CA1210404A

CA1210404A - 1-carbonyl-1-phenyl-2-azolylethanol-derivatives

Info

Publication number: CA1210404A
Application number: CA000441619A
Authority: CA
Inventors: Walter Kunz; Elmar Sturm
Original assignee: Ciba Geigy Investments Ltd
Current assignee: Novartis AG
Priority date: 1982-11-23
Filing date: 1983-11-22
Publication date: 1986-08-26
Also published as: ES8506566A1; GB8530463D0; GB8330970D0; ES527439A0; GB2130584B; GR79723B; PL141026B1; EP0114567A3; PT77700B; ZA838695B; BR8306422A; JPS59106467A; IL70284A0; AU584000B2; PH19709A; AU2158283A; TR21666A; DK534083D0; JPS59106468A; PL244693A1

Abstract

Abstract of the Disclosure Novel 1-carbonyl-1-phenyl-2-azolylethanol-derivatives The invention relates to novel 1-carbonyl-1-phenyl-2-azolylethanol derivatives of the general formula I

(I), wherein R1, R2 and R3 each independently are hydrogen, halogen, C1-C4 alkyl, CF3, unsubstituted or substituted phenyl or unsubstituted or substituted phenoxy, R4 is hydrogen, C1-C10alkyl, C3-C6cycloalkyl or unsubstituted or substituted phenyl, X is -CH= or -N=, and R5 is hydrogen, C1-C12alkyl, C2-C4alkenyl, or unsubstituted or substituted benzyl, or an acid addition salt, a quaternary azolium salt or a metal complex thereof.

The invention further relates to methods of preparing these compounds and to agrochemical compositions which contain them. Also described is a method of controlling phytopathogenic microorganisms and/or of regulating plant growth with the aid of these compounds.

Description

~2~

, Case 5-14196~A

~ovel l-carbonyl-l-phenyl-2-azolyl-ethanol-derivatives The present invention relates to novel l-carbonyl-l-phenyl-2-azolyl-ethanol derivatives of the formula I below and to the acid addition salts, quaternary azolium salts and metal complexes thereof. The invention relates further to preparation of these compounds and to microbicidal and growth regulating compositions ~hich 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 novel compounds or compositions for regulating-plant growth and for controlling harmful microorganisms.

Accordingly, the present invention relates to novel compounds of the formula I
Rl R ~D OR X=7

2~ ~ 1 5 ; o - C - CH - N (I), o~o C=O o=

wherein Rl, R2 and R3 each independently are hydrogen, halogen, Cl-C4alkyl, CF3, unsubstituted or substituted phenyl or unsubstituted or substituted phenoxy, R4 is hydrogen, Cl-ClOalkyl, C3-C6cycloalkyl or unsubstituted or substituted phenyl, X is -CH= or -N=, and R5 is hydrogen, Cl-C12alkyl, C2-C4alkenyl, or unsubstituted or substituted benzyl, ., ;i, ~``~7 4(~

and to the acid addition salts, quaternary azolium salts and metal complexes thereof.

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, nonyl, decyl etc., and their isomers, e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc.

Throughout this specification, halogen denotes fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

Alkyenyl is is e.g. propen-l-yl, allyl, buten-l-yl~ buten-2-yl or buten-3-yl. Alkynyl is e.g. propion~l-yl or propargyl. Depending on the number of carbon atoms, cycloalkyl denotes e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl etc.
Possible substituents of unsubstituted or substituted phenyl, phenoxy or benzyl, regardless of the position of the phenyl, phenoxy or benzyl in the molecule, are Cl-C4alkyl, Cl-C4alkoxy, Cl-C3halo-alkyl, halogen and/or cyano. Haloalkyl denotes here a mono- to perhalogenated alkyl substituent, e.g. CHC12, CHF2, CH2Cl, CC13, CH2F, CH2CH2Cl, CHBr2 and preferably CF3.

Accordingly, the present invention relates both to the free organic compounds of the formula I in the form of aldehydes and ketones and to the acid addition salts, quaternary azolium salts and metal complexes thereof. The free compounds are preferred, in particular lH-1,2,4-triazoles.

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, phos-phorous 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, benzene-, ., ~2~ 4~4 sulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid.

~etal 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, trifluoro-acetates, 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 eighth 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 monocyclic or polycyclic, i.e. they can contain one or more parts of the organic molecule as ligands. Conplexes 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 phyto-pathological microorganisms and for regulating plant growth, for which utility the triazolyl-l-methyl derivatives falling within the scope of formula I are preferred. The compounds of formula I are very well tolerated by cultivated plants. In addition, they are most suitable for the preparation of microbicides and/or growth regulators.

On account of their pronounced growth regulation and/or microbicidal action, preferred compounds of the formula I, in increasing order of preference, are those compounds which contain the following substi-tuents or combinations thereof:

, ` lZ~

For Rl, R2 and R3, each independently of the other, a) hydrogen, halogen, Cl-C3alkyl, CF3, phenyl, phenoxy, or phenyl or phenoxy each substituted by Cl-C4alkyl, Cl-C4alkoxy, Cl-C3halo-alkyl, halogen or cyano;

b) H, F, Cl, Br, CH3, C2H5, CF3, phenyl, phenoxy, C6H4C1(4), C6H4CH3(4), C6H3C12(2,4), OC6H4Cl(4), OC6H4CH3(4), OC6H3C12(2,4).

c) Rl: H, 2-Cl, 2-Br, 2-F, 2-CF3, 2-C6H5, 2-OC6H5, 3-F, 3-Cl, 3-Br~

3-CF3, 3-C6H5, 3-OC6H5.

R2: H, 4-Cl, 4-Br, 4-F, 4-CF , 4-C H 4-OC H 4-C H C1(4)

4-C6H4CH3(4), 4-C6H3C12(2,4), 4-OC6H4C1(4), 4-OC6H4CH3(4), 4-OC6H3C12(2,4), 4-~-C6H4F(4), 5-Cl, 5-Br, 5-F,

5-CF3.
R3: H, 6-F, 6-Cl, 6-Br, 6-CF3.

d) Rl: 2-H, 2-F, 2-Cl, 2-Br, R2: 4-F, 4-Cl, 4-Br, 4-CF3, : H.

For R4:
a) hydrogen, Cl-C6alkyl, C3-C6cycloalkyl, phenyl, or phenyl substi-tuted by Cl-C4-alkyl~ Cl-C4alkoxy, Cl-C3haloalkyl, halogen or cyano;

b) hydrogen, Cl-C4alkyl, C3-C6cyclohexyl, phenyl or phenyl substituted by methyl, methoxy CF3, F, Cl, Br or CN;

c) hydrogen, ~ethyl, phenyl, 2,4-dichlorophenyl.

4(~91 For R5:
a) hydrogen, Cl-C8alkyl, C2-C4alkenyl, propargyl, benzyl, or benzyl which is mono- or disubstituted by fluorine, chlorine, bromine and/or Cl-C3alkyl;

b) hydrogen, Cl-C6alkyl, C3-C4alkenyl, propargyl, benzyl, or benzyl which is mono- or disubstituted by fluorine, chlorine and/or methyl;

c) hydrogen, Cl-C5alkyl, allyl, propargyl, benzyl, 2-halobenzyl, 4-halobenzyl, 2,4-dihalobenzyl, 2,6-dihalobenzyl, 3,4-dihalo-benzyl, wherein halo denotes halogen;

d) hydrogen, C1-C5-alkyl, allyl, propargyl, benzyl, 2,6-dichloro-benzyl, 4-chlorobenzyl, 4-fluorobenzyl, 2,4-dichlorobenzyl.

For X:
a) -CH=, -N=;
b) -N=.

Accordingly, the following groups of compounda for example are preferred in increasing order of preference:

a) compounds of the formula 1, wherein Rl, R2 and R3 are each independently hydrogen, halogen, Cl-C3alkyl, C~3, phenyl, phenoxy, or phenyl or phenoxy each substituted by Cl-C4alkyl, Cl-C4alkoxy, Cl-C3haloalkyl, halogen or cyano; R4 is hydrogen, Cl-C6alkyl, C3-C6cycloalkyl, phenyl~ or phenyl substituted by Cl-C4alkyl, Cl-C4alkoxy, Cl-C3haloalkyl, halogen or cyano; R5 is hydrogen, Cl-C8alkyl, C2-C4alkenyl, propargyl, benzyl, or benzyl which is mono- or disubstituted by fluorine, chlorine, bromine and/or Cl-C3alkyl, and X is -CH= or -~=, and the acid addition salts, quaternary azolium salts and metal complexes thereofl ~Z~ )4 b) compounds of the formula I, wherein Rl, R2 and R3 are each independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl~ CF3, phenyl, phenoxy, C6H4C1(4), C6H4CH3(4), C6H3C12(2,4), OC6H4C1(4)1 oC6H4CH3(4) or OC6H3Cl2(2,4); R4 is hydrogen, Cl-C4alkyl, C3-C6cycloalkyl, phenyl, or phenyl substituted by methyl, methoxy, CF3, F, Cl, Br or CN; R5 is hydrogen, Cl-C6-alkyl, C3-C4alkenyl, propargyl, benzyl or benzyl which is mono-or disubstituted by fluorine, chlorine and/or methyl, and X is -N=; and the acid addition salts, quaternary azolium salts and metal complexes thereof;

c) compounds af the formula I, wherein Rl is hydrogen, 2-Cl, 2-Br, 2-F~ 2-CF3, 2-C6H5~ 2-C6H ~ 3-F 3-C1 3-Br 3-CF 3-C H or 3-OC6H5; R2 is hydrogen, 4-Cl, 4-Br, 4-F, 4-CF3, 4-C6H5, 4-OC6H5, 4-C6H4C1(4), 4-C6H4CH3(4), 4-C6H3C12(2,4), 4-0C6H4C1(4), 4-OC6H4CH3(4), 4-OC6H3Cl2(2,4), 4-0-C6H4F(4), 5-Cl, 5-Br, 5-F or 5-CF3; R3 is hydrogen; R4 is hydrogen, methyl, phenyl or 2~4-dichlorophenyl; R5 is hydrogen, Cl-C5alkyl, allyl, propargyl, benzyl, 2-halobenzyl, 4-halobenzyl, 2,4-dihalobenzyl, 2,6-dihalo-benzyl or 3,4-dihalobenzyl and X is -N=; and the acid addition salts, azolium salts and metal complexes ehereof;

d) compounds of the formula I, wherein Rl is 2-H, 2-F, 2-Cl or 2-Br;
R2 is 4-F, 4-Cl, 4-Br or 4-CF3; R3 is hydrogen; R4 is hydrogen, methyl, phenyl or 2,4-dichlorophenyl; R5 is hydrogen, Cl-C5alkyl, allyl, propargyl, benzyl, 2,6-dichlorobenzyl, 4-chlorobenzyl, 4-fluorobenzyl or 2,4-dichlorobenzyl, and X is -N=; and the acid addition salts, quaternary azolium salts and metal complexes thereof.

Particularly preferred individual compounds are e.g.:

2-(2,4-dichlorophenyl)-2-hydroxy-3-(lH-l,2,4-triazol-1'-yl)propanal (compound 1.54);
2-(2,4-dichlorophenyl)-2-hydroxy-l-(lH-l,2,4-triazol-1'-yl)-butan-3-one (compound 1.2);

2-(2,4-dichlorophenyl)-2-hydroxy-1-(lH-1,2,4-triazol-1'-yl)-pentan-3-one (compound 1.6);
2-(2,4-dichlorophenyl)-2-methoxy-1-(lH-1,2,4-triazol-1'-yl)-butan-3-one ~compound 2.2);
2-(2-chloro-4-fluorophenyl)-2-hydroxy-1-(lH-1,2,4-triazol-1'-yl)-butan-3-one (compound 1.16);
2-[2-methyl-4-(4'-chlorophenoxy)~-2-hydroxy-1-(lH-1,2,4-triazol-1'-yl)-butan-3-one (compound 1.36).

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

R t---C--CH2 (~I) el:~ C=O

with an azole of the formula III
X=~
/
M-N (III), =N
to give first a compound of the formula Ia Rl R ~- OH X=o I
;~ - C - CH -2~ (Ia) ~ C=O =~ I

~2~34~4 or by reacting an ~-haloketone or a a-haloalde'nyde of the formula IV
Rl R ~- Hal 2~ ~ I
; - C-H (IV), ~ C=O

with paraformaldehyde and a strong non-nucleophilic base, e.g. an alkali metal hydride or alkali metal alcoholate (LiH, NaH, KH, potassium tert-butylate, NaOC2H5 etc., and, by subsequent addition of an azole of the formula III, further reacting the intermediate to give a corresponding alcohol of the formula Ia and, in both variants, if desired, converting the alcohol Ia in conventional manner, e.g. by reaction with a compound of the formula V

R5-W (V) into an ether of the formula I, in which formulae Ia, II, III, IV
and V above the substituents Rl, R2, R3, R4, R5 and X are as defined for formula I, M is hydrogen or preferably a metal atom, most preferably an alkali metal atom such as Li, Na or K, Hal is halogen, preferably chlorine or bromine, and W is OH or a customary leaving group, by which is meant throughout this specification a substituent such as a halogen atom (e.g. fluorine, chlorine, bromine or iodine, preferably chlorine or bromine), a sulfonyloxy group, preferably -OSO2-Ra, an acyloxy group, preferably -OCO-R and an isourea radical, preferably -O-C=NR
¦ , where Ra, Rb and R are each independently c Cl-C3alkyl, Cl-C3haloaLkyl, phenyl, or phenyl substituted by halogen, methyl, nitro, trifluoromethyl and/or methoxy.

4~4 g The reaction of the oxirane II with the azole III to give the alcohol Ia 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 and pyridine bases ~4-dimethylaminopyridine, 4-pyrrolidylaminopyridine etc.), oxides, hydrides and hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals (CaO, BaO, NaOH, LioH, KOH~ NaH~ Ca(H)2~ KHC03, NaHC03~ Ca(HC3)2' K2C3' Na2C3)' as well as alkali acetates such as CH3COONa or CH3COOK. Also suitable are alkali alcoholates such as C2H50Na, C3H7-nONa etc. In some cases it may be advantageous to convert the free azole of the formula III
~ = hydrogen) first - e.g. in situ with an alcoholate - into the corresponding salt, and then to react 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 deriva-tivesl 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.

The reaction of the oxirane of the formula II with the azole of the formula III to give the alcohol of the formula Ia 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 150C, prefer-ably from 20 to lOO~C.

In other respects, this reaction may be carried out in the same manner as already known reactions of other oxiranes with azoles (cf.
German Offenlegungsschrift 29 12 288).

' ~Zl~O~

The reaction of compounds of the formula IV to give compounds of the formula Ia is carried out by reaction with paraformaldehyde in the presence of a strong non-nucleophilic base such as an alkali metal hydride (NaH), and subsequent addition of triazole, or preferably an alkali salt thereof, or of a mixture of both. The reaction is normally conducted in the temperature range from 0 to 140C, preferably from 10 to 80C, and normally in a non-aqueous solvent, e.g. N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl-sulfoxide, hexamethylphosphoric triamide, N-methylpyrrolidone, a nitrile such as acetonitrile, an ether or ethereal compound such as a dialkyl ether, tetrahydrofuran or dioxan and the like. It is preferred to carry out the reaction in dimethylsulfoxide.

In the above partial reactions, the intermediates can be isolated from the reaction medium and, if desired, before the further reaction, purified by one of the conventional methods, e.g. by washing, stirring in a mixture of solvents, extraction, crystalli-sation, chromatography, distillation and the like.

The further reaction of the compound Ia to the compound of formula I, where W in formula I is a customary leaving group, is carried out in the absence or preferably in the presence of an inert solvent.
Examples of suitable solvents are: N,M-dimethylformamide, N,N-di-methylacetamide, hexamethylphosphoric triamide, dimethylsulfoxide, 2-methyl-2-pentanone and the like. It is also possible to use mixtures of these solvents with each other or with other customary inert organic solvents, e.g. with aromatic hydrocarbons such as benzene, toluene, xylenes and the like. It may sometimes be convenient to carry out the reaction in the presence of a base, e.g.
an alkali metal hydride, hydroxide or carbonate, to speed up the reaction rate. However, it can also be advantageous to convert the alcohol of the formula Ia (R5=OH) first into a suitable metal salt in a manner known per se, e.g. by reaction with a strong base.

~, ~Z~(~4~

Examples of suitable strong bases are alkali metal and alkaline earth metal hydrides (Na~, KH, CaH2 and the like) and organic alkaline compounds such as butyllithium or alkali tert-butoxide.
Further, it is also possible to use alkali metal hydroxides such as NaOH or KOH if the process is carried out in an aqueous two-phase system and in the presence of a phase transfer catalyst.

However, before the further reaction, the alcohol of the formula Ia can also be converted into an alkali metal alcoholate and then reacted with a compound of the formula V (wherein W is a leaving group), in which case the reaction is conveniently carried out in the presence of a crown ether. The preferred crown ethers are 18-crown-6 (where M = K) and 15-crown-5 (where M = Na). The reaction i9 advantageously conducted in an inert medium. Examples of suitable solvents are ethers and ethereal compounds, e.g. di-lower alkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether and the like), tetrahydrofuran, dioxan and aromatic hydro-carbons such as benzene, toluene or xylenes.

The following solvents for e~ample are suitable for the organic water-immiscible phase: aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylenes etc.; halogenated hydrocarbons such as dichloro-methane, chloroform, carbon tetrachloride, ethylene dichloride, 1,2-dichloroethane, tetrachloroethylene and the like, or aliphatic ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether etc. Examples of suitable phases transfer catalysts are:
tetraalkylammonium halides, hydrogen sulfates or hydroxides, e.g.
tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl-ammonium iodide, triethylbenzylammonium chloride or triethylbenzyl-ammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide or tetrapropylammonium iodide etc. Suitable phase transfer catalysts are also phosphonium salts. The reaction temperatures are generally in the range from 30 to 130C or may also be at the boiling point of the solvent or mixture of solvents.

~LZ~

Where W in formula V is hydroxy, it is advantageous to carry out a condensation reaction. Both reactants are heated under reflux in a suitable solvent.

For the above reaction it is in principle possible to use solvents which are inert to the reactants and conveniently form azeotropes with water. Examples of such solvents are aromatic hydrocarbons such as benzene, toluene, xylene or halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloro-ethane, tetrachloroethylene, chlorobenzene, and also ethereal compounds such as tert-butylmethyl ether, dioxan and the like. In some cases the compound of formula III itself can be used as solvent. This condensation reaction is advantageously carried out in the presence of a strong acid, e.g. paratoluenesulfonic acid, and at the boiling temperatures of the mixture of azeotropes.

To prepare the ethers of the formula I, it is also possible to replace the free OH group in the compound of formula Ia first by one of the above mentioned customary leaving groups W, and then to carry out a conversion reaction with a compound of the formula V (W =OH).

The replacement of the free hydroxyl group in the compounds of formula V by a leaving group A is preferably carried out in an inert solvent. Examples of such solvents are: aromatic and aliphatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether, ligroin or cyclohexane; halogenated hydrocarbons such as chloro-benzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachloroethylene; ethers and ethereal compounds such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, dimethoxyethane, dioxan, tetrahydrofuran or anisole; esters such as ethyl acetate, propylacetate or butylacetate; nitriles such as acetonitrile; or compounds such as dimethylsulfoxide, dimethyl-formamide and mixtures of such solvents.

, ., L04~9~

The introduction of the leaving group is effected by conventinal methods. If ~ is chlorine, then e.g. phosphoroxy chloride, phos-phorus trichloride, phosphorus pentachloride or, preferably, thionyl chloride, is used as reagent. The reaction is generally carried out in the temperature range from 0 to 120C. If W is bromine, the preferred reagent is phosphorus tribromide or phosphorus penta-bromide and the reaction is carried out in the temperature range from O to 50 C. If W is one of the groups -OS02R , -OCO-R or -O-C=NRb a a NHR , then the reagent will normally be the corresponding acid halide, in particular acid chloride. In this case, it is expedient to carry out the reaction in the temperature range from -20 to +50C, with the preferred range being from -10 to ~30C, and in the presence of a weak base such as pyridine or triethylamine.

The starting compounds of the formulae III and V are generally known or they can be prepared 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 com-pounds of the formula I. Their structural nature makes it possible for them to be converted in simple manner into compounds of the formula I.

Further, some of the compounds of formula II are fungicidally active against harmful fungi of the families Ascomycetes, Basidiomycetes or Fungi imperfecti.

The oxiranes of the formula III can be prepared in a manner known per se by epoxidation from the corresponding styrene derivatives of the formula VI

-- ~Z~04Q4 R2~
; -C=CH2 (VI), ~o f=o wherein Rl to R4 are as defined for formula I, for example by oxidation with peracids such as peracetic acid, tert-butylhydro-peroxide, m-chloroperbenzoic acid, H202 and the like, and optionally in the presence of a base such as NaO~, KOH, ~aHCO3, in conventional inert solvents. Mo(CO)6 can be used as catalyst in this reaction.

Styrene derivatives of the formula VI, can be obtained from the corresponding per se known starting ketones of the formula VII

Rl R ~ ~3 ; / 1 2 (VII), :~o' C=O

wherein Rl to R4 are as defined for formula I, in a manner similar to that described in Angew. Chem., 1976, 261, by reaction with dimethylmethyleneimmonium halides.

The compounds of formula IV are known or they can be prepared by methods which are known per se, e.g. from the corresponding known -hydroxyketones or a-hydroxyaldehydes, by conventional replacement of the hydroxyl groups by halogen.

~nless 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.

~2~ 4 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.), anisole, dioxane, tetrahydrofurane; nitriles such as aceto-nitrile, propionitrile; N,N-dialkylated amides such as dimethyl formamide; dimethylsulfoxide; 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 compounds of the formula I

I * X=
; ~_f - CU2 - N ~ (I), ~o f=o c=N

always contain an asymmetrical carbon atom (*) vicinal to the substituents A and OR5 and can therefore be obtained in the form of two enantiomers. Normally a mixture of both enantiomers is obtained in the preparation of these substances, which mixture can be resolved in conventional manner into the pure optical antipodes, e.g. by fractional crystallisation of salts with optically active strong acids. The enantiomers can have different biological proper-ties. For example, the one enantiomer can have fungicidal properties and the other growth regulating properties. There may also be a graduated difference in activity while the activity spectrum remains the same. The acetalisation of ketones of the formula I with uns~mmetrical 1,2- or 1,3-diols leads to a further centre of 04~4 asymmetry in the resultant dioxolane or dioxan ring. Four stereo-isomers in the form of pairs oE diastereoisomers (cis- and trans-form) are obtained. The individual diastereoisomers can be separa-ted in conventional manner, e.g. by column chromatography, and, if desired, resolved into the enantiomers.

The present invention relates to all pure stereoisomers, enantiomers and mixtures thereof.

The above described preparatory process, including all partial steps, constitutes an important object of the present invention.

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 develop-ment makes it possible to use the compounds of formula I for different purposes, especially for those in connection with in-creasing the yield of useful plants, with facilitating harvesting, and with labour-saving in measures taken in crops of cultivated plants.

The compounds of formula I can accordingly be used for regulating plant growth.

Plant growth regulators can be used e.g. for inhibiting vegetative plant growth.

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 I it 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 Erom 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 microorganlSmS.

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:

3 z~a4~

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, peas, 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, onioas, 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 desiccation 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 agriculture 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 prepara~ions that influence plant growth. They can also be selective herbicides, 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 corres-pond to the substances ordinarily employed in formulation tech-nology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, binders or fertilisers.
Phospholipids are also useful formulation assistants.

A preferred method of applying a compound of the formula I or an agrochemical composition which contains at least one of said compounds, is foliar application. The number of applications and the ~ ~.Z~4~

rate of application depend on the risk of infestation by the corresponding pathogen (type of fungus). However, the compound of Eormula 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 unmodified 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. As with 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 normally from 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to 600 g a.i./ha.

The formulations, i.e. the compositions or pr~parations 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).

Suitalbe 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, dimethylsulfoxide or dimethylformamide, 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 adsorp-tive 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. Phospholipids can also be used with particular advantage.

Depending on the nature of the compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic sufactants 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 surface-active 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 benz-imidazole derivatives or alkylarylsulfonates.

The Eatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or sub-stituted ammonium salts and contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic 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 sulfona-ted benzimidazole derivatives prefer.ably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-ethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic 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-nonyl-phenol with 4 to 14 moles of ethylene oxide.

~on-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 ~ to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

~urther 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 nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/
polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyo~yethylene 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. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium 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, ~ew Jersey, 1981, Helmut Stache "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981.

The agrochemical compositions usually contain 0.1 to 99 ~, preferably 0.1 to 95 ~, of a compound of the formula I, 99.9 to l ~, preferably 99.8 to 5 ~, of a solid or liquid adjuvant, and O to 25 ~, preferably 0.1 to 25 ~, of a surfactant.

Whereas commercial products are preferably formulated as concen-trates, 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.

~2~ 4 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.

~xample Pl: Pre~aration of o-- OH O
// ~ 1 11 --C--C--C6H5 (1.1) = CH2 N
g N
Il 11 N - o l-Benzoyl-l-phenyl-2-rlH-1,2,4,-triazol-1'-yllethanol With cooling and good stirring, 5 g of paraformaldehyde and Z.25 g of a 55% dispersion of sodium hydride in oil are added in succession and in portions at 15-30C and under nitrogen to a ready prepared solution of 11.5 g of desyl chloride in 75 ml of absolute dimethyl-sulfoxide. Towards the end of this addition, a clear solution forms and some evolution of gas is observed. After the exothermic reaction has subsided, the reaction mixture is stirred for 3 hours and then cooled to room temperature. Then a solution of 6.9 g of 1,2,4-tri-azole and 4.6 g of the sodium salt of 1,2,4-triazole in 75 ml of absolute dimethylsulfoxide is added dropwise, while the temperature remains constant without cooling. After it has been stirred over-night at room temperature, the reaction mixture is heated for 5 hours to 60C, then cooled and ice/water is added. The turbid solution is neutralised with dilute hydrochloric acid and extracted with ethyl acetate. The extract is washed with water, dried and concentrated, affording an oil which crystallises after addition of a small amount of diethyl ether. The crystals are filtered and the filter residue is washed with ether, to give crystals with a melting point of 185C-190C.

., ~2~ Q~

Example P2: a) Preparation of the starting material Cl /

--o O
// ~ 11 Cl~ C - C - CH

= CH2 2-(2,4-Dichlorophenyl)-l-buten-2-one 30.5 g of 2,4-dichlorophenylacetone and 15.4 g of ~,N-dimethyl-methyleneimmonium chloride are refluxed for 44 hours. The mixture is then cooled to room temperature, poured into ice/water and extracted with ethyl acetate. The extract is partially evaporated and filtered through a short column packed with silica gel with a 1:1 mixture of methylene chloride/ether as eluant. After evaporation, the product is obtained as a brownish red oil.

Preparation of a further intermediate Cl /

~_~ O
// ~ 11 C1-o ~ - C - C - CH
\ / \ 3 ~=o /0 C 'H2 l-Acetyl-1-(2,4-Dichloroph nyl)oxirane With stirring, 22.2 ml of 30% hydrogen peroxide are added dropwise to 13.3 g of 2-(2,4-dichlorophenyl)-1-buten-1-one in 225 ml of methanol, followed by the dropwise addition of 12.4 ml of 3~ sodium hydroxide solution over 3/4 hour at a maximum temperatur of ~3 C, with cooling. The reaction mixture is stirred for a further 5 hours, decomposed with ice/water and extracted with methylene chloride. The extracts are washed with sodium hydrogen sulfate (peroxide test) and concentrated in vacuo and dried, affording 7.3 g of crude epoxide which can be used without further purification.

~ 2~ ~Q~

c) Preparation of the final product ~-o OH O
// ~ 1 11 C~--o - C - C - CH (1.2) \ / 1 3 =~ CH2 /\
~ N
Il 11 N - -3-Hydroxy-3-(2,4-dichlorophenyl)-4-rlH-1,2,4-triazol-1'-yll-2-butanone 7.3 g of 1-acetyl-1-(2,4-dichlorophenyl)-oxirane in 20 ml of absolute dimethylsulfoxide are added dropwise at room temperature to a ready prepared solution of 3.5 g of free 1,2,4-triazole and 5.6 g of its sodium salt in 80 ml of absolute dimethylsulfoxide, and the mixture is then warmed or 6 hours to 40. The reaction mixture is cooled to room temperature, neutralised with lN hydrochloric acid and poured into ice/water. The precipitate is isolated by filtration and thoroughly washed with water. The pure product is obtained after treatment with ether/hexane. Melting point:l76-179~C.

The intermediates and final products listed in the following tables can be prepared in corresponding manner (in the form of mixtures of diastereoisomers, unless otherwise stated):

- - ~2~ 4 Table 1: Compounds of the formula R~
R ~t. OH X=o 2~
;o - C - CH2 - N (I), o~o C=O ~=1 ~

Nr. Rl -R2 R3 R4X Physical data . . ..... _~ _ 1.1 H H H C6H5 N m.p. 185-190 1.2 2-C1 4-Cl H CH3 N m.p. 176-179 1.3 H H H C(CH3)3 N
1.4 H H H C6H3C12(2,4) N
1.5 H H H C6H4Cl(4) N
: 1.6 2-Cl 4-Cl H C2H5 N r~sin 1.7 2-C1 4-Cl H 3 7 N
1.8 2-Cl 4-Cl H 3 7 N
; l.9 2-C1 4-C1 H C4N9~n N
1.10 . 2-C1 4-C1 H 4 9 N
1.11 2-C1 4-C1 H 4 9 N
1.12 2-C1 4-Cl H 5 11 CE
1.13 2-C1 4-Cl H 6 13 N
1.14 2-C1 4-Cl H 8 17 N
1.15 2-C1 4-Cl H C12H25-n N
1.16 2-Cl 4-F H CH3 N resin 1.17 2-C1 4-F H C2H4 N
1.18 2-Cl 4-F H CH3 CH

, Tab l e 1: c ont inuat ion Compoond R~ __ R3 ~ Phys cal data 1.19 2-Cl 4-F H 3 7 N
1.20 2-Cl 4-F H C4Hg-t N
1.21 2-Cl 4-F H C12H25-n CH
1.22 2-Cl 4-Br H CH3 N
1.23 2-Cl 4-Br H C2H5 N
1.24 2-Cl 4-Br H 3 7 N
1.25 2-Cl 4-Br H 4 9 N
1.26 2-Br 4-Br H CH3 N
1.27 H 4-Cl H C2H5 N
1.28 H 4-Br H CH3 N
1.29 H 4-F H CH3 CH
1.30 2-Cl H H CH3 N
1.31 2-F H H C2H5 N
1.32 2-CF3 H H CH3 N
1.33 H 4-CF3 H C(CH3)3 N
1.34 H 4-C6H5 H CH3 N
1.35 H 4-OC6H5 H CH3 N
1.36 H4-oc6H4cl(4) H CH3 N resin 1.37 H 4-OC6H4CH3(4) H CH3 N .
1.38 2-CH3 4-OC6H5 H CH3 N
1.39 2-Cl 4-Cl H cyclopropyl N
1.40 2-Cl 4-Cl H cyclobutyl N
1.41 2-Cl 4-Cl H cyclopentyl N
1.42 2-Cl 4-Cl H cyclohexyl N
_ 4~

Table 1: continuation Compo~nd R I R2 R 3 4 X ~PhyFical data 1.43 2-Cl 4-F H cyclopropyl N
1.44 2-Cl 4-Br H cyclopropyl N
1.45 2-Br 4-Br H cyclopentl N
1.46 2-Cl 4-Cl H C6H5 N m.p. 98-99 1.47 2-Cl 4-Cl H C6H3C12(2,4) N m.p. 167-168 1.48 2-Cl 4-Cl H 6 4 (4) N
1.49 2-Cl 4-C1 6-Cl C6H4Cl(2) CH
1.50 2-C1 4-C1 H C6H4F(2) N
1.51 H 4-C1 H C6H4Cl(4) CH
1.52 H 4-Br H C6H4Br(4) N
1.53 H 4-CF3 H C6H4CF3(4) N
1.54 2-C1 4-Cl H H N resin 1.55 2-Cl 4-F H H N
1.56 2-CH3 H H H N
1.57 3-CF3 H H H N
1.58 2-Cl 4-Cl H H CH
1.59 2-Cl 4-Cl H cyclohexyl CH
1.60 2-Cl 4 Cl H CH3 CH m.p. 203-204 1.61 2-Cl 4-Cl H 6 3( 3)2( ~4) N m.p. 146-147 1.62 2-C1 4-Cl H C6H5 CH m.p. 234-235 1.63 2-Cl 4-Cl H C6H3C12(2,4) CH m.p. 140-144 1.64 2-C1 4-C1 H C6H3cl2(2l4) CH oil 1.65 ~ 3-CF3~ H H ~ CH3 ¦ N ¦

z~

Table 1: continuation Compound Rl R2 - - R3 R4 X Y (C) ._ _ 1.66 3-CF3 H H CH3 CH
1.67 4-OCH3 H H CH3 N
1.68 2-CH3 4-OC6H4cl(4) H CH3 N
1.69 2-CH3 4-OC6H4Br(4~ H C2H5 N
1.70 2-CH3 4-OC6N4Cl(4) H CH3~ _ CH

Table 2- Compounds of the formula R2 ~ 1OR5 X=~ 5 3 ( ) ; / IC CH2 - N R5 = C2H5 = (2) Rs = C3H7-n = (3) Compound Hl 22 R3 _ _ R5 X Phys(ical data , : 2.1 H H H C6H5 1 N
2.2 2-Cl 4-Cl H CH3 1 N resin 2.3 H H H C(CH3)3 1 N
2.4 H H HC6H3C12t2,4) 1 N
2.5 H H H C6H4Cl(4) 1 N
2.6 2-Cl 4-Cl H C2H5 1 N
2.7 2-Cl 4-Cl H 3 7 1 N
2.8 2-Cl 4-Cl H 3 7 1 N
2.9 2-Cl 4-Cl ¦ H C4H9~n 1 N _ _ Table 2:continuation Compound Rl R2 --- R3 -R-4~ -R5 X Physical data _ _ _ 2.10 2-Cl 4-Cl H C4Hg-i 3 N
2.11 2-Cl 4-Cl H C4Hg-t 1 N
2.12 2-Cl 4-Cl H 5 11 1 CH
2.13 2-Cl 4-Cl H 6 13 1 N
2.14 2-Cl 4-Cl H 8 17 1 N
2.15 2-Cl 4-Cl H C12H25-n 3 N
2.16 2-Cl 4-F H CH3 1 N
2.17 2-Cl 4-F H C2H5 1 N
2.18 2-Cl 4-F H CH3 1 CH
2.19 2-Cl 4-F H C3H7~n 1 N
2.20 2-Cl 4-F H C4Hg-t 1 N
2.21 2-Cl 4-F H C12H25-n 1 CH
2.22 2-Cl 4-Br H CH3 1 N
2.23 2-Cl 4-Br H C2H5 2 N
2.24 2-Cl 4-Br H 3 7 1 N
2.25 2-Cl 4-Br H C4Hg-n 1 N
2.26 2-Br 4-Br H CH3 3 N
2.27 H 4-Cl H C2H5 1 N
2.28 H 4-Br H CH3 1 N
2.29 H 4-F H CH3 - 1 CH
2.30 2-Cl H H CH3 1 N
2.31 2-F H 2H5 1 N
2.32 ~ 2-CF3~ H ~ CH3~ _ N

~04(:~

Table 2: continuation Compound Rl R2 R3 R4 R5 X Physical data 2.33 H 4-CF3 H C(CH3)3 1 N
2.34 H 6 5 H CH3 1 N
2.35 H 4-OC6H5 H CH3 1 N
2.362-CH3 4-OC6H4cl(4) H CH3 1 N
2.37 H 6 4 3 H CH3 1 N
2.382-CH3 4-OC6H4Br(4) H CH3 2 N
2.39 2-Cl 4-Cl H cyclopropyl 1 N
2.40 2-Cl 4-Cl H cyclobutyl 2 N _ _ Table 2: continuation (R5 = CH3) Nr. Rl R2 ~~- R3 R4 X Y (C) ,.. _ .
2.41 2-Cl 4-Cl H cyclopentyl N
2.42 2-Cl 4-Cl H cyclohexyl N
2.43 2-Cl 4-F H cyclopropyl N
2.44 2-Cl 4-Br H cyclopropyl N
2.45 2-Br 4-Br H cyclopentyl N
2.46 2-Cl 4-Cl H C6H5 N
2.47 2-Cl 4-Cl H 6 3 2( ~4) N
2.48 2-Cl 4-Cl H 6 4 ( ) N
2.49 2-Cl 4-Cl 6-Cl C6H4Cl(2) CH
2.50 2-Cl 4-Cl H C6H4F(2) N
2.51 H 4-Cl N 6 4 ( ) CH

4~4 Tabl~ 2: continuation (R5 = CH3) Compou~d R~ R2 R3 R4 X Physic al dat a 2.52 H 4-Br H C6H4Br(4) N
2.53 H 4-CF3 H C6H4CF3(4) N
2.54 2-C1 4-C1 H H N resin 2.55 2-C1 4-F H H N
2.56 2-CH3 H H H N
2.57 3-CF3 H H H N
2.58 2-Cl 4-Cl H H CH
2.59 2-Cl 4-Cl H cyclohexyl CH
2.60 2-Cl 4-Cl H CH3 CH m.p. 203-204 2.61 2-Cl 4-Cl H 6 3( 3)2( ' ) N
2.62 2-Cl 4-Cl H 6 3( 3)2( ' ) N
2.63 H H H CH3 N
2.64 3-CF3 3 R CU3 N __ _ _ )4 Table 3: Compounds of the formula R ~- O

~o C=O

Compound R~ 2 Z3 R4 3.1 H H H C6H5 3.2 2-Cl 4-Cl H CH3 3.3 H H H C( CH3 ) 3 3 .4 H H H C6H3C12(2,4) 3.5 H H H C6H4Cl (4) 3 . 6 2-Cl 4-Cl H C2H5 3.7 2-C1 4-C1 H C3H7~n 3.8 2-Cl 4-Cl H C3H7-i 3.9 2-Cl 4-Cl H C4Hg-n 3.10 2-Cl 4-Cl H C4H9-i 3.11 2-Cl 4-Cl H C4Hg-t 3 .12 2-Cl 4-Cl H C5Hl l~n 3 .13 2-Cl 4-Cl H C6H1 3~n 3.14 2-Cl 4-Cl H C8H1 7~n 3 .15 2-Cl 4-Cl H Cl 2H25-n 3.16 2-Cl 4-F H CH3 3. 17 Z-CI 4-F ___ 2 5 i- ~2~ 4 Table 3: continuation CmPrund R1 R2 R3 _ ... __ _ . __ 3.18 2-Cl 4-F H CH3 3.19 2-Cl 4-F H C3H7 3.20 2-Cl 4-F H C4Hg-t 3.21 2-C1 4-F H C12H25-n 3.22 2-C1 4-Br H CH3 3.23 2-Cl 4-Br H C2H5 3.24 2-Cl 4-Br H C3H7-i 3.25 2-C1 4-Br H C4Hg-n 3.26 2-Br 4-Br H CH3 3.27 H 4-Cl H C2H5 3.28 H 4-Br H CH3 3.29 H 4-F H CH3 3.30 2-C1 H H CH3 3.31 2-F H H C2H5 3,32 2-CF3 H H CH3 3.33 H 4-CF3 H C(CH3)3 3.34 H 4-C6H5 H CH3 3.35 H 4-OC6H5 H CH3 3.36 H 4-OC6H4cl(4) H CH3 3.37 H 6 4 3( ) H CH3 3.38 2-CH 4-oC6H5 H CH3 ~z~o~

Table 3: continuation . _ ComNpo-und Rl R2 R3 R4 .
3.39 2-Cl 4-Cl H cyclopropyl 3.40 2-Cl 4-Cl H cyclobutyl 3.41 2-Cl 4-Cl H cyclopentyl 3.42 2-Cl 4-Cl H cyclohexyl 3.43 2-Cl 4-F H cyclopropyl 3.44 2-Cl 4-Br H cycl opropyl 3.45 2-Br 4-Br H cyclopentyl 3.46 2-Cl 4-Cl H C6H5 3.47 2-Cl 4-Cl H C6H3C12(2,4) 3.48 2-Cl 4-Cl H C6H4F(4) 3.49 2-Cl 4-Cl 6-Cl C6H4Cl(2) 3.50 2-Cl 4-Cl H C6H4F(2) 3.51 H 4-Cl H C6H4Cl(4) 3.52 H 4-Br H C6H4Br(4) 3.53 H 4-CF3 H C6H4CF3(4) 3.54 2-Cl 4-Cl ~1 H
3.55 2-Cl 4-F H H
3.56 2-CH3 H H H
3.57 3-CF3 H H H
3.58 2-Cl 4-Cl H H
_ _ 2-C1 4-Cl cyclohexyl -lZ3~409~

Formulation Examples Formulation Examples for liquid active ingredients of the formula I
(throughout, percentages are by weight) Fl. 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 (36 moles of ethylene oxide) 5 ~ - -tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) 12 % 4 cyclohexanone - 15 % 20 ~
xylene mixture 65 ~ 25 ~ 20 %

Emulsion3 of any required concentration can be produced from such concentrates by dilution with water.

F2. 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 160-190) - - 9~ %

These solutions are suitable for application in the form of microdrops.
F3. Granulates a) ~ b) a compound of tables 1 to 3 5 ~ 10 kaolin 94 %
highly dispersed silicic acid 1 ~ -attapulgite - 9o %

~Z~ 4 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

F4. Dusts a) b) a compound of tables 1 to 3 2 ~ 5 highly dispersed silicic acid 1 5 talcum 97 ~ ~
kaolin - go ~

Ready-for-use dusts are obtained by intimately mixing the carriers with the acitve ingredient.

Formulation examples for solid acti~e ingredients of the formula I
(throughout, percentages are by weight) F5. 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 (7-8 moles of ethylene oxide) _ 2 %
highly dispersed silicic acid5 % 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.

F6. Emulsifiable concentrate a compound of tables 1 to 3 10 %
octylphenol polyethlene glycol ether (4-5 moles of ethylene oxide) 3 %
calcium dodecylbenzenesulfonate 3 ~2~

~ 38 -castor oil polyglycol ether (36 moles of ethylene oxide) 4 cyclohexanone 30 xylene mixture 50 ~

Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

F7. 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.

F8. Extruder granulate . . . _ 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 strem of air.

F9. 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 polyethlene glycol. Non-dusty coated granulates are obtained in this manner.

~Z~04~1~

F10. Suspension concentrate a compound of tables 1 to 3 40 ethylene glycol 10 nonylphenol polyethylene glycol (15 moles of ethylene oxide) 6 sodium lignosulEonate 10 carboxymethylcellulose 1 37 % aqueous formaldehyde solution 0.2 silicone oil in the form of a 75 %
aqueous emulsion 0.8 X
water 32 ~

The finely ground active ingredient is intimately mixed with the aduvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biological Examples Example Bl: 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 (0.002 ~). After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours at 95-100 ~ relative humidity and about 20C
and then stood in a greenhouse at about 22C. 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 95-100 ~
relative humidity and about 20C and then stood in a greenhouse at about 22C. Evaluation or rust pustule development is made 12 days ~LZ~Q~4 after infection. Compounds of Tables 1 to 3 are very effective against Puccinia fungi. Puccinia attack is 100 % on untreated and infected control plants. Compounds 1.1, 1.2, 1.6, 1.16, 1.36, 1.46, 1.47, 1.54, 1.60 to 1.64 and 2.2 and others inhibit Puccinia attack to 0-5~.
xample B2: Action against Cercospora arachidicola in groundnut plants . _ Residual protective action .
Groundnut plants 10-15 cm in height are sprayed with a spray mixture (0.006 %) prepared from a wettable powder formulation of the test compound, and infected 48 hours later with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at about 21C 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.

Compared with untreated and infected controls (number and size of the specks = 100%), Cercospora attack on groundnut plants treated with compounds of Tables 1 and 2 is substantially reduced. In this test, compounds 1.1, 1.2, 1.6, 1.16, 1.36, 1.54 and 2.2 inhibit the occurrence of specks almost completely (1-10~).

Example B3: Action against Erysiphe graminis on barley a) Residual protective action Barley plants about 8 cm in height are sprayed with a spray mixture (0.002 %) 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 22C. The extent of the infestation is evaluated after 10 days.

121~4~4 b) Systemic action Barley plants about 8 cm in height are treated with a spray mixture (0.002 %), based on the volume of the soil) prepared from the tese ccmpound 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 22C and evaluation of infesta-tion 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. Compounds 1.1, 1.2, 1.6, 1.16, 1.54 and 2.2 and other compounds of Tables 1 and 2 inhibit fungus attack on barley to 0 to 5%.
xample B4: Residual-protec~ive action against Venturia inaequalis on _pple shoots Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.006 %) prepared from a wettable powder formulation of the test compound. The plants are infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100 ~ relative humidity and stood in a greenhouse for a further 10 days at 20-24C. Scab infestation is evaluated 15 days after infection.

Compounds 1.1, 1.2, 1.6, 1.47, 1.60 to 1.64, 2.2 and others inhibit attack to less than 20~. Venturia attack is 100~ on untreated and infected shoots.

~;~lQ~4 Example B5: ~ction against Botrytis cinerea on apples Residual protective action Artificially damaged apples are treated by dropping a spray mixture (0.02%) prepared from the test compound formulated as wettable powder onto the injury sites. The treated fruit is then inoculated with a spore suspension of Botrytis cinerea and incubated for 1 week at high humidity and about 20 C. Fungicidal action is evaluated by examining the fruit for the presence of rot and the size of the injury sites attacked by rot. After treatment with compounds of Tables 1 and 2, e.g. compounds 1.1, 1.6, 1.46 and 2.2, no or almost no injury sites attacked by rot are observed.

Claims

What is claimed is:

1. A compound of the formula I

(I), wherein R1, R2 and R3 each independently are hydrogen, halogen, C1-C4alkyl, CF3, unsubstituted or substituted phenyl or unsubstituted or substituted phenoxy, R4 is hydrogen, C1-C10alkyl, C3-C6cycloalkyl or unsubstituted or substituted phenyl, X is -CH= or -N=, and R5 is hydrogen, C1-C12alkyl, C2-C4alkenyl, or unsubstituted or substituted benzyl, or an acid addition salt, a quaternary azolium salt or a metal complex thereof, and wherein any substituents in a phenyl, phenoxy or benzyl group are chosen from C1-C4 alkyl, C1-C4 alkoxy, C1-C3-haloalkyl, halogen, and/or cyano.

- 43a -

2. A compound of the formula I according to claim 1, wherein R1, R2 and R3 are each independently hydrogen, halogen, C1-C3alkyl, CF3, phenyl, phenoxy, or phenyl or phenoxy each substituted by C1-C4-alkyl, C1-C4alkoxy, C1-C3haloalkyl, halogen or cyano; R4 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl, phenyl, or phenyl substituted by C1-C4alkyl, C1-C4 alkoxy, C1-C3 haloalkyl, halogen or cyano; R5 is hydrogen, C1-C8alkyl, C2-C4alkenyl, propargyl, benzyl, or benzyl which is mono- or disubstituted by fluorine, chlorine, bromine and/or C1-C3alkyl, and X is -CH= or -N=, or an acid addition salt, a quaternary azolium salt or a metal complex thereof.

3. A compound of the formula I according to claim 2, wherein R1, R2 and R3 are each independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl, CF3, phenyl, phenoxy, C6H4Cl(4), C6H4CH3(4), C6H3Cl2(2,4), OC6H4Cl(4), OC6H4CH3(4) oder OC6H3Cl2(2,4); R4 is hydrogen, C1-C4alkyl, C3-C6cycloalkyl, phenyl, or phenyl substituted by methyl, methoxy, CF3, F, Cl, Br or CN; R5 is hydrogen, C1-C6-alkyl, C3-C4alkenyl, propargyl, benzyl or benzyl which is mono- or disubstituted by fluorine, chlorine and/or methyl, and X is -N=; or an acid addition salt, a quaternary ammonium salt or a metal complex thereof.

4. A compound of the formula I according to claim 3, wherein R1 is hydrogen, 2-Cl, 2-Br, 2-F, 2-CF3, 2-C6H5, 2-OC6H5, 3-F, 3-Cl, 3-Br, 3-CF3, 3-C6H5 or 3-OC6H5; R2 is hydrogen, 4-Cl, 4-Br, 4-F, 4-CF3, 4-C6H5, 4-OC6H5, 4-C6H4Cl(4), 4-C6H4CH(4), 4-C6H3Cl2(2,4), 4-OC6H4Cl(4), 4-OC6H4CH3(4), 4-OC6H3Cl2(2,4), 4-O-C6H4F(4), 5-Cl, 5-Br, 5-F or 5-CF3; R3 is hydrogen; R4 is hydrogen, methyl, phenyl or 2,4-dichlorophenyl; R5 is hydrogen, C1-C5alkyl, allyl, propargyl, benzyl, 2-halobenzyl, 4-halobenzyl, 2,4-dihalobenzyl, 2,6-dihalo-benzyl or 3,4-dihalobenzyl and X is -N=; or an acid addition salt, a quaternary azolium salt or a metal complex thereof.

5. A compound of the formula I according to claim 4, wherein R1 is 2-H, 2-F, 2-Cl or 2-Br; R2 is 4-F, 4-Cl, 4-Br or 4-CF3; R3 is hydrogen; R4 is hydrogen, methyl, phenyl or 2,4-dichlorophenyl; R5 is hydrogen, C1-C5alkyl, allyl, propargyl, benzyl, 2,6-dichloro-benzyl, 4-chlorobenzyl, 4-fluorobenzyl or 2,4-dichlorobenzyl, and X
is -N=; or an acid addition salt, a quaternary azolium salt or a metal complex thereof.

6. A compound of the formula I according to claim 1, selected from the group consisting of:
2-(2,4-dichlorophenyl)-2-hydroxy-3-(1H-1,2,4-triazol-1'-yl)-propanal 2-(2,4-dichlorophenyl)-2-hydroxy-1-(1H-1,2,4-triazol-1'-yl)butan-3 one 2-(2,4-dichlorophenyl)-2-hydroxy-1-(1H-1,2,4-triazol-1'-yl)-pentan-3-one 2-(2,4-dichlorophenyl)-2-methoxy-1-(1H-1,2,4-triazol-1'-yl)-butan-3-one 2-(2-chloro-4-fluorophenyl)-2-hydroxy-1-(1H-1,2,4-triazol-1'-yl)-butan-3-one 2-[2-methyl-4-(4'-chlorophenoxy)]-2-hydroxy-1-(1H-1,2,4-triazol-1'-yl)-butan-3-one

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

(II) with an azole of the formula III

(III), to give first a compound of the formula Ia (Ia) or by reacting an .alpha.-haloketone or an .alpha.-haloaldehyde of the formula IV

(IV), with paraformaldehyde and a strong non-nucleophilic base, and, by subsequent addition of an azole of the formula III, further reacting the intermediate to give a corresponding alcohol of the formula Ia and, in both variants, if desired, converting the alcohol Ia in conventional manner R5-W (V) into an ether of the formula I, in which formulae Ia, II, III, IV
and V above the substituents R1, R2, R3, R4, R5 and X are as defined for formula I, M is hydrogen or a metal atom, Hal is halogen, and W is OH or a customary leaving group.

8. A method of controlling microorganisms or of preventing attack by such microorganisms, and/or of regulating plant growth, which comprises applying to plants or to the locus thereof an effective amount of a compound of the formula I as claimed in any one of claims 1 - 3.

9. A process according to claim 7 where in Hal is bromine or chlorine.