organic molecule as ligands. Complexes with copper, zinc, manganese and tin are preferred.

The compounds of formula I are oils, resins or mainly solids which are stable at room temperature and have very valuable microbicidal and growth regulating properties. They can be used in agriculture or related fields preventively and curatively for controlling phytopathological microorganisms and for regulating plant growth, for which utility the triazolylmethyl derivatives falling within the scope of formula I are preferred. The compounds of formula I are very well tolerated by cultivated plants.

On account of their pronounced growth regulating and/or microbicidal action, preferred compounds of the formula I are those compounds which contain the following substituents or combinations thereof: For R,: a) 1H-1,2,4-triazole, 4H-1,2,4-triazole, 1H-imidazole.

b) 1H-1,2,4-triazole, 4H-1,2,4-triazole c) 1H-1,2,4-triazole.

For R2: a) methyl, ethyl, isopropyl, tert-butyl, phenyl, phenyl susbtituted by C1-C3alkyl, C1-C3alkoxy.

CF3, halogen and/or phenyl b) methyl, isopropyl, tert-butyl, phenyl, halophenyl, dihalophenyl, biphenyl c) tert-butyl, halophenyl, dihalophenyl d) tert-butyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dichlorophenyl, 2-chloro-4-bromophenyl e) tert-butyl, 4-chlorophenyl, 2,4-dichlorophenyl f- tert-butyl, 2,4-dichlorophenyl g) tert-butyl.

For R3 and R4, sach independently of the other.

a) hydrogen, C1-C4alkyl b) hydrogen, methyl or ethyl c) hydrogen, methyl d) hydrogen.

For X: a) oxygen, sulfur b) oxygen.

For R5: a) a radical selected from the group consisting of C1-C8alkyl, C3-C6cycloalkyl, C3-C8alkenyl, C3-C6alkynyl and aralkyl, which radical may be unsubstituted or mono- or polysubstituted by halogen, cyano, C1-C3alkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkyl, C1-C3haloalkylthio and/or nitro;; b) a radical selected from the group consisting of C1-C8alkyl, C3-C7cycloalkyl, C3-C6alkenyl, C3-C6alkynyl and aralkyl, which radical may be unsubstituted or mono- or polysubstituted by halogen, cyano, C1-C2alkyl, C1-C2alkoxy, C1-C2haloalkoxy, C1-C2alkylthio, C1-C2haloalkyl, C1-C2haloalkylthio and/or nitro;; c) a radical selected from the group consisting of C1-C8alkyl, C3-C7cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, benzyl, CH2CH2-phenyl and CH2-naphthyl, which radical may be unsubstituted or mono- or polysubstituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, methylthio, halomethyl and/or nitro.

Accordingly, preferred compounds of the formula I are e.g. those of the groups a) to e) set forth below: a) compounds of the formula I, wherein R, is a 1 H-1,2,4-triazolyl, 4H-1,2,4-triazolyl or 1 Himidazolyl group; R2 is methyl, ethyl, isopropyl, tert-butyl, phenyl or phenyl which is unsubstituted or substituted by C1-C3alkyl, C1-C3alkoxy, CF3, halogen and/or phenyl; each of R3 and R4 independently of the other is hydrogen or C1-C4alkyl ;R5 is a radical selected from the group consisting of C1-C3alkyl, C3-C8cycloalkyl, C3-C8alkenyl, C3-C8alkynyl and aralkyl, which radical may be unsubstituted or mono- or polysubstituted by halogen, cyano, C1-C3alkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkyl, C1-C3haloalkylthio and/or nitro; and X is oxygen or sulfur; b) compounds of the formula I, wherein R1 is a 1 H-1,2,4-triazolyl, 4H-1,2,4-triazolyl or 1 Himidazolyl group;R2 is methyl, ethyl, isopropyl, tert-butyl, phenyl or phenyl which is mono- or polysubstituted by C1-C3alkyl, C1-C3alkoxy, CF3, halogen and/or phenyl; each of R3 and R4 independently of the other is hydrogen or C1-C4alkyl; R5 is a radical selected from the group consisting of C1-C8alkyl, C3-C7cycloalkyl, C3-C6alkenyl, C3-C6alkynyl and aralkyl, which radical may be unsubstituted or mono- or polysusbtituted by halogen, cyano. C1-C2alkyl, C1-C2alkoxy, C1-C2haloalkoxy, C1-C2alkylthio, C1-C2haloalkyl, C1-C2haloalkylthio and/or nitro ; c) compounds of the formula I, wherein R1 is a 1 H-1,2,4-triazolyl, 4H-i ,2,4-triazolyl or 1 Himidazolyl group; R2 is methyl, isopropyl, tert-butyl, phenyl, halophenyl, dihalophenyl or biphenyl; each of R3 and R4 independently of the other is hydrogen, methyl or ethyl;X is oxygen or sulfur; and R5 is a radical selected from the group consisting of C1-C8alkyl, C3-C7cycloalkyl, C3-C6alkenyl, C3-C6alkynyl and aralkyl, which radical may be substituted or mono- or polysubstituted by halogen, cyano, C1-C2alkyl, C1-C2alkoxy, C1-C2haloalkoxy, C1-C2alkylthio, C1-C2alkylthio, C1-C2haloalkyl, C1-C2haloalkylthio and/or nitro; d) compounds of the formulal, wherein R1 is a 1H-1,2,4-triazolyl or 4H-1,2,4-triazolyl group ; R2 is tort-butyl, halophenyl or dihalophenyl ; each of R3 and R4 independently is hydrogen or methyl ;X is oxygen; and R5 is a radical selected from the group consisting of C1-C8alkyl, C3-C7cycloalkyl, C3-C6alkenyl, C3-C6al kynyl, benzyl, CH2CH2-phenyl and CH2-naphthyl, which radical may be unsubstituted or mono- or polysubstituted by fluorine, chlorine, bromine, cyano, methyl, methylthio, halomethyl and/or nitro; e) compounds of the formula I, wherein R, is a 1 H-1 ,2,4-triazolyl group; R2 is tert-butyl, halophenyl or dihalophenyl; each of R3 and R4 independently of the other is hydrogen or methyl;X is oxygen; and R5 is a radical selected from the group consisting of C1-C5alkyl, C3-C6cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, benzyl, CH2CH2-phenyl and CH2-naphthyl, which radical may be unsubstituted or polysubstituted by fluorine, chlorine, bromine, cyano, methyl, methylthio, halomethyl and/or nitro.

Particularly preferred compounds are those of groups d) and e). Among the growth regulating compounds, those compounds of the formula I are especially preferred in which R2 is a branched C3-C4alkyl group, in particular the tert-butyl group. Among the microbicidal compounds, those compounds of the formula I are especially preferred in which R2 is unsubstituted or substituted aryl, in particular monohalogenated or dihalogenated phenyl, in which the most preferred halogen substituents are fluorine and/or chlorine.

Those compounds within the scope of formula I are also preferred in which R3 and R4 are hydrogen, as well as those in which R1 is a 1 H-1 ,2,4-triazolyl group.

The following individual compounds are especially preferred: 1 -ethoxy-2-(2 ,4-dich lorophenyl)-2-hydroxy-3-[1 H-l ,2,4-triazolyl]-propa ne, 1-n-butoxy-2-[2,4-dichlorophenyl]-2-hydroxy-3-[1H-1,2,4-triazolyl]-propane, 1-n-butoxy-2-tert-butyl-2-hydroxy-3-[1H-1,2,4-triazolyl]-propane, 1 -n-butylthio-2-tert-butyl-2-hydroxy-3-[ 1 H- 1 ,2 ,4-triazolyl]-propane, 1-allyloxy-2-tert-butyl-2-hydroxy-2-[1H-1,2,4-triazolyl]-propane, 1 -benzyloxy-2-tert-butyl-2-hydroxy-3-[ 1 H- 1 ,2,4-triazolyl]-propane, 1-[4-chlorobenzyloxy]-2-tert-butyl-2-hydroxy-3-[1H-1,2,4-triazolyl]-propane, 1 -methoxy-2-tert-butyl-2-hydroxy-3-[ 1 H-1 ,2,4-triazolyl]-propa ne, 1-[4-fluorobenzyloxy]-2-tert-butyl-2-hydroxy-3-[1H-1,2,4-triazolyl]-propane, 1 -cyclohexyloxy-2-tert-butyl-2-hydroxy-3-[ 1 H- 1 ,2,4-triazolyl]-propane, 1 -methoxy-2-phenyl-2-hyd roxy-3-[ 1 H- 1 ,2 ,4-triazolyl]-propane, 1 -benzyloxy-2-tert-butyl-2-hydroxy-3-[4H- 1 ,2,4-triazolyl]-propa ne, 1 -[4-chlorobenzyloxy]-2-tert-butyl-2-hyd roxy-3-[4H- 1 ,2,4-triazolyl]-propane, 1 -[4-fluorphenoxyl-2-tert-butyl-2-hydroxy-3-[4H- 1 ,2,4-triazolyl]-propane.

The compounds of formula I are prepared by reacting an oxirane of the formula II

wherein R2, R3, R4, X and R5 are as defined for formula I, with an azole of the formula Ill M-R, (III), wherein M is hydrogen or preferably a metal atom, especially an alkali metal atom, and R1 is as defined for formula I.

The reaction is conveniently conducted in the presence of a condensing agent or of an acid acceptor. Examples of such compounds are organic and inorganic bases, e.g. tertiary amines such as trialkylamines (trimethylamine, triethylamine, tripropylamine etc.), pyridine bases (4 d'methylaminopyridine. 4-pyrrolidylaminopyridine etc.), oxides hydrides and hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals (CaO, BaO, NaOH, LiOH, KOH, NaH, Ca(OH)2, KHCO3, NaH CO3, Ca(HCO3)2, K2CO3, Na2CO3), as well as alkali acetates such as CH3COONa or CH3COOK. Also suitable are alkali alcoholates such as C2H5ONa, C H -nONa etc.In some cases it may be advantageous to convert the free azole of the formula III (M = hydrogen) first - e.g. in situ with an alcoholate-into the corresponding salt, and then reacting this latter with the oxirane of the formula II in the presence of one of the bases specified above. Parallel to the formation of the 1 ,2,4-triazolyl derivatives, there are usually also obtained 1 ,3,4-triazolyl isomers, which can be separated from one another in conventional manner, e.g. with different solvents. In some cases, hydrogen halide can be expelled from the reaction mixture by introducing inert gas, e.g. nitrogen, or by adding a molecular sieve.

The reaction of the oxirane of the formula II with the azole of the formula Ill is preferably carried out in a relatively polar, but inert, organic solvent, e.g. N,N-dimethylformamide, N-N-dimethylacetamide.

dimethylsulfoxide, acetonitrile, benzonitrile and others. Such solvents may be employed in combination with other inert solvents, e.g. benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene etc. The reaction temperature is in the range from 0 to 1 500 C, preferably from 200 to 1000C.

In other respects, this reaction may be carried out in the same manner as already known reactions of other oxiranes with azoles (cf. European published patent specification 0 01 5 756 and German Offenlegungsschrift 29 12 288).

The azoles of formula Ill are known or they may be obtained by methods which are known per se.

The oxiranes of formula II are novel and constitute specially developed intermediates for the preparation of the valuable compounds of the formula I. Their structural nature makes it possible for them to be converted in simple manner into compounds of the formula I.

The oxiranes of formula II which form one aspect of the present invention can be prepared by reacting the ketones of the formula IV

with dimethylsuifonium methylide or dimethyloxosulfonium methylide, in dimethylsulfoxide or another suitable solvent. In formula IV, the substituents are as defined for formula I. The reaction is carried out in the temperature from 0 to 1200C.

Similar reactions are known from the literature [q.v. JACS, 87, 1353 (1965) and Angew. Chem.

85, 867 (1973)1. In principle, the reaction may be carried out in the same manner as the reactions described therein.

Ketones of the formula IV can be prepared either according to equation a) from the or-haloketones known per se of the formula V

with compounds of the formula VI, in conventional inert solvents, and optionally at elevated temperature, or according to equation b) to give compounds of the formula lvi

from known oxiranes of the formula VII by reaction with an alcohol or this of the formula VIII, advantageously in the presence of catalytic amounts of the formula VIII, advantageously in the presence of catalytic amounts of a compound of the formula VI, to give an alcohol of the formula IX, and by oxidation of this latter. The oxidation is carried out e.g. in conventional manner in an inert solvent with a chromium compound, e.g. CrO3, a manganese compound, e.g. Mono2, a dimethylsulfoxide/sulfur trioxide/pyridine complex or a similar oxidising agent. The reaction of compound (VII) to (IX) may be carried out at elevated temperature, e.g. ~ 1 800C, in an autoclave.

However, in accordance with equation c)

a nitrile of the formula X may be converted into a compound of the formula IV by conventional reaction with a Grignard compound of the formula Xl and subsequent hydrolysis.

In the formulae of equations a) to c) above, the susbtituents R2, R3, R4, Rs and X are as defined for formula I. Hal is halogen, preferably chlorine or bromine, and M is a metal atom, especially sodium or potassium.

The compounds VII to Xl are known or they can be prepared by methods which are known per se.

The compounds of formula VI are likewise known or may be obtained by methods which are known per se.

Unless otherwise expressly specified, one or more inert solvents or diluents may be present in the preparation of all starting materials, intermediates and final products mentioned herein. Examples of suitable inert solvents or diluents are: aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.), anisoíe, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile;N,N-dialkylated amides such as dimethyl formamide; dimethyl sulfoxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with each other. It can often be convenient to carry out the reaction, or partial steps of a reaction, under an inert gas atmosphere and/or in absolute solvents. Suitable inert gases are nitrogen, helium, argon or, in certain cases, also carbon dioxide.

The process for obtaining the compounds of formula I, including all partial steps, constitutes an important object of the present invention.

The compounds of formula I

contain an asymmetrical carbon atom (*) vicinal to the hydroxyl group and, where the substituents R3 and R4 are different, a further such carbon atom vicinal to the --XR, group. Accordingly, the compounds of formula I are usually obtained in the form of mixtures of enantiomers and diastereoisomers and may either subsequently be separated by conventional methods into the pure isomers or obtained as pure isomers by selective synthesis from opticaliy pure starting materials.The different individual isomers have different biological properties and, like the mixtures, constitute an important object of the invention, i.e. the pure diastereoisomers and the pure enantiomers, like the mixtures thereof, are an object of the present invention. For successful application in the field of agriculture it is sufficient to use the mixtures, although the pure isomers make it possible to lower the concentration in certain cases.

Surprisingly, it has now been found that the novel compounds of the formula I and compositions containing them are characterised in particular by their selective influence on plant metabolism. This selective influence on the physiological processes of plant development makes it possible to use the compounds of formula I for different purposes, especially for those in connection with increasing the yield of useful plants, with facilitating harvesting, and with labour-saving in measures taken in crops of cultivated plants.

Previous experience with the application of growth regulators has shown that the active ingredients can induce one or more different responses in the plants. These different responses depend largely on the time of application, based on the development stage of the seed or plant, as well as on the concentrations of active ingredient applied to the plants or the locus thereof. Growth regulators should at all events induce positive responses in the cultivated plants in the desired manner.

Growth regulators may be used e.g. for inhibiting vegetative plant growth. Such a growth inhibition is of economic interest, inter alia, in respect of grasses, as the frequency of cutting in flower gardens, parks, sports fields or road shoulders can thereby be reduced. Of importance too is the inhibition of growth of herbaceous and ligneous plants on road shoulders and near transmission lines, or generally in areas in which strong growth is undesirable.

The use of growth regulators for inhibiting the growth in height of cereals is also important, as shortening the stalks diminishes or completely eliminates the danger of lodging before harvesting. In addition, growth regulators are able to bring about a strengthening of the stalks in crops of cereals and this too counteracts lodging.

In many cultivated plants inhibition of vegetative growth permits more plants to be sown in a crop area, so that a higher yield may be obtained per unit of area. A further mechanism or yield increase using growth regulators resides in the fact that nutrients are able increasingly to promote flower formation and fruiting, whilst vegetative growth is restricted.

Growth regulators are also frequently able to promote vegetative growth. This is of great value when the vegetative parts of plants are to be harvested. However, promotion of vegetative growth can also result simultaneously in promotion of generative growth, so that e.g. more or larger fruit is formed.

Yield increases may also often be obtained by influencing the plant metabolism without any visible changes in vegetative growth. Growth regulators can also induce a change in the composition of plants, so that the quality of the harvest produce is improved. For example, it is possible to increase the sugar content of sugar beet, sugar cane, pineapples and citrus fruit, or to increase the protein content of soya beans or cereals.

The use of growth regulators can lead to the formation of parthenocarpic fruit. The sex of blossoms can also be influenced. The production or flow of secondary plant substances can also be positively influenced by growth regulators, for example the stimulation of the flow of latex in rubber trees.

During plant growth, the development of side-shoots can also be promoted by the chemical interruption of apical dominance using growth regulators. This is of interest e.g. in the propagation of plant cuttings. However, it is also possible to inhibit the growth of side-shoots, e.g. in tobacco plants after decapitation in order to prevent the formation of side-shoots and thus to promote leaf growth.

Plant foliage can be so controlled under the influence of growth regulators that defoliation of the plants is effected at a desired time. Such a defoliation is of interest in order to facilitate mechanical harvesting, e.g. in vines or cotton, or to lower transpiration at a time when it is desired to transplant the plant. Premature fruit drop can be prevented by the use of growth regulators. However, it is also possible to promote fruit drop - e.g. in fruit crops - by means of chemical thinning up to a specific degree. Growth regulators can also be used for reducing the force necessary for detaching fruit at harvesting, thus making possible mechanical harvesting of plants or facilitating manual harvesting.

With growth regulators it is also possible to speed up or delay the ripening of harvest products before or after harvesting. This is particularly advantageous, because a best possible accomodation to market requirements can thereby be achieved. In addition, growth regulators can often improve the colour of fruit. With the aid of growth regualtors it is also possible to concentrate ripening at a particular time. The conditions are thus created for a complete mechanical harvesting of e.g. tobacco, tomatoes or coffee, or for manual harvesting, in only one single operation.

The application of growth regulators can also make it possible to influence the dormancy of seeds and buds of plants, i.e. the endogenic annual rhythm, so that plants such as pineapples or ornamentals in nurseries germinate, sprout or blossom at a time when they would normally not tend to do so.

With growth regulators it is also possible to delay budding or the germination of seeds, e.g. in order to avoid damage by late frosts in areas endangered thereby. Conversely, root growth and/or the formation of shoots can be stimulated, so that growth may be restricted to a shorter period.

Growth regulators can also impart halophilic properties to cultivated plants. The conditions are thus created for cultivating plants in salty soil. Growth regulators can also impart to plants resistance to frost and drought.

Under the influence of growth regulators, the ageing (senescence) of plants or parts of plants can be inhibited or delayed. Such an action can be of great economic importance, as the storabiiity of treated parts of plants or whole plants such as fruit, berries, vegetables, salads or ornamentals can be improved or prolonged after harvesting. Likewise, a substantial yield increase can be obtained by treating cultivated plants by prolonging the phase of photosynthetic activity.

A further important field of use for growth regulators is the inhibition of excessive growth of tropical cover crops. In tropical and subtropical monocultures, e.g. in palm tree plantations, cotton and maize fields etc., cover crops, especially species of leguminosae, are often planted, with the object of maintaining or improving the quality of the soil (prevention of desiccation, supplying nitrogen) and for preventing erosion. By applying the compounds of this invention it is possible to control the growth of these cover crops and so keep the growth in height of these plants at a low level, thus ensuring healthy growth in height of these plants at a low level, thus ensuring healthy growth of the cultivated plants and the maintenance of favourable soil conditions.

Surprisingly, it has also been found that, in addition to their advantageous growth regulating properties, the compounds of formula I and the compositions containing them also have for practical purposes a very useful microbicidal spectrum. A further field of use of the compounds of formula I is therefore the control of harmful microorganisms, especially phytopathogenic fungi. The compounds of formula thus have for practical purposes a very useful curative, preventive and systemic action for protecting plants, especially cultivated plants, without adversely affecting these. With the compounds of formula lit is possible to inhibit or destroy the microorganisms which occur in plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by such microorganisms.

The compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g. Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria). In addition, the compounds of formula I have a systemic action. They can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic microorganisms which occur in the soil.

The compounds of the invention are also especially well tolerated by plants.

Accordingly, the invention also relates to microbicidal compositions and to the use of compounds of the formula I for controlling phytophatogenic microorganisms, especially harmful fungi, and for the preventive treatment of plants to protect them from attack by such microorganisms.

The invention further embraces the preparation of agrochemical compositions which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein. The invention furthermore relates to a method of treating plants, which comprises applying thereto the compounds of the formula I or the novel compositions.

Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, sorghum and related crops), beet (sugar beet and fodder beet), drupes, pomes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, rasberries and blackberries), leguminous plants (beans, lentils, peans, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons) fibre plants (cotton, flax, hemp,jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (composites), areas of grass, embankments or general low cover crops which counteract erosion or desication of the soil and are useful in cultures of trees and perennials (fruit plantations, hop plantations, maize fields, vineyards etc.).

The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These compounds can be both fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application-promoting adjuvants customarily employed in the art of formulation. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, binders orfertilisers.

A preferred method of applying a compound of the formula I or an agrochemical composition which contains at least one of said compounds, is leaf application. The number of applications and the rate of application depend on the intensity of infestation by the corresponding pathogen (type of fungus). However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing a compound of the formula I, or coating them with a solid formulation.In special cases, further types of application are also possible, e.g. selective treatment of the plant stems or buds.

The compounds of the formula I are used in unmodifed form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g.

polymer substances. Like the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normallv from 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 1 00 g to 2 kg a.i./ha, mostpreferably from 200 g to 600 g a.i./ha.

The formulations, i.e. the compositions or preparations containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g.

solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers.

Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used. e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of the formula I to be formulated, suitable surfaceactive compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surfaceactive compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammoniums salts and contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignonsulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.Examples of alkylarylsulfonates are ths sodium, calcium or triethanolamine salts or dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 1 4 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 1 8 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethyiammonium bromide.

The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ringwood, New Jersey, 1979, and Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc.

New York, 1980.

The agrochemical composition usually contain 0.1 to 99%, preferably 0.1 to 95%, of a compound of the formula 1, 1 to 99.9%, preferably 99.8 to 5%, of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant.

Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.

Such agrochemical compositions also constitute an object of the present invention.

The invention is illustrated in more detail by the following Examples, without implying any restriction to what is described therein. Parts and percentages are by weight.

Preparatory Examples EXAMPLE 1 Preparation of

1-cyclohexyloxy-2-tert-butyl-2-hydroxy-3-[1H-1,2,4-triazolyl]-propane a) Preparation of the starting material

1 -cyclohexyloxy-2-hydroxy-3,3-dimethylbutane 1 6 g of tert-butyl ethylene oxide, 35 g of cyclohexanol and 2 g of NaH (50% dispersion in oil) are mixed and stirred at room temperature until no more evolution of hydrogen can be detected. The reaction mixture is then heated in an autoclave for 24 hours to 1 800C and subsequently poured into ice/water and extracted with diethyl ether. The ethereal extract is dried over Na2SO4 and concentrated.

Distillation of the residue at 85 -86 /4.1 10- torr gives a colourless oil.

b) Preparation of the intermediate

1, -dimethyl-4-cyclohexyloxy-butan-3-one 22 g of the alcohol obtained in a) is dissolved in 100 ml of dimethylsulfoxide and to this solution are added 67.6 g of triethylamine. 44.6 g of sulfur trioxide/pyridine complex are dissolved in 100 ml of dimethylsulfoxide and this solution is added dropwise at 250C to the above mixture while cooling from time to time with ice/water. The reaction mixture is poured into a mixture of ice/water/hydrochloric acid after 36 hours and extracted with diethyl ether. The organic phase is washed with dilute hydrochloric acid, water and brine, dried over sodium sulfate and concentrated, affording 25 g of an oil ( < 95%, analysis by gas chromatography), which is further used without purification.

c) Preparation of the intermediate

1 -tert-butyl- 1 -cyclohexyloxymethyl-oxirane 26.7 g of trimethylsulfoxonium iodide and 20.5 g of a 30% solution of sodium methylate in methanol are added to 80 ml of dimethylsulfoxide and 20.5 g of the ketone are added dropwise thereto.

The mixture is kept overnight at 600 C, then poured into ice/water and extracted with ethyl acetate. The organic phase is dried over Na2SO4 and concentrated. Distillation of the residue at 57 0---600 C/9.1 0-2 torr yields 1 7.5 g of a colourless oil.

Content of epoxide: approx. 65%, remainder ketone.

d) Preparation of the final product: 1 -cyclohexyloxy-2-tert-butyl-2-hydroxy-3[1 H- 1 ,2,4-triazolyli-propane 17 g of the oil obtained in c), 3.9 g of 1 ,2,4-triazole and a catalytic amount of potassium tertbutylate are heated overnight to 1 300C in 100 ml of dimethylsulfoxide. The reaction mixture is poured into ice/water and extracted with dichloromethane. The organic phase is washed with water, dried over Na2SO4 and concentrated. The residual oil is crystallised from hexane. Yield: 9.1 g of crystals with a melting point of 1 100--1 1 20C.

Calcualted: C 64.03% H 9.67% N 14.94% Found: C 64.4% H 9.7% N 15.2% EXAMPLE 2 Preparation of

1 -n -n-butoxy-2-[2,4-dichlorophenylf -2-hydroxy-3-/ 1 H- 1 2,4- triazolylI-pro pane a) Preparation of the intermediate

1 -(2,4-dichlorophenyl)-2-n-hutoxyethanol 3 g of 2,4-dichlorophenyloxirane, 30 ml of n-butanol and 0.2 g of 50% aqueous sodium hydroxide are heated for 3 hours under reflux. Excess butanol is then removed in vacuo, the residue is taken up in water and diethyl ether, and the ethereal extract is separated and concentrated. Yield: 4.2 g of crude 1 (2,4-dichlorophenyl)-2-n-butoxyethanol in the form of a dark oil.

b) Preparation of a further starting material

a-n-butoxy-2,4-dichloroacetophenone 37 g of 1 -(2,4-dichlorophenyl)-2-n-botoxyethanol and 97 g of triethylamine are dissolved in 1 50 ml of dimethylsulfoxide. To this solution are added over 30 minutes and at room temperature 56 g of sulfur trioxide/pyridine complex in portions. In the course of this addition the temperature rises to 37 C.

The reaction mixture is stirred for 2 hours at room temperature, then poured into 1 litre of ice/water and the product is extracted with diethyl ether. The ethereal extract is concentrated, affording 36 g of crude cr-n-botoxy-2,4-dich loroacetophenone, which is purified by column chromatography.

c) Preparation of the intermediate

2-(2,4-dichlorophen yl)-2-(n-butoxy)me thyl oxirane 3.1 g of 80% sodium hydride are added to 200 ml of absolute dimethylsulfoxide and to this solution are added 26 g of trimethylsulfoxonium iodide in portions. When the weakly exothermic reaction has subsided, the mixture is stirred for 90 minutes at room temperature and then a solution of 23 g of cr-n-butoxy-2,4-dichloroacetophenone in 100 ml of tetrahydrofuran is added dropwise. The brownish solution is heated to 600--700C and stirring is continued for 15 hours. The reaction mixture is cooled and then poured into brine and ice and extracted repeatedly with diethyl ether.The etheral phases are washed and dried, affording 24 g of 2-(2,4-dichlorophenyl)-2-(n-butoxy)methyl oxirane in the form of a brownish oil.

d) Preparation of the final product: To a solution of 11.4 g of 1 H-i ,2,4-triazole and 1.6 g of potassium tert-butoxylate in 200 ml of dimethylformamide are added 23 g of 2-(2,4-dichlorophenyl)-2-(n-butoxy)methyl-oxirane and the mixture is heated for 16 hours to 850 C. The bulk of the dimethylformamide is stripped off n vacuo and the residue is taken up in water and extracted with hexane/methylene chloride (4:1 voi.%). The extracts are dried and filtered and the solvent removed, affording 18 g of a brown oil. Purification by column chromatography yields 7 g of 1-n-butoxy-2-[2,4-dichlorophenyl]-2-hydroxy-3-[1 H-1 2,4-triazolyl]- propane in the form of a brownish oil.

EXAMPLE 3 Preparation of

1 -methoxy-2-f2-chlorophenyl)-2-hydroxy-3-(l H- 1,2,4-triazol- 1 -yl)-propane a) Preparation of the starting material

&alpha;-methoxy-2-chloroacetophenone With cooling, a solution of 6 g of methoxyacetonitriie in 50 ml of diethyl ether is added to the Grignard compound obtained from 19.1 g of 2-bromochlorobenzene and 2.4 g of magnesium in 100 ml of diethyl ether. The resultant suspension is stirred for 2 hours at room temperature, then 100 ml of water are added, followed by the addition of 30 ml of 30% sulfur acid. The organic phase of the dark mixture is separated, washed with sodium chloride solution, and concentrated. Yield: 16 g of a brown oil which boils at 680-700C//0.02 mbar.

Distillation yields 1 0 g of the pure c-methoxy-2-chloroacetophenone in the form of a clear oil.

b) Preparation of the intermediate

2-methoxymethyl-2-(2-chlorophenyl)oxirane 1.6 g of 80% sodium hydroxide are added to 70 ml of dimethylsulfoxide under nitrogen. Then 12.8 g of trimethylsulfoxonium iodide are added in portions. After the exothermic reaction has subsided, the reaction mixture is stirred for 1 hour and then 9.1 g of a-methoxy-2-chloroacetophenone in 30 ml of tetrahydrofurane are added. The reaction mixture is stirred for 4 hours at 60"C, then poured into ice/water and the product is extracted with diethyl ether. The extract is washed with brine and yields 9 g of the crude oxirane in the form of a yellow oil, which is reacted further without purification.

c) Preparation of the final product: 9 g of 2-methoxymethyl-2-(2-chlorophenyl)-oxirane, 6.2 g of 1,2,4 -triazole and 0.5 g of potassium tert-butanolate are stirred in 70 ml of absolute tetrahydrofuran for 1 2 hours at 800C. The mixture is cooled, then poured into ice/water and extracted twice with 100 ml of diethyl ether. The combined extracts are washed with brine, dried, filtered and concentrated. The oily residue is digested with hexane/diethyl ether, affording 2.5 g of the final product in the form of colourless crystals with a meiting point of 103 -105 C.

The following compounds may be prepared in analogous manner.

TABLE 1 Compounds of the formula

Physical data Compound R2 R3 R4 R5 X [ C] 1.1 C4H9-t H H C4H9-n O m.p. 47-48 1.2 C4H9-t H H C4H9-n S oil;;nD20 1.5076 1.3 CH2 CH3 CH3 CH2CH2C6H4(CH3) (2) 0 resin 1.4 C6H3Ci2(2,4) H H C4H9-n O oil 1.5 4-biphenyl H H C4H9-n O 1.6 C4H9-t H H CH2CH=CH2 0 resin 1.7 C4H9-t H H CH2C=CH O 1.8 C4H9-t H H C2H, O 1.9 C4H9-t H H C3H7-n O 1.10 C4H9-t H H C8Hl7-n 0 resin 1.11 C4Hg-t H H C3H7-i O 1.12 C4H9-t H H CH2C6H, 0 viscous oil 1.13 C4H9-t H H CH2CH2CN O 1.14 C4H9-t H H CH2CF3 O 1.15 C4H9-t H H CH2C6H4Cl(4) 0 viscous oil 1.16 C4H9-t H H CH2C6H4CI(4) 1.17 C4H9-t H H CH2C6H3Cl2(3,4) 0 1.18 C4Hg-t H H CH2C6H3CI2(2,4) 0 1.19 C4Hg-t H H CH2 O oil n20 1A838 1.20 C4H9-t H H CH2C6H3CI2(3,5) O 1.21 C4H9-t H H CH2C6H4F(4) 0 viscous oil 1.22 C4H9-t H H CH2C6H4(0CH3) (4) 0 1.23 C4H9-t H H CH2C6H4NO2(4) O 1.24 C4H9-t H H CH2C6H4(CH3) (4) 0 1.25 C4H 9-t H H C(CH3)2-C=CH O TABLE 1 (Continued)

Physical data Compound R2 R3 R4 R5 X [*C} 1.26 C4H9-t H H CH2CH20CH3 O 1.27 $C4H9-t H H CH2CH2OC4H9-n O 1.28 C4H9-t H H CH2CH2C6H4Cl(4) O 1.29 C4Hg-t H H CH2CH2C6H4F(4) O 1.30 C4H9-t H H CH2CH2N(CH3)2 O 1.31 C4H9-t H H Cyclopentyl 0 1.32 C4Hg-t H H Cyclopenty| S 1.33 C3H7-i CH3 CH3 CH2CH=CH2 O 1.34 C3H7-j CH3 CH3 CH2C=CH O 1.35 C2H7-j CH3 CH3 CH2CH2OCH2 O 1.36 C3H7-i CH3 CH3 C4H9-n O 1.37 C4H9-t H H Cyclohexyl O m.p. 109-110 1.38 C6H5 H H CH2CH-CH2 O 1.39 C6H5 H H C4H9-n O 1.40 C6H5 H H CH2C=CH O 1.41 C6H8 H H C3H7-n O 1.42 C6H5 H H C2H5 O 1.43 C6H5 H H CH2CH20CH3 O 1.44 C6H3CI2(2,4) H H CH2CH=CH2 O 1.45 C6H3CI2(2,4) H H CH2-C=CH O 1.46 C6H3CI2(2,4) H H CH2CH20CH3 O 1.47 C6H4CI(4) H H CH2CH2OC6H4F(4) O 1.48 CH3 H H CH3 O 1.49 C4H9-t H CH3 Cyclohexyl O 1,50 C4H9-t H CH3 C4H9-n O 1.51 C4Hg-t H CH3 CH2C6H4C1(4) O 1.52 C4H9-t H C2H5 Cyclohexyl O 1.53 C4H9-t H C2H5 C4H9-n O 1.54 C4H9-t H C3H7-n Cyclohexyl O 1.55 C4H9-t H C3H7-n C4H9-n O TABLE 1 (Continued)

Physical data Compound R, R, R4 R, X [^c] 1.56 C4Hg-t H C4Hg-n cyclohexyl 0 1.57 C4Hg-t H H CH3 0 viscous oil 1.58 C4Hg-t H OH3 CH3 O 1.59 C4H$ H C2H,, CH3 0 1.60 C4Hg-t H H ZitCH3 0 viscous oil CH3 1.61 C4Hg-t H CH3 ;;GH3 0 CH3 CH3 1.62 C4Hg-t H C2H5 9 O 0 CH3 CH3 1.63 C4Hg-t H H 0 viscous oil CH3 1.64 C4H$ H CH3 X O CH3 1.65 C4Hg-t H CH3 cycloheptyl 0 1.66 C4Hg-t H CH3 cyclooctyl 0 1,67 C4H9-t CH3 CH3 cycIoocty i 0 1,68 C4H9-t H H cyclooctyl 0 1.69 C6H3C12(2,4) H H cyclopropyl 0 1.70 C,H,C1,(2,4) H cy H cyclopentyl 0 TABLE 1 (Continued)

Physical data Compound R2 R3 R4 R5 X [ C] 1.71 C6H3CI2(2,4) H H cyclohexyl 0 1.72 C6H3CI2(2,4) H H benzyl O 1.73 C6H3CI2(2,4) H H C3H7-n O 1.74 C6H3CI2(2,4) H H C2H5 O oil 1.75 C6H3CI2(2,4) H H CH3 O 1.76 C6H4Cl(4) H H C2H5 O 1.77 C6H4CI(4) H H C3H7-n O 1.78 C6H5 H H CH3 O oil 1.79 a-naphthy I H H C3H7-n O 1.80 a-naphthy I H CH3 CH3C=CH O 1.81 &alpha; ;-naphthyl CH3 CH3 CH2CH=CH2 O 1.82 ss-naphthyl H H CH3 O 1.83 ss-naphthyl H H CH2C6H5 O 1.84 ss-naphthyl H CH3 C4H9-n O 1.85 C4H5Cl(2) H H CH3 O m.p. 103-105 1.86 C6H3(OCH3) (4) H H C4H9-n O 1.87 C6H3Cl2(2.4) H H C3H17(1) O 1.88 C6H3Cl2(2.4) H H 4-Cl-benzyl O TABLE 2 Compounds of the formula

Physical data Compound R2 R3 R4 R5 X [ C] 2.1 C4H9-t H H C4H9-n O 2.2 C4H9-t H H CH2CH=CH2 O 2.3 C4H9-t H H CH2C=CH O 2.4 C4H9-t H H C2Hs O 2.5 C4H9-t H H C3H7 O 2.6 C4H9-t H H C8Hl7-n O 2.7 C4H9-t H H C3H7-i O 2.8 C4H9-t H H CH2C6H5 O 2.9 C4H9-t H H CH2CH2CN O 2.10 C4Hg-t H H CH2CF3 O 2.11 C4H9-t H H CH2C6H4C1(4) O 2.12 C4H9-t H H CH2C6H4CI(4) S 2.13 C4H9-t H H CH2C6H3Cl2(3,4) O 2.14 C4Hg-t H H CH2C6H3CI2(2,4) 0 2.15 C4Hg-t H H CH2C6H3Cl2(3,5) 0 2,16 C4H9-t H H CH2C6H4F(4) O 2.17 C4H9-t H H CH2C6H4(OCH3) (4) O 2.18 C4H9-t H H CH2C6H4NO2(4) O 2.19 C4Hg-t H H CH2C6H4CH3(4) 0 2.20 C4Hg-t H H C(CH3)2-C=CH O 2.21 C4H9-t H H CH2CH2OCH3 O 2.22 C4H9-t H H CH2CH2OC4H9-n O 2.23 C4H9-t H H CH2CH2C6H4Cl(4) H H CH2CH2OC4H9-n O O 2.24 C4Hg-t H H CH2CH2C6H4Cl(4) O 2.25 C4H9-t H H CH2CH2N(CH3)2 O TABLE 2 (Continued)

Physical data Physical data Compound R, R3 R4 R, X [1C] 2.26 C4Hg-t H H cyclopentyl 0 2.27 C4Hg-t H H cyclopentyl S 2 - 2 0 2.28 C3H7-i CH3 CH3 CH2CH=CH2 O OH-OH 2.29 C3H7-i CH3 CH3 CH2C-CH O 2.30 C3H7-i CH3 CH3 CH2CH20CH3 O 2.31 C3H7-i CH3 -CH3 C4Hg-n O 2.32 C, H H CH2CH=CH2 O 2.33 06H, H H C4Hg-n O 2.34 C6H,, H H CH,CCH O 2.35 C6H5 H H C3H7-n O 2.36 C6H5 H H 02H3 O 2.37 C, H H CH2CH2OCH3 O 2.38 C6H3C i2(2,4) H H CH2CH=CH2 O 2.39 C,H,C1(2,4) H H CH2C-CH O 2.40 t6H3Cl(2,4) H H CH2CH20CH3 O 2.41 C6H4CI (4) H H CH2CH20C6H4F(4) O 2.42 QH$ g-t H CH3 QH9-n O 2.43 C4Hg-t H CH3 cyclohexyl 0 2.44 C4Hg-t H H cyclohexyl 0 2.45 CH3 H H CH3 O 2.46 C4Hg-t H CH3 cyclohexyl 0 2.47 C4Hg-t H CH3 C4Hg-n 0 2.48 C4Hg-t H CH3 CH2C6H4Cl(4) D 2.49 C4H g-t H QH, cyclohexyl 0 2.50 C4Hg-t H 02H3 C4Hg-n O 2.51 C4Hg-t H C3H7-n - cyclohexyi 0 2.52 C4Hg-t H C3H7-n C4Hg-n O 2.53 C4Hg-t H C4Hg-n . cyclohexyl O 2.54 04H9-t H H s XCH3 O TABLE 2 (Continued)

Physical data Compound R, R3 R, R, X [ C] 2.55 QH$ 9- H OH3 CH3 o 2.56 04H$ g-t H C2Hs eCH3 O 2.57 C4Hg-t H H {tCH3 0 resin 2.58 C4Hg-t H CH3 CH3 H3 0 CH3 CH3 2.59 C4Hg-t H C2H3 < O CH3 CH3 2Ò C4Hg-t H CH3 2.61 04H9-t H CH3 0 CH3 2.62 C4Hg-t H CH3 cycloheptyl 0 2.63 C4Hg-t H CH3 cyclooctyl 0 2.64 C4Hg-t CH3 CH3 cyclooctyl 0 2.65 C4H9-t H H cyclooctyl 0 2.66 C6H3CI2(2,4) H H cyclopropyl 0 2.67 C6H3CI2(2,4) H H cyclopentyl 0 2.68 06H3012(2,4) H H cyclohexyl 0 2.69 C6H3CI2(2,4) H H benzyl 0:: 2.70 C6H3CI2(2,4) H H C3H7-n O 2.71 06H3012(2,4) H H 02H5 O TABLE 2 (Continued)

Physical data Compound R2 R3 R4 R5 X [ C] 2.72 C6H3CI2(2,4) H H CH3 O 2.73 C6H4C1(4) H H C2H5 O 2.74 C6H4Cl(4) H H C3H7-n O 2.75 C6Hs H H CH3 O 2.76 &alpha; ;-naphthyl H H C3H,-n O 2.77 a-naphthy I H CH3 CH2C=CH O 2.78 a-naphthy I CH3 CH3 CH2CH=CH2 O 2.79 ss-naphthyl H H CH3 O 2.80 ss-naphthyl H H CH2C6Hs O 2.81 ss-naphthyl H CH3 C4H9-n O 2.82 C6H4NO2(2) H H C4H9-n O 2.83 C6Hs(OCH3) (4) 'H H C4H9-n O TABLE 3 Compounds of the formula

Physical data Compound R2 R3 R4 R5 X [ C] 3.1 C4H9-t H H C4Hg-n O m.p. 164-165 3.2 C4H9-t H H CH2C=CH O 3.3 C4H9-t H H C2H5 O 3.4 C4H9-t H H C3H7-n O 3.5 C4Hg-t H H C3H17-n O m.p. 141-144 3.6 C4H9-t H H C3H7-i O 3.7 C4H9-t H H CH2C6H6 O m.p. 198-200 3.8 C4Hg-t H H CH2CH2CN O 3.9 C4H9-t H H CH2CF3 O 3.10 C4H9-t H H CH2C6H4Cl(4) O m.p. 194-198 3.11 C4H9-t H H CH2C6H4Cl(4) S 3.12 C4Hg-t H H CH2C6H3Cl2(3,4) 0 3.13 C4H9-t H H CH2C6H3Cl2(2,4) O 3.14 C4H9-t H H CH2C6H3C12(3s5) O 3.15 C4H,-t H H CH2C6H4F(4) O m.p. 194-197" 3.16 C4Hg-t H CH3 cyclohexyl 0 3.17 C4H9-t H H CH2C6H4(OCH)3(4) O 3.18 C4H9-t H H CH2C6H4NO2(4) O 3.19 C4Hg-t H H CH2C6H4(CH3)(4) O 3.20 C4H9-t H H C(CH3)2-C=CH O 3.21 C4H9-t H H CH2CH2OCH3 O 3.22 C4H9-t H H CH2CH2OC4H9-n O 3.23 C4H9-t H H CH3CH2C6H4Cl(4) O 3.24 C4H9-t H H CH2CH2C6H4F(4) 0 3.25 C4H9-t H H CH2CH2N(CH3)2 O TABLE 3 (Continued)

Physical data Compound R, F,, Rd Rs X [ C] 3.26 C4Hg-t H H cyclopentyl 0 3.27 04H$ g-t H H cyclopentyl S 3.28 C3H,-i CH3 CH3 CH2CH=CH2 O 3.29 C3H 7-i CH3 CH 3 CHz=CH O 3.30 C3H,-i CH3 CH3 CH2CH20CH3 O 3.31 CHA CH3 CH3 C4Hg-n O 3.32 O,H H H CH2CH=CH2 O 3.33 C H H C,H,n O 3.34 O,H H H CH2C=CH O 3.35 OH3 H H C3H7-n O 3.36 C6H3 H H 03H5 O 3.37 C6Hs H H CH2CH20CH 3 O 3.38 06H301(2,4) W H CH2CH=CH2 O 3.39 C6H3CI(2,4) H H OH -C"'OH O 3.40 C,H3Ol(2,4) H H CH2CH2oCH3 O 3.41 'C6H4C1(4) H H CH2CH20C6H4F(4) 0 3.42 CH3 H H I CH3 O 3.43 C4H9-t H CH3 cyclohexyl 0 3.44 C4Hg-t H CH3 C4H9-n O 3.45 C4Hg-t H CH3 CH2C6H4CI (4) O 3.46 C4Hg-t H 03H5 cyclohexyl 0 3.47 04H$ g-t H O3H C4H g-n O 3.48 C4Hg-t H C3H7-n cyclohexyl 0 3.49 C4Hg-t H C3H7-n 04H,-n O 3.50 C4Hg t H C4Hg-n cyclohexyl 0 3.51 C4Hg-t H H -(1H CH3 O m.p. 16F1705C 3.52 C4Hg-t I H CH3 CH3 O TABLE 3 (Continued)

Physical data Compound R, R, R4 F,, X nC] 3.53 C4H9-t H C2HE }CH3 O 3.54 C4Hg-t H H CH3 O m.p. 179-181" CH3 3.55 C4H9-t H CH3 &commat; O 0 CH3 CH3 3.56 C4Hg-t H 02H5 < 0 CH3 CH3 3.57 C4Hg-t H H O m.p. 166-171" CH3 3.58 C4Hg-t H CH3 3 CH3 3.59 ; C4H9-t H CH3 cycloheptyl 0 3.60 C4Hg-t H CH3 cyclooctyl 0 3.61 C4Hg-t CH3 CH3 cyclooctyl 0 3.62 04H$ H H cyclooctyl 0 3.63 06H3O12(2,4) H H cyclopropyl 0 3.64 C6H3CI2(2.4) H H cyclopentyl C 3.65 C6H3CI2(2.4) H H cyclohexyl 0 3.66 C6H3CI2(2.4) H H benzyl 0 3.67 C6H3CI2(2.4) H H C3H,-n O 3.68 C6H3CI2(2.4) H H QH5 O 3.69 C6H3CI2(2,4) H H CH3 O 3.70 C,,H40I(4) H H 02H3 O 3.71 C6H4CI(4) H H C2H7-n O TABLE 3 (Continued).

Physical data Compound R2 R3 R4 R5 X [ C] 3.72 C6Hs H H CH3 O 3.73 &alpha;-naphthyl H H C3H,-n O 3.74 &alpha;;-naphthyl H CH3 CH2C=CH O 3.75 a-naphthy I CH3 CH3 CH2CH=CH2 O 3.76 ss-naphthyl H H CH3 O 3.77 ss-naphthyl H H CH2C6H5 O 3.78 ss-naphthyl H CH3 C4H9-n O 3.79 C6H5NO2(2) H H C4H9-n O 3.80 C6H5(OCH3) (4) H H C4H9-n O TABLE 4 Intermediates of the formula II

Physical data Compound R2 R3 R4 R5 X [ C] 4.1 C4Hg-t H H C4H9-n 0 oil 4.2 C6H3Cl2(2,4) H H C4H9-n O 4.3 4-Biphenyl H H C4H9-n 0 4.4 C4H9-t H H CH2CH=CH2 O oil 20D=1.4562 4.5 C4Hg-t H H CH2C=CH 0 4.6 C4H9-t H H C2H5 O 4.7 C4H9-t H H C3H7-n 0 4.8 C4H9-t H H C3H17-n O oil 4.9 C4H9-t H H C3H7-1 O 4.10 C4H9-t H H CH2C6H5 O oil 20D=1.4962 4.11 C4H9-t H H CH2CH2CN 0 4.12 C4H9-t H H CH2CF3 O 4.13 C4H9-t H H CH2C6H4Cl(4) O oil n20D=1.5110 4.14 C4H9-t H H CH2C6H4Cl(4) S 4.15 C4H9-t H H CH2C6H3Cl2(3,4) O 4.16 C4H9-t H H CH2C6H3Cl2(2,4) O 4.17 C4H9-t H H CH2C6H3Cl2(3,5) O 4.18 C4H9-t H H CH2C6H4F(4) O oil n20D=1.5010 4.19 C4H9-t H H CH2C6H4(OCH)3(4)O 4.20 C4H9-t H H CH2C6H4NO2(4) O 4.21 C4H9-t H H CH2C6H4(CH3)(4) O 4.22 C4H9-t H H C(CH3)2-C=CH O 4.23 C4H9-t H H CH2CH2OCH3 O 4.24 C4H9-t H H CH2CH2OC4H9-n O 4.25 C4H9-t H H CH2CH2C6H4Cl(4) O TABLE 4 (Continued)

physical data Compound 2 R, R, Rs X physical data 4.26 QH$ ,- H H CH2CH2C6H4F(4) O 4.27 C4H g-t H H CH2CH2N(CH3)2 O 4.28 C4Hg-t H H cyclopentyl 0 4.29 C4Hg-t H H cyclopentyl S 4.30 C3H7-i CH3 CH3 CH2CH=CH2 O 4.31 C3H7-i CH3 OH3 OH C=OH O 4.32 C3H7-i CH3 CH3 CH;;CH20CH3 O 4.33 C3H7-i CH3 CH3 C4Hg-n O 4.34 O3' 5 H H CH2CH=CH2 O 4.35 03H3 H H C4Hg-n O 4.36 06H3 H H CH2C=CH O 4.3To 06H5 H H C3H7-n O 4.38 06H3 H H 02H3 O 4.39 06H3 H H CH2CH20CH3 O 4.40 C6H3CI2(2,4) H H CH2CH=CH2 O 4.41 06H301(2,4) H H -OH -C=CH O 4.42 C6H3CI(2,4) H H CH2CH2OCH3 0-..

4.43 C.6 H4CI(4) H H CH2CH20C6H4F(4) O 4.44 CH 3 CH 3 CH3 CH2CH2C6H4( CH 3) (2) 0 oil 4.45 C4Hg-t H CH3 cyclohexyl 0 4.46 QH$ ,- H CH3 C4Hg-n O 4.47 C4H g-t H CH 3 ~ CH2C6H4C 1(4) O 4.48 04H,-t H 02H5 cyclohexyl 0 4.49 04H$ g-t H 02H5 C4H9-n O 4.50 C4Hg-t H C3H7-n cyclohexyl 0 4.51 C4Hg-t H C3H7-n C4Hg-n O 4.52 C4Hg-t H i::4Hg-n cyclohexyl 0 4.53 C4H g-t H H CH3 O oil 4.54 C4H 9-t H CH, {i}CI CH3 0 TABLE 4 (Continued)

Physical data Compound R, R, R, Rs X ['C] 4.55 C4H9-t H O2H,, CH3 O 4.56 C4H 9-t H H CH3 O oil 4.57 C4H g-t H CH 3 ss O CH3 CH3 4.58 QH$ 5-t H QH3 < O CH3 OH3 4.59 C4Hg-t H H O oil OH3 4.60 C4Hg-t H CH3 < O OH3 4.61 04H,-t H CH3 cycloheptyl 0 4.62 C,H,-t H CH3 cyclooctyl 0 4.63 C4Hg-t CH3 CH3 cyclooctyl 0 4.64 04H$ ,- H H cyclooctyl Q 4.65 C,H,C1,(2,4) H H cyclopropyl 0 4.66 C6H3CI2(2,4) H H cyclopentyl 0 4.67 C6H3CI2(2,4) H H cyclohexyl 0 4.68 C6H 3C 12 (2,4) H H benzyl 0 4.69 C6H3Ci2(2,4) H H C3H7-n O 4.70 C6H3C 12(2,4) H H 02H3 O 4.71 C6H3CI2(2,4) H H CH3 O 4.72 C6H4C 1(4) H H 02H3 O 4.73 06H401(4) H H C3H7-n 0 TABLE 4 (Continued)

Physical data Compound R2 R3 R4 R5 X [ C] 4.74 C6H5 H H CH3 O 4.75 a-naphthyl H H C3H,-n O 4.76 a-naphthyl H CH3 CH2C=CH O 4.77 &alpha;-naphthyl CH3 CH3 CH2CH=CH2 O 4.78 ss-naphthyl H H CH3 O 4.79 ss-naphthyl H H CH2C6H4 O 4.80 ss-naphthyl H CH3 C4H9-n O 4.81 C6H5NO2(2) H H C4H9-n O 4.82 C6Hs(OCH3) (4) H H C4H9-n O FORMULATION EXAMPLES Formulation Examples for liquid active ingredients of the formula I (throughout, percentages are by weight) 4.Emulsifiable concentrates a) b) c) a compound of tables 1 to 3 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether 5% - - (36 moles of ethylene oxide) tributylphenol polyethylene glycol ether - 12% 4% (30 moles of ethylene oxide) cyclohexanone - 15% 20% xylene mixture 65% 25% 20% Emulsions of any required concentration can be produced from such concentrates by dilution with water.

5. Solutions a) b) c) d) a compound of tables 1 to 3 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol 400 - 70% - N-methyl-2-pyrrolidone - 20 - epoxidised coconut oil - - 1% 5% petroleum distillate (boiling range - - 94% 160-190 ) These solutions are suitable for application in the form of microdrops.

6. Granulates a) b) a compound of tablets 1 to 3 5% 10% kaolin 94% highly dispersed silicic acid 1% attapulgite - 90% The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

7. Dusts a) b) a compound of tables 1 to 3 2% 5% highly dispersed silicic acid 1% 5% talcum 97% kaolin - 90% Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.

Formulation examples for solid active ingredients of the formula I (throughout, percentages are by weight) 8. Wettable powders a) b) c) a compound of tables 1 to 3 25% 50% 75% sodium lignosulfonate 5% 5% sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalenesulfonate - 6% 10% octylphenol polyethylene glycol ether - 2% (7-8 moles of ethylene oxide) highly dispersed silicic acid 5% 10% 10% kaolin 62% 27% The active ingredient is thoroughly mixed with the adjuvants and the mixtures is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

9. Emulsifiable concentrate a compound of tables 1 to 3 10% octylphenol polyethylene glycol ether 3% (4-5 moles of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether 4% (36 moles of ethylene oxide) cyclohexanone 30% xylene mixture 50% Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

10. Dusts a) b) a compound of tables 1 to 3 5% 8% talcum 95% kaolin - 92% Ready-for-use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.

11. Extrudergranulate a compound of tables 1 to 3 10% sodium lignosulfonate 2% carboxymethylcellulose 1% kaolin 87% The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.

12. Coated granulate a compound of tables 1 to 3 3% polyethylene glycol 200 3% kaolin 94% The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

13. Suspension concentrate a compound of tables 1 to 3 40% ethylene glycol 10% nonylphenol polyethylene glycol (15 moles of ethylene oxide) 6% sodium lignosulfonate 10% carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% aqueous emulsion 0.8% water 32% The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biological Examples EXAMPLE 14 Action against Puccinia graminis on wheat a) Residual-protective action Wheat plants are treated 6 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.06%). After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours at 95100% relative humidity and about 200C and then stood in a greenhouse at about 220C. Evaluation of rust pustule development is made 12 days after infection.

b) Systemic action Wheat plants are treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.006% based on the volume of the soil). After 48 hours the treated plants are infected with a uredospore suspension of the fungus. The plants are then incubated for 48 hours at 95100% relative humidity and about 200C and then stood in a greenhouse at about 220C. Evaluation of rust pustule development is made 1 2 days after infection. Compounds of Tables 1 to 3 are effective against Puccinia fungi. Puccinia attack is 100% on untreated and infected control plants.Among others, compounds 1.1 to 1.4,1.6,1.10,1.12,1.15, 1.19,1.21,1.37, 1.78,3.5, 3.7, 3.10,3.15 and 3.72 inhibit attack by Puccinia to 0 to 15%.

EXAMPLE 1 5 Action against Cercospora arachidicola in groundnut plants a) Residual pro tective action Groundnut plants 10-15 cm in height are sprayed with a spray mixture (0.02%) prepared from a wettable powderformulation of the active ingredient, and infected 48 hours later with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at about 21 C and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the fungicidal action is made 12 days after infection, and is based on the number and size of the specks.

b) Systemic action Groundnut plants 10-1 5 cm in height are sprayed with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.06%, based on the volume of the soil). The treated plants are infected 48 hours later with a conidia suspension of the fungus and then incubated for 72 hours at about 21 or and high humidity. The plants are then stood in a greenhouse and evaluation of fungus attack is made 11 days later. Compared with untreated and infected controls (number and size of the specks = 100%), the plants treated with compounds of Tables 1 to 3 exhibit greatly reduced attack by Cercospora.

In the above tests, compounds 1.1 to 1.4,1.6,1.12,1.15,1.21, 1.37,1.78,3.5,3.10,3.15 and 3.72 prevent speck development almost completely (0 to10%).

EXAMPLE 16 Action against Erysiphe graminis on barley a) Residualprotective action Barley plants about 8 cm in height are sprayed with a spray mixture (0.02%) prepared from the active ingredient formulated as a wettable powder. The treated plants are dusted with conidia of the fungus after 3-4 hours. The infected barley plants are then stood in a greenhouse at about 220C. The extent of the infestation is evaluated after 1 0 days.

b) Systemic action Barley plants about 8 cm in height are treated with a spray mixture (0.006%, based on the volume of the soil) prepared from the active ingredient formulated as wettable powder. Care is taken that the spray mixture does not come in contact with the parts of the plants above the soil. The treated plants are infected 48 hours later with a conidia suspension of the fungus. The infected barley plants are then stood in a greenhouse at about 220C and evaluation of infestation is made after 10 days.

Compounds of the formula I are very effective against Erysiphe fungi. Erysiphe attack is 100% on untreated and infected control plants. Among other compounds of Tables 1 to 3, compounds 1.1, 1.2, 1.6,1.10,1.12,1.15, 1.12,1.15,1.19,1.21,1.37,1.78,3.5,3.7,3.10,3.15 reduce fungus attack in barley to O to 1 5%.

EXAMPLE 1 7 Residual-protective action against Venturia inaequalis on apple shoots Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.06%) prepared from a wettable powder formulation of the active ingredient. The plants are infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90100% relative humidity and stood in a greenhouse for a further 10 days at 200--240C. Scab infestation is evaluated 1 5 days after infection.

Compounds 1.1 to 1.4,1.6,1.10,1.12,1.15, 1.19,1.37, 1.78,3.5,3.7,3.10,3.15and3.72 inhibit attack to less than 10%. Venturia attack is 100% on untreated and infected shoots.

EXAMPLE 18 Action against Botrytis cinerea on beans Residual protective action Bean plants about 10 cm in height are sprayed with a spray mixture (0.02% concentration) prepared from the active ingredient formulated as wettable powder. After 48 hours, the treated plants are infected with a conidia suspension of the fungus. The infected plants are incubated for 3 days at 95100% relative humidity and 21 C, and evaluation of the fungus attack is then made. Many compounds of Tables 1 to 3 very strongly inhibit fungus attack. For example, at a concentration of 0.02% compounds 1.1,1.2,1.6,1.10,1.12, 1.12,1.15,1.19,1.21,1.37,1.78,3.5,3.7,3.10,3.15and3.72 are very effective (0 to 15% attack).Botrytis attack is 100% on untreated and infected bean plants.

EXAMPLE 1 9 Growth inhibition of cereals Summer barley (Hordeum volgare) and summer rye (Secale) are sown in sterilised soil in plastic beakers in a greenhouse and watered as required. The cereal shoots are treated about 21 days after sowing with an aqueous spray mixture of a compound of the formula I. The concentration corresponds to 0.5 and 2.5 kg respectively of active ingredient per hectare. Evaluation of the growth of the cereals is made 10 to 21 days after application. Compared with untreated controls, the growth of cereal plants treated with compounds of the formula I is greatly reduced. Compounds of Tables 1 to 3 are particularly effective. For example, compounds 1.1 to 1.4,1.6,1.10,1.12,1.15, 1.19,1.21,1.37, 1.78,3.78,3.5, 3.7, 3.10,3.1 5 and 3.72 reduce the growth rate to less than 20%.

EXAMPLE 20 Growth inhibition of grasses Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina, and Cynodon dactylon are sown in plastic dishes filled with an earth/peat/sand mixture (6 :3 :1), in a greenhouse, and watered as required. The emergent grasses are cut back weekly to a height of 4 cm above the soil and, 50 days after sowing and 1 day after the last cut, are sprayed with an aqueous spray mixture of an active ingredient of the formula I. The concentration of active ingredient corresponds to a rate of application of 0.5 and 2.5 kg per hectare respectively. The growth of the grasses is evaluated 10 and 21 days after application. The compounds of Tables 1 to 3 effect a marked reduction in growth.For example, compounds 1.1 to 1.4, 1.10, 1.15, 1.19, 1.37,3.5,3.7,3.10 and 3.15 reduce growth almost completely (growth rate 0 to 10%).

EXAMPLE 21 Increase in crop yield by regulating the growth of soybeans Soybeans of the "Hark" variety are sown in plastic containers in an earth/peat/sand mixture (6:3:1). The containers are put into a climatic chamber and the plants develop to the 5-6 trefoil leaf stage after about 5 weeks by optimum control of temperature, light, fertiliser addition, and watering.

The plants are then sprayed with an aqueous mixture of a compound of the formula I until thoroughly wetted. Evaluation is made about 5 weeks after application. Compared with untreated controls, the compounds of the formula I markedly increase the number and weight of the harvested siliques. The compoundsofTables 1 to3 are particularly effective. In particular, compounds 1.1 to 1.4,1.10,1.15, 1.19, 1.37, 3.5, 3.7, 3.10 and 3.15 effect an increase in yield of 5 to 12%.

EXAMPLE 22 Growth inhibition of cover crops Test plants of the varieties Centrosema plumieri and Centrosema pubescens are reared from cuttings in plastic pots filled with an earth/turf/sand mixture (1:1:1). After they have grown roots, the plants are transplanted into 9 cm pots and watered as required. For further growth the plants are then kept in a greenhouse at a day temperature of 270C and a night temperature of 21 or. The average light exposure is 14 hours (6000 lux) and the humidity is 70%. The plants are cut back to a height of about 1 5 cm and sprayed 7 days later with a spray mixture of the active ingredient (corresponding to a rate of application of 0.3 and 3 kg/a.i./ha respectively). Four weeks after application the growth of the plants is compared with that of untreated control plants which have been cut back.Compounds of Tables 1 to 3 effect a marked growth inhibition of the cover plants. In particular, compounds 1.1, 1.2, 1.6, 1.10, 1.12, 1.15, 1.19, 1.21, 1.37, 1.78, 3.5, 3.7, 3.10, 3.15 and 3.72 induce a pronounced growth inhibition.

EXAMPLE 23 Inhibition of senescence in cereal plants Summer wheat of the "Svenno" variety is sown in pots with compost soil and reared without special climatic conditions. About 10 days after emergence, 10 to 12 cm primary leaves are cut off and put individually into the test tubes containing 10 ml of an active ingredient suspension (1.25 to 10 ppm). The test tubes are kept in a climatic room at 230C and 70% relative humidity and irradiated daily for an average of 14 hours (10,000 lux). Evaluation of senescence is made 7 days later by comparing the degree of yellowing with still fresh, green leaves. This test shows that compounds of Tables 1 to 3 markedly inhibit the senescence of the test plants. In particular, compounds 1.1 to 1.4, 1.6, 1.10, 1.12, 1.15, 1.19, 1.21, 1.37, 1.78, 3,5, 3.7, 3.10, 3.15 and 3.72 inhibit yellowing of the leaves by more than 80% during the test period.

Claims (29)

1. A compound of the formula I

wherein R1 is an azolyl group, R2 is C1-C4alkyl or an aryl group which is unsubstituted or substituted by halogen, cyano, C1-C3alkyl C1-C3alkoxy, nitro, thiocyano, C1-C3 alkylthio and/or C1-C3haloalkyl, R3 and R4, each independently of the other, are hydrogen or C1-C4alkyl, R5 is an unsubstituted or mono- or polysubstituted radical selected from the group consisting of C1-Csalkyl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C6alkynyl and aralkyl, said substituents being selected from the group consisting of halogen,

cyano, C1-C3alkyl, C1-C5alkoxy, C1-C5haloalkoxy, C1-C3alkylthio, C1-C3haloalkyl, C1-C3haloalkylthio, nitro and/or thiocyano; and X is oxygen or sulfur, or an acid addition salt, quaternary azolium salt or metal complex thereof.

2. A compound of the formula I according to claim 1, wherein R1 is a 1 H-1,2,4-triazolyl, 4H-1,2,4triazolyl or 1 H-imidazolyl group; R2 is methyl, ethyl, isopropyl, tert-butyl, phenyl or phenyl which is unsubstituted or substituted by C1-C3alkyl, C1-C3alkoxy, CF3, halogen and/or phenyl; each of R3 and R4 independently of the other is hydrogen or C1-C4alkyl; R5 is a radical selected from the group consisting of C1-C8alkyl, C3-C8cycloalkyl, C3-C8alkenyl, C3-C6al kynyl and aralkyl, which radical may be unsubstituted or mono- or polysubstituted by halogen, cyano, C1-C3alkyl, C1-C3alkoxy, 01-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkyl, C1-C3haloalkylthio and/or nitro; and X is oxygen or sulfur.

3. A compound of the formula I according to claim 2, wherein R1 is a 1 H-1,2,4-triazolyl, 4H-1,2,4triazolyl or 1 H-imidazolyl group; R2 is methyl, ethyl, isopropyl, tert-butyl, phenyl or phenyl which is mono- or polysubstituted by C1-C3alkyI, C1-C3alkoxy, CF3, halogen and/or phenyl; each of R3 and R4 independently of the other is hydrogen or C1-C4alkyl ; R5 is a radical selected from the group consisting of C1-C3alkyl, C3-C7cycloalkyl, C3-C8alkenyl, C3-C6alkynyl and aralkyl, which radical may be unsubstituted or mono- or polysubstituted by halogen, cyano, C1-C2alkyl, C1-C2alkoxy, C1-C2haloalkoxy, C1-C2alkylthio, C1-C2haloalkyl, C1-C2haloalkylthio and/or nitro ; and X is oxygen or sulfur.

4. A compound of the formula I according to claim 3, wherein R1 is a 1 H-1,2,4-triazolyl. 4H-1,2,4triazolyl or 1 H-imidazolyl group; R2 is methyl, isopropyl, tert-butyl, phenyl, halophenyl, dihalophenyl or biphenyl; each of R3 and R4 independently of the other is hydrogen, methyl or ethyl;X is oxygen or sulfur; and R5 is a radical selected from the group consisting of C1-C8alkyl, 03-C7cycloalkyl, C3-C6alkenyl, C3-C6al kynyl and aralkyl, which radical may be unsubstituted or mono- or polysubstituted by halogen, cyano, C1-C2alkyl, C1-C2alkoxy, C1-C2-haloalkoxy, C1-C2alkylthio, C1-C2haloalkyl, C 1-C2haloalkylthio and/or nitro.

5. A compound of the formula I according to claim 4, wherein R1 is a 1 H-1 ,2,4-triazolyl or 4H 1 ,2,4-triazolyl group; R2 is tert-butyl, halophenyl or dihalophenyl; each of R3 and R4 independently is hydrogen or methyl; X is oxygen; and R5 is a radical selected from the group consisting of C1-C8alkyl, C3-C7cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, benzyl, CH2CH2-phenyl and CH2-naphthyl, which radical may be unsubstituted or mono- or polysubstituted by fluorine, chlorine, bromine, cyano, methyl, methylthio, haiomethyl and/or nitro.

6. A compound of the formula I according to claim 5, wherein R1 is a 1 H-1,2,4-triazolyl group; R2 is tert-butyl, halophenyl or dihalophenyl; each of R3 and R4 independently of the other is hydrogen or methyl; X is oxygen; and R5 is a radical selected from the group consisting of C1-C8alkyl, C3-C6cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, benzyl, CH2CH3-phenyl and CH2-naphthyl, which radical may be unsubstituted or polysubstituted by fluorine, chlorine, bromine, cyano, methyl, methylthio, halomethyl and/or nitro.

7. A compound of the formula I according to claim 1, wherein R1, R3, R4, R5 and X are as defined for formula I and R2 is a branched C3-C4alkyl group.

8. A compound of the formula I according to claim 1, wherein R1, R2, R5 and X are as defined for formula 1 and R3 and R4 are hydrogen.

9. A compound of the formula | according to claim 1, wherein R2, R3 R4 R5 and X are as defined for formula 1 and R1 is a triazolylmethyl group.

10. A compound selected from the group consisting of 1 -n-butoxy-2-[2 ,4-dichlorophenyl] -2-hydroxy-3-[ 1 H-l ,2,4-triazolyl]-propa ne, 1 -ethoxy-2-(2,4-dichlorophenyl)-2-hydroxy-3-[1 H-l ,2,4-triazolyl]-propane, 1 -n-butoxy-2-tert-butyl-2-hydroxy-3-[ 1 H-l ,2,4-triazolyl]-propane, 1 -n-butylthio-2-tert-butyl-2-hydroxy-3-[l H-l ,2,4-triazolyl]-propa ne, 1 -allyloxy-2-tert-buryl-2-hydroxy-3-[l H-l ,2,4-triazolyl]-propane, 1-benzyloxy-2-tert-butyl-2-hydroxy-3[1H-1,2,4-triazolyl]-propane, 1 -[4-ch lorobenzyloxy]-2-tert-butyl-2-hydroxy-3-[ 1 H-l ,2,4-triazolyl]-propane, 1 -m ethoxy-2-tert-butyl-2-hydroxy-3-[ 1 H-l ,2,4-triazolyl]-propa ne, 1 -[4-fluorobenzyloxy]-2-tert-butyl-2-hydroxy-3-[ 1 H-l 2,4-triazolyl]-propane, 1 -cyclohexyloxy-2-tert-butyl-2-hydroxy-3-[ 1 H-l ,2,4-triazolyl]-propane, 1 -methoxy-2-phenyl-2-hydroxy-3-[1 H-l ,2,4-triazolylj-propane, 1 -be nzyloxy-2-tert-butyl-2-hydroxy-3-[4H- 1 ,2,4-triazolyl]-propane, 1-[4-chlorobenzyloxy]-2-tert-butyl-2-hydroxy-3-[4H-1,2,4-triazolyl]-propane, 1-[4-fluorophenoxy]-2-tert-butyl-2-hydroxy-3[4H-1,2,4-triazolyl]-propane.

11. A compound of formula 1 substantially as desenibed with reference to any of Examples 1 to 3.

12. A process for the preparation of a compound of the formula I as defined in claim 1, which process comprises reacting an oxirane of the formula II

wherein R2, R3, R4, X and R5 are as defined in claim 1, with an azole of the formula Ill M-R1 (III) wherein M is hydrogen or a metal atom and R, is as defined in claim 1.

13. A process according to claim 12, wherein the reaction is conducted in a relatively polar, inert organic solvent.

14. A process according to claim 13, wherein the solvent is N,N-dimethylformamide, N,Ndimethylacetamide, dimethylsulfoxide, acetonitrile or benzonitrile or a mixture of said solvents with one another or together with other customary inert organic solvents.

1 5. A process according to claim 12, wherein the reaction is carried out in the presence of a condensing agent or an acid acceptor.

16. A process for the preparation of a compound of formula I susbtantially as described with reference to any of Examples 1 to 3.

17. A compound of formula I when produced by a process claimed in any of claims 12 to 1 6.

18. A composition for controlling or preventing attack by microorganisms and/or for regulating plant growth, which composition comprises at least one compound of the formula I as claimed in claim 1.

19. A composition according to claim 1 8 which comprises at least one compound of the formula I as claimed in claim 2.

20. A composition for controlling microorganisms according to claim 1 8, which comprises at least one compound of the formula I as claimed in claim 2.

21. A composition according to claim 1 8, which comprises at least one compound of the formula I as claimed in any one of claims 4 to 11.

22. A composition according to any one of claims 18 to 21, which comprises 0.1 to 99% of a compound of formula 1, 99.9 to 1% of a solid or liquid adjuvant and 0 to 25% of a surfactant.

23. A composition according to claim 22, which comprises 0.1 to 95% of a compound of formula 1, 99.8 to 5% of a solid or liquid adjuvant and 0.1 to 25% of a surfactant.

24. A composition acording to claim 18 substantially as described with reference to any of Examples 4 toy 3.

25. A method of preparing an agrochemical composition as claimed in any one of claims 18 to 24, which method comprises homogeneously mixing at least one compound of the formula I as defined in any one of claims 1 to ii with suitable solid or liquid adjuvants and surfactants.

26. A method of controlling phytopathogenic microorganisms or of protecting cultivated plants from attack by said microorganisms, which method comprises applying to plants or to the locus thereof a microbiocidally effective amount of a compound of the general formula I as defined in any one of claims 1 to 11.

27. A method of regulating plant growth, which method comprises applying to plants an effective amount of a compound of the formula I as defined in any one of claims 1 to 11.

28. A method of controlling phytopathogenic microorganisms, of protecting cultivated plants from attack by said microorganisms or of regulating plant growth substantially as described with reference to any one of Examples 14 to 23.

29. An oxirane of the formula II

wherein R2, Rs, R4, X and R5 are as defined in claim 1.