CA1215374A - Microbicidal 1-carbonyl-1-phenoxyphenyl-2- azolylethanol-derivatives - Google Patents

Abstract

Case 5-14196/B

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

(I) wherein R1 and R2 are each independently hydrogen, halogen C1-C4alkyl or CF3, and Rn denotes one to three alkyl, alkoxy, haloalkoxy, halo-alkyl, halogen and/or cyano groups, R4 is hydrogen, C1-C10alkyl, C3-C6cycloalkyl or unsubstituted or substituted phenyl, X is -CH= or -N=, R5 is hydrogen, C1-C12alkyl, C2-C4alkenyl, C2-C4alkynyl, or unsub-stituted or substituted benzyl; and A is the radical wherein R6 and R7 are each independently C1-C12alkyl, unsubstituted or substituted phenyl, or both together form a C2-C4alkylene bridge which is unsubstituted or substituted by one or more identical or different members selected from the group consisting of C1-C4alkyl, C2-C4alkenyloxymethyl or C1-C3alkoxymethyl; and to the acid addition salts, quaternary azolium salts and metal complexes 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

~2153~

Case 5-14196/B

Microbicidal l-carbonyl-l-phenoxyphenyl-2-azolylethanol derivatives The present invention relates to novel l-carbonyl-l-phenoxyphenyl-2-azolylethanol derivatives of the formula I below and to ~he 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 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 novel compounds or compositions for regulating plant growth and for controlling harmful microorganisms.

Accordingly, the invention relates to compounds of the general formula I

! - O 1 2 \ i (I) R =o ~ / A =N

wherein Rl and R2 are each independently hydrogen, halogen Cl-C4alkyl or CF3, and R denotes one to three alkyl, alkoxyl haloalkoxy, haloalkyl, halogen and/or cyano groups, R4 is hydrogen, Cl-ClOalkyl, C3-C6cycloalkyl or unsubstituted or substituted phenyl, X is -CH= or -N=, d en C -C alkyl~ C2-C4alkenyl, 2 4 unsubstituted or substituted benzyl; and A is the radical .

1.' wherein R6 and R7 are each independently Cl-C12alkyl, unsubstituted or substituted phenyl, or both together form a C2-C4alkylene bridge which is unsubstituted or substituted by one or more identical or different members selected from the group consisting of Cl-C4alkyl, C2-C4alkenyloxymethyl or Cl-C3alkoxymethyl;
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.
Alkenyl 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~ CMBr2 and preferably CF3-~L215374 Wher~ R6 and R7 in the molecular fragment I

together form a C2-C4alkylene bridge, said fragment, depending on the number of carbon atoms, is an unsubstituted or substituted 1,3-dioxolan, 1,3-dioxan or 1,3-dioxepane ring.

Accordingly, the invention relates to the free organic compounds of the formula I in the form of open or cyclised ketals, in particular acetals, and to the acid addition salts, quaternary azolium salts and metal complexes thereof. The free compound are preferred, in particular the lH-1,2,4-triazoles. The acetals are preferred to the ketals.

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-sulfonic 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, trifluoro-acetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates etc. of the elements of the third and fourth main grcup of the Periodic Table such as aluminium, tin or lead, and of the first to eighth auxiliary group such as chromium, manganese, 2~5374 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. 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 phyto-pathological microorganisms and for regulating plant growth, for which utility the triaPolyl-l-methyl derivatives falling within the scope of formula I are preferred. The compounds of forrnula I are very well tolerated by cultivated plants.

On account of their pronounced microbicidal action, preferred compounds of the formula I, in increasing order of preference, are those compounds which contain the following substituents or combinations thereof:

For Rl and R2, each independently of the other:

a) hydrogen, halogen, Cl-C3alkyl, CF3;

b) H, F, Cl, Br, CH3, C2H5, CF3.

c) Rl: H, 2-Cl, 2-Br, 2-F, 2-CF3, 3-F, 3-Cl, 3-Br, 3-CF3, 4-Cl, 4-Br, 4-F, 4-CF3, 5-Cl, 5-Br, 5-F, 5-CF3.
R2: H.

d) Rl: 2-H, 2-F, 2-Cl, 2-Br, 2-CH3.
R2: H-12~S374 For R :a) hydrogen, Cl-C4alkyl, Cl-C4alkoxy, Cl-C4haloalkoxy, Cl-C3haloalkyl, halogen and/or cyano;

b) hydrogen, chlorine, dichloro, fluorine, bromine, methyl, difluoro, CF3, OCF3;

c) hydrogen, 4-chloro, 2,4-dichloro, 4-fluoro, 2,4-difluoro, 4-bromo, 4-methyl, 4-CF3, 4-OCF3;

d) All meanings as under c), except that for the p-phenoxyphenyl group:

For A: a) -f-O(Cl-C4alkyl), -f-O(Cl-C4alkyl), o~Cl-C4alkYl) O(unsubstituted or substituted phenyl) --C-- --C-- --C--/\ /\ /\
O O O O O O
l l l l l l ~ -Cl-C4alkyl. C -C alkyl-- - -C -C alkyl, --C-- --C --C--/\ /\ /\
O O O O O O

2 3 ' -CH2cH2cH=cH2 C-- C-- --C--/\ /\ /\
O O O O O O
l l l l l l . . .
\/\ \/ /\/\
Cl-C4alkyl ; Cl-C4-alkyl Cl-C4-alky Cl-C4alkyl Cl-C4alkyl 12~s37g C--C--/\ /\
o o o o ; ~-Cl-C4alkyl, ; /-/\ \
Cl-C4alkyl cl-C4alkyl Cl-C4alkyl, b) _1_0CH3 -C-OC2H5 0/ \ / \
1CH3C2H5 I f f l -Cl-C3alkYl ~

c c c c /\ /\ /\ /\
o o o o o o o o - -CH20CH3 , CH3-- - -CH3 --C-- --C-- --C--/\ /\ /\
O O O O O
l l l l l l . . . .
/\/\ \/ \/
C~3 ~ CH3 1 / ;

or R4 a) hydrogen~ Cl-C alkyl, C3-C6cycloalkyl, phenyl, or phenyl substituted by Cl-C4alkyl, Cl-C4alkoxy, Cl-C4haloalkyl, halogen or cyano;

b) hydrogen, Cl-C4alkyl, C3-C6cycloalkyl, phenyl or phenyl substituted by methyl, methoxy, CF3, F, Cl, Br or CN;

c) hydrogen, methyl, phenyl, 2,4-dichlorophenyl;

d) hydrogen.

~S374 or R5: a) hydrogen, Cl-C8-alkyl, 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-halo-benzyl, 4-halobenzyl, 2,4-dihalobenzyl, 2,6-dihalobenzyl,

3,4-dihalobenzyl, where halo denonotes halogen;

d) hydrogen.

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

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

a) compounds of the formula I, wherein Rl and R2 are each independently hydrogen, halogen, Cl-C3alkyl or CF3; R is hydrogen, Cl-C4alkyl, Cl-C4alkoxy, Cl-C4haloalkoxy, Cl-C3haloalkyl, halogen and/or cyano; A is one of the molecular fragments -C-O(Cl-C4alkyl ), -C-O(Cl-C4alkyl ), O(Cl-C4alkyl) O(unsubstituted or substituted phenyl) C --C --C--O O O O O O
~ _ O , - -Cl-C4alkYll C -C alkyl-^ - -C -C alkyl, 153~4 --c-- C-- C
/\ /\ /\
o o o o o o 20CH3 , ---CH2CH2CH=C~2 ' ;

--c-- --c --c--/\ /\ /\
o o o o o o \/\ \/ /\/\ .
Cl-C4alkyl ; Cl-C4-alkyl Cl-C4-alkyl Cl-C4alkyl Cl-C4alkyl --c-- --c--/\ /\
o o o o ; /--Cl-C4alkyl or ;!

/\ \
Cl-C4alkyl Cl-C~alkyl Cl-C4alkyl , R4 is hydrogen, Cl-C6alkyl, C3-C6cycloalkyl, phenyl or phenyl substitued 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 -N=; and the acid addition salts, quaternary azolium salts and metal complexes thereof, b) compounds of the formula I, wherein each of Rl and R2 are independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl or CF3; R is hydrogen, chlorine, dichloro, fluorine, bromine, methyl, difluoro, CF3 or OCF3; A is one of the molecular fragments -O- -O--C-OCH3 2 5 / \ / \
O O O O
oc~3 C2H5 ---Cl -C3 C-- C C --c--/\ /\ /\ /\
o o o o o o o o - -CH20CH3 , CH3-~ - ~-CH3 ~ CH3 --C-- --C--/\ /\
O O O o or ~ ;
\ / O
/\

R4 is hydrogen, Cl-C4alkyl, C3-C6cycloalkyl, phenyl or phenyl substituted by methyl, methoxy, CF3, F, Cl, Br or CN; R5 is hydrogen, Cl-C6alkyl, 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 a~olium salts and metal complexes thereof;

c) compounds of the formula I, wherein Rl is hydrogen, 2-Cl, 2-Br, 2-F, 2-CF3, 3-F, 3-Cl, 3-Br, 3-CF3, 2-CH3, 4-Cl, 4-Br, 4-F, 4-CF3, 5-Cl, S-Br, 5-F or 5-CF3; R2 is hydrogen; Rn is hydrogen, 4-chloro, 2,4-dichloro, 4-fluro, 2,4-difluoro, 4-bromo, 4-methyl, 4-CF3 or

4-OCF3; A is one of the molecular fragments -O- -O--C-OCH3-C-Oc2H5 / \ / \

._~, ---Cl-C3alkYl, C-- C-- --C-- --C--/ \ / \ / \ / \ -O O O O O O O O
- -CH20CH3 , CH3-- - -CH3 ~Z15;~74 --c----c-- --c--/\ /\ /\
o o o o o o ~ or ~ ;
/\/\ \/ \/
CH ~ CH ~
3 3 1 / \

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-dihalobenzyl; and X is -N=; and the acid addition salts, quaternary azolium salts and metal complexes thereof;

d) compounds of the formula I, wherein Rl is 2-H, 2~F,2-Cl, 2-Br or 2-CH3; R2 is hydrogen; R in a para-positioned phenyl group is hydrogen, ~-chloro, 2,4-dichloro, 4-fluoro, 2,4-difluoro, 4-bromo, 4-methyl, 4-CF3 or 4-OCF3; A is one of the molecular fragments -O- -O--C-OCH3 C OC2 5 0/ \0/ \

3 ~ _ ~, - -Cl-C3alkYl , --C-- C --C --C--/ \ / \ / \ / \
O O O O O O O O
l l l l l l l l - ~-CH20CH3 , CH3-~ - -CH3 --C-- --C-- C--/\ /\ /\
O O O O O O
l l l l l l ~ . , or /\/\ \/ \/
CH3 CH3 1 / ;

R4 is hydrogen; R5 is hydrogen; and X is -N=; and the acid addition salts, quaternary azolium salts and metal complexes thereof.

~Z~374 Examples of particularly pre~erred compounds are:

l-(lH-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl~-3,3-di-methoxypropan-2-ol (compound 1.1);

l-(lH-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl]-2-(1,3-dioxolan-2-yl)-ethan-2-ol (compound 1.2);

l-(lH-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl]-2-(4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol (compound l.S);

l-(lH-1,2,4-triazol-1'-yl)-2-[p-(4-bromophenoxy)phenyl~-3,3-di-methoxypropan-2-ol (compound 1.6);

l-(lH-1,2,4-triazol-1'-yl)-2-[p-(4-bromophenoxy)phenyl]-2-(4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol (compound 1.7);

l-(lH-1,2,4-triaæol-1'-yl)-2-[p-(4-chlorophenoxy)-2-methylphenyl~-3,3-dimethoxy-propan-2-ol (compound 1.8);

l-~lH-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)-2-methylphenyl]-2-(1,3-dioxolan-2-yl)-ethan-2-ol (compound 1.9);

l-(lH-imidazol-l'-yl)-2-~p-(4-chlorophenoxy)phenyl]-3,3-dimethoxy-propan-2-ol (compound 2.1);

l-(lH-imidazol-l'-yl)-2-[p-(4-chlorophenoxy)phenyl~-2-(4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol (compound 2.5);

l-(lH-imidazol-l'-yl)-2-[p-(4-bromophenoxy)phenyl]-3,3-dimethoxy-propan-2-ol (compound 2.6);

l-(lH-imidazol-l'-yl)-2-[p-(4-chlorophenoxy)phenyl]-3,3-diethoxy-propan-2-ol (compound 2.25);

~L~1S374 l-(lH-1,2,4-triazol-1 -yl)-2-[p-(4-chlorophenoxy)-2-chlorophenyl]-3,3-dimethoxypropan-2-ol (compound 1.24);

l-(lH-1,2,4-triazol-1 -yl)-2-~p-(2,4-dichlorophenoxy)phenyl]-3,3-dimethoxypropan-2-ol (compound 1.26);

l-(lH-1,2,4-triazol-l -yl)-2-[p-(2,4-dichlorophenoxy)phenyl~-2-(4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol (compound 1.27);

l-(lH-1,2,4-triazol-1 -yl)-2-[p-(4-chlorophenoxy)phenyl]-2-(2-methyl-1,3-dioxolan-2-yl)-ethan-2-ol (compound 1.13);

l-(lH-1,2,4-triazol-l -yl)-2-[p-(4-chlorophenoxy)-2-methylphenyl]-2-(4-methyl-1,3-dioxolan-2-yl)-ethan-2-ol (compound 1.42);

l-(lH-1,2,4-triazol-1 -yl)-2-[p-(4-chlorophenoxy)-2-methylphenyl~-2-(1,3-dioxan-2-yl)-ethan-2-ol (compound 1.43);

l-(lH-1,2,4-triazol-1 -yl)-2-~p-(phenoxy)phenyl~-2-(2-phenyl-4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol (compound 1.45);

l-(lH-imidazol-l -yl)-2-~p-(phenoxy)phenyl]-2-(2-phenyl-4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol (compound 2 42).

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

~ 2 0 ! . o ~ ~ c - CH2 (II) Rn~

with an a~ole of the formula III
X=-M-N ~ (III) -N
to give first an alcohol of the formula Ia OH X=~
~ - ~ ~f - CH2-N ~ (Ia) R ~ / A =N

and converting the alcohol la 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 and III and V above the su 1' 2' n' 4' 5' defined 'or 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-R , an acyloxy group, preferably -OCO-R and an isourea radical, preferably -O-C=NR
¦ b , where R , Rb and R are each independently Cl-C3alkyl, Cl-C3haloalkyl, phenyl, or phenyl substituted by halogen, methyl, nitro, trifluoromethyl and/or methoxy.

~ZlS374 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. ~xamples 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, NaO~, LioH, KOH, NaH, Ca(OH)2, KHC03, NaHC03, Ca(HC03)2, K2C03, Na2C03), 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
(M = 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-tives, there are usually also obtained l,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 100C.

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).

~Z~S374 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 V 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,N-dimethylformamide, N,N-di-methylacetamide, hexamethylphosphoric triamide, dimethylsulfoxid~, 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=H) first into a suitable metal salt in a manner known per se, e.g. by reaction with a strong base.

Examples of suitable strong bases are alkali metal and alkaline earth metal hydrides (NaH, 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 is advantageously conducted in an inert medium. Examples of suitable solvents are ethers and ethereal compounds, e.g. di-lower alkyl ~Z~5374 16 ~

ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether and the like), tetrahydrofuran, dioxan and aromatic hydrocarbons such as benzene, toluene or xylenes.

The following solvents for example are suitable for the organic wa~er-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.

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, l,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.

12~374 To prepare the ethers of the formula I, it is also possible to replace the free OH group in the compound of formula la 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.

The introduction of the leaving group is effected by conventinal methods. If W 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 0 to 50C. If W is one of the groups -OS02R , -OCO-R or o-f =NRb NHR , then the reagent will normally be the corresponding acid halide, in particular acid chloride or amidinochloride. 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.

~Z15374 The starting compounds of the formulae III 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 II can be prepared in a manner known per se by epoxidation from the corresponding styrene derivatives of the formula VI

~ O ~ ~ A=CH2 (VI) I

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 NaOH, KOH, NaHC03, in conventional inert solvents. Mo(CO)6 can be used as catalyst in this reaction.

The styrene derivatives of the formula VI can be prepared as described in Org. Synth. 60, 6, from the known styrenes of the formula VIII

R R
~ 2 - O ~ ~ CH=CH2 (VIII) R =0 ~ /

wheren Rl to R3 are as defined for formula I, by reaction with dichlorocarbene (CHC13/NaOH) and subsequent alcoholysis with alcohols of the formula R60H, R70H and/or HO-R6R7-OH.

Epoxides of the formula II, w'nerein the molecular fragment A is the group can be prepared in a manner known per se from ketones of the formula IX

/; \\~ R¦ ~OR 7, o - O ~ ¦¦ C - C ' (IX) R ~o ;\ / OR6 by reaction with dimethylsulfonium methyl imide or dimethylo~.o-sulfonium methyl imide (Corey and Chaykovsky, JACS, 1962, 84, 3782).

The ketones of formula IX are obtainable by different methods which are known from the literature, e.g. where R4 is hydrogen, e.g. by reacting known substituted acetophenones with the corresponding known alcohols R6-OH or R7-OH, in the presence of nitrosyl chloride, or with the alkyl nitriles R60-NO or R70-No (q.v. DE-OS 2 730 462 and DE-OS 2 432 563).

~;Z15374 Further, substituted phenylglyoxals can also be converted selectively into the acetals of the formula IX. Acetals or ketones of the formula IX, wherein e.g. R4 is hydrogen and R6 and R7 are alkyl, can also be prepared from -halo-~-acetoxyacetophenone by reaction with alcohols [W. Madelung and M.E. Oberwegner, Chem. Ber.
65, 931 (1932)].

If the molecular fragment A in formula I is a dioxolan, dioxan or dioxepine ring, then it is advantageous to subject a compound of the formula I, wherein A is -f-O-lower alkyl O-lower alkyl with a corresponding alkanediol, to a transacetylation reaction.

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.), 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.

~1S374 The compounds of the formula I
R R
2 OR5 X=j ~ t ~ C - CH2-N
Rn ~ / l =N

always contain an asymmetrical carbon atom (*) vicinal to the subs~ituents 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 unsymmetrical 1,2- or 1,3-diols leads to a further centre of asymmetry in the resultant dioxolane or dioxan ring. ~our stereo-isomers in the form of pairs of diastereoisomers (cis- and trans-form) are obtained. The individual diastereoisomers can be separated 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-1;i~1~;3~4 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 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.

A further i~portant 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 legumi-nosae, 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 componds of this invention it is possible to control the growth of these cover crops and so to keep the growth in height of these p]ants 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 I it is possible to inhibit or destroy the microorganisms which occur in plants or parts of plants (fruit, lZ1537~

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:

1215;~74 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, sun-flowers, coconuts, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, rnarrows, 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 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 preparations 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 rate of application depend on the risk of infestation by the ~LZlS374 corresponding pathogen (type of fungus). However, the compound 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 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 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).

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 l;ZlS374 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 powder~, 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.

~~S374 More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benz-imidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubsLituted 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 preferably contain 2 sulfonic acid grOupa 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.

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 18 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.

~L2~374 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 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. 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 anc Emulsifiers Annual", MC Publishing Corp. Ringwood, New 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 1 ~, 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 formulate~ 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.

~;~lS37~ 1 The invention is illustrated in more detail by the following Examples, without implying any restriction to w~at i9 described therein. Parts and percentages are by weight.

Preparatory Examples Example Pl: a~ Preparation of the intermediate -- o-- OCH
// ~ // ~ / 3 Cl-~ -0-- -C-CH
\ / \ / 11 \
~=~ 0=~ o OCH3 4-(4-Chlorophenoxy)phenylglyoxal dimethyl acetal 158 g of a-acetoxy-~-bromo-4-(4-chlorophenoxy)acetophenone in 800 ml of absolute methanol are heated to 60C for 1 hour. After half of the methanol has been distilled off, the solution i5 poured into water and extracted with diethyl ether. The combined extracts are dried over sodium sulfate, filtered, and concentrated in vacuo. The residue is recrystallised from diisopropyl ether. Yield: 61 g of yellowish crystals with a melting point of 63-64C.

b) Preparation of a further intermediate // ~ // ~ / 3 Cl-- -0-- -C CH
\ / \ / \
~ = CH2 OCH3 o 2-r4-(4-Chlorophenoxyphenyll-2-dimethoxymethyloxirane To a dispersion of 80 ~ sodium hydride in 400 ml of absolute dimethyl sulfoxide are added 47.9 g of trimethyloxosulfonium iodide in portions under nitrogen. After the exothermic reaction has subsided, the mixture is stirred for 90 minutes and then a solution of 55 g of 4-(4 chlorophenylglyoxal dimethyl acetal in 150 ml of tetrahydrofuran is added dropwise at normal temperature. The mixture is heated to 60C and stirred for 1 hour. Then the reaction mixture ~Z~374 is poured into ice/water and extracted repeatedly with diethyl ether. The combined extracts are washed with brine and water, dried over sodium sulfate, filtered, and concentrated in vacuo, affording 59 g of a brown oil which can be either purified by column chromato-graphy or further processed as crude product.

c) Preparation of the final product OH OCH
~ / 3 Cl-- -o-c -C-CH
\ / \ / I \
=o=~ CH2 OCH3 N
N
Il 11 N - ~

2-(lH-1,2,4-Triazol-l'-yl)-r4-(4-chlorophenoxy)phenyl-3,3-dimethoxypropanol 38 g of 2-[4-(4-chlorophenoxy)phenyl~-2-dimethoxymethyloxirane, 12.3 g of lH-1,2,4-triazole and 1.3 g of potassium tert-butanolate are dissolved in 300 ml of absolute dimethylformamide, and the solution is stirred for 4 hours at 110C. After it has been cooled to room temperature, the dark solution is poured into ice/water and extracted repeatedly with diethyl ether The combined extracts are washed in succession with brine and water, dried, filtered, and concentrated in vacuo. The residue is treated with a small amount of cold diethyl ether. Yield: 30 g of the title compound in the form of beige coloured crystals with a melting point of 135-137C.

~ZlS374 Exa~ple P2: Preparation of o-- -- OH O-o R ~ // ~ I /
Cl-- ~-0-^ -C-CH
\ / \ / I \
f 2 2 5 N

/\
N
Il 11 N - -l-r4-(4-Chlorophenoxy)phenyl~ (4'-ethyl-1,3-dioxolan-2'-yl)-2-(lH-1,2,4-triazol-1'-yl)ethanol 8 g of 1-(lH-1,2,4-triezol-1'-yl)-2-~4-(4-chlorophenoxyphenyl]-2-hydroxy-3, 3-dimethoxypropane, 2.7 g of 1,2-butanediol and 4.3 g of p-toluenesulfonic acid in 150 ml of toluene are slowly heated to the boil in a descending cooler. The distillate contains methanol (confirmation by gas chromatography). No more methanol can be detected after 4 hours. The solution i9 then cooled to room temperature, diluted with diethyl ether, and extracted with sodium carbonate solution. The organic phase is washed with water until neutral, dried over sodium sulfate, filtered, and concentrated in vacuo. Yield: 8 g of a clear yellow oil which is a mixture of diastereoisomers.

lS37~

Example P3: Preparation of CH o-.
~ 3/
Cl-- -0-- -C-CH (= coumpound 5.1) \ / \ / I \

N
N
Il 11 N - o l-r4-(4-Chlorophenoxy)phenyll-1-(4'-ethyl-1,3-dioxolan-2'-yl)-l-methoxy-2-(lH-1,2,4-triazol-1'-yl) ethane 8 g of the alcohol prepared in Example P2 are dissolved in 100 ml of absolute dimethylformamide and to this solution are added, in portions, an equimolar amount of 50 ~ sodium hydride (the sodium hydride is freed from mineral oil beforehand by washing it twice with absolute diemthylformamide). After the evaluation of hydrogen has ceased, 4 g of methyl iodide are stirred in dropwise and the reaction mixture is kept for 6 hours at 40C-50C. The reaction mixture i8 then cooled to room temperature and poured into ice/
water. The reaction product is extracted repeatedly with diethyl ether. The combined extracts are washed with water, dried over sodium sulfate, filtered, and concentrated. The oily crude product is purified over a short column of silica gel with a 10:1 mixture of methylene chloride/methanol as eluant. Yield: 6.8 g of a colourless oil with n5D = 1.5621.

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

1~1$37~

Table 1: Compounds of the formula Rl OH

R ~- I .=

, _ I
Com- R R R R4 A Physical pound 1 2 n ~ata [C]
1.1 H H Cl(4) H /C\ m.p.

1.2 H H Cl(4) H /C\ m.p.
l ! 158-160 1.3 H H F(4) HH5C20 C2H5 1.4 Cl(2) H Cl(4) HCH30 OCH3 1.5 H H Cl(4) H O~C\!o-c2H5 vniDsoclou5s58ogil 1.6 H H Br(4) H /C\ m.p.

C- viscous o~
1.7 H H Br(4) H . - .-C2H5 nD 1. 5684 ¦

121S37~

-Table 1: continuation Co~- R R ~ - R A Phvsical pound 1 2 n 4 data [~C3 1.8 CH3(2) H Cl(4) H CH30 OCH3 r~Slln5671 1.9 CH3(2) H Cl(4) H ~/ \O resin 1,10CH3(2) H Br(4) H CH30 b CH3 1.11CH3(2) H Cl(4) H H5C20 \OC2H5 1.12CH3(2) H F(4) H

1.13 H H Cl(4) CH3 /C\

1.14 H H Br(4) CH3 H5C20/ \OC2H5 1.15 CH3(2) H H CH3 /C\

1.16 CH3(2) H OCF3 CH3 H5C20 C2H5 .

1.17 CH3(2) H Cl(4) C2H5 O./c\~

1.17a CH3(2) H H CH3 0/c\~-CH3 resin ~Z1~374 Table 1: continuation _ _ poumnd Rl R2 R R4 A Physical 1.18CH3(2) H Br(4) C2H5 CH30 OCH3 1.19 CH3(2) H F(4) C3H7~n lO/c\lo 1.20 CH3(2) H Cl(4) C(CH3)3 -C-n-H~C30 ~C3H7-n 1.21 CH3(2) H Br(4) C3H7-iH3CO OCH3 1.22 Cl(2) Cl(6) H CH3 . - !

1.23 CH3(2) H Cl~4) CH3 ~/ \0 ~ \./-1.24 Cl(2) H Cl(4) H /C\ m.p.

1.25 H H Cl(4) H H5C20 OC2H5 1.26 H H C12(2,4) H /C\ m.p.
. CH30 OCH3 114-115 .Z7 11 ~ r~ ~ ~ ~b~

Table 1: continuation Com- ¦ R R R l A Physical pound 1 2 n 4 data [C]
. .__.
1 28 I ~ H C1(4) I H ~ /C\

1.29CH3(2) H Cl(4) H ~CH20CH3 1.30CH3(2) H H H ~-CH20CH3 1.31CH3(2) H Cl(4) HcH3_~./C\~_cH3 1.32Cl(2) H Cl(4) HCH3-. - ~-CH3 1.33 H H Cl(4) H CH3 1.34CH3(2) H Cl(4) H~,/,S/ \CH3 : C'~',~ `' 12~S374 Table l: conti~uation Com- R R~ R R A ?hysical pound l 4 data [C]
1.36 Cl(2) H C12(2,4) H ~C~?-c2H5 1.37 CH3(2) H Cl(4) H ~/C\~-C2H5 1.38 CH3(2) H Cl(4) H ~ C H -n 1.39 CH3(2) H Cl(4) CH3q./C\~_c2H5 1.40 CH3(2) H Cl(4) CH3 /C\

\-/ \CH3 1.41 Cl(2) H Cl(4) CH3 ol/C\~

1.42 CH3(2) H Cl(4) H ~/ \0 n51.5557 1.43 CH3(2) H Cl(4) H /C\ m.p.
. \./ 148-151 1.44 Cl(2) H CH3(4) H \ /

: l.45 R H H C6H5 . - !-C2H~ resin J~21S374 Table 2: Compounds of the formula R

Com- R R R R A ¦ Physical pound 1 2 n 4 data [C]

2.1 H H Cl(4) H /C\ m.p.

2.2 H H Cl(4) H /C\

2.3 H H F(4) HH5C20 \OC2H5 2.4Cl(2) H Cl(4) HCH30 OCH3 2.5 H H Cl(4) H~/C\~-C2H5 ;60-164 2.6 H H Br(4) H /C\ m.p.

2.7 H H Br(4) H. - !-C2H5 2.8CH3(2) H Cl(4) HCH30 OCH3 ~21537~

Table 2: continuation pound Rl 2 ~ n R4 ~ d Yta ~C]

2.9 CH3(2) H Cl(4) H C\

2.10 CH3(2) H Br(4) H CH30 OCH3 CH3(2) H ; C1(4) ~ H H C o/ OC

2.12 H H H CH3 o./c\o!

2.13 H H Cl(4) CH3 CH30 OCH3 2.14 H H Br(4) CH3 H5C20 OC2H5 2.15 CH3(2) H H CH3 o./c\o!

2.16 CH3(2) H Cl(4) CH3 H5C20 OC2H5 2.17 CH3(2) H ~C1(4) C2H5 o./c\

L~ H ¦ H ~ CH3 ~ _ !-CH~

~Z~;374 Table 2: continuatiOn Com- R R R Physical pound 1 2 n 4 data [C]
.
2.18 CH3(2) H Br(4) C2H5 CH30 OCH3 2.19 CH~(2) H F(4)C3H7~n 10./C\~_c2H5 2.20 CH3(2) H Cl(4)C(CH3)3 -C-H C 0/ \OC H

2.21 CH3(2) H Br(4)C3H7-i H3C0/ 0CH3 2.22 Cl(2) Cl(6) H CH3 1 !

2.23 CH3(2) H Cl(4) CH3 /C\

2.24 Cl(2) H Cl(4) HCH30 OCH3 2.25 H H Cl(4) 1 5 2 2 5 2.26 H H C12(2,4) H I /C\ .

.~ ¦ CH30 OCH3 2.27 H H C12(2,4) H ¦ /C\

L L I . -C2H5 .

~Z1537~

Table 2: continuation ¦ Com- R R A I Physical ~ound 1 2 n 4 data [C]
. .
2 . 28 H H Cl (4) H ~/C\~-cH2ocH3 2 . 29 CH3 (2) HCl (4) H---CH20CH3 ~230 ~C113(2) 1 I I ! \g-c32oc3 .31 C113(2) ~Cl(4) C~3 ~. - g-cll3 2 . 32 Cl ( 2) H~ Cl (4) ~ ~/ \g .33 3 , Cl(4) 11o/c\q 2 . 34 CH3 (2) , H Cl (4) H /C\

~ ' CH3 .

.35 CI(2) , 3 .C1(4) ~ H ~ /G\

2.36 CH3(2) H ~ ~ ~/ \g i21~374 Table-2: continuation Com- ¦ R R R A Physical pound I 1 2 4 data [c]
2.37 CH3~2) H Cl(4) H~/C~-c2H5 .38 ~CH3(2) ~ H Cl(4) 2.39 CH3(2) H Cl(4) CH3~./C\~_c2H5 2.40 CH3(2) H Cl(4) CH3 /C\

\-/ \CH3 2.41 Cl(2) H Cl(4) CH3 /C\
¦ ---CH20CH3 2.42 H H H C6H5~/C\~-C2H5 resin lZ~537~

Table 3: Compound of the formula Rl OH

X ~ CH2~

Com- Rl R2 l R A X data [ C~
_~
3.1 H H 3-OC6H4cl(4) CH30 OCH3 N

3.2 H H 3-OC6H4cl(4) CH20 OCH3 CH

3.3 H H 3-OC6H4cl(4) ~ _ ~ N

.4 H H ~ 3-OC6H4c~3~4) ~C\ N

5 ¦CH3(2) I ~ I C H ¦

.6 CH3(4) 5-C1 2-OC6H5 0 ~0 ¦CI~21 H 3-0~6H4CI(4) 0 0 12~5374 Table 2: continuation Com- R ¦ R ¦ X Physical pound 1 1 2 l data [C]
. . ___ 3.8 C 3(2) H-OC6H4Cl(4) -C- N

3.9 CH3(2) H3-OC6H4cl(4) ~ CH OCH3¦

3.10 Cl(2) H 3-OC6H4cl(4) ~ CH20CH3 N

lZ~5374 Table 4: Intermediates of the formula ~0~

obtained as viscous oils or resins.
. _ COomund Rl R2 R A R4 4.1 H H 4-OC6H4cl(4)CH30 OCH3 H

4.2 H H 4-OC6H4Clt4) C\ H

4.3 H H 4-OC6H4F(4)H5C20 OC2H5 H

4.4 Cl(2) H 4-OC6H4cl(4)H3CO OCH3 H

.5 H H ¦ 4-OC6H4C1 4) ¦ r/c\ ~ H

4.6 H H 4-OC6H4Br(4) /C\
CH30 OCH3 ¦ H

4.7 U H 4-OC6U4Br(4) q - q C H H

4.8 CH3(2) H 4-OC6H4CI(4) CH ~ CU L

~2~5374 - 46 ~

Table 4: continuation Com- ~ Rl ~ R2 R

4.9 CH3(2) H 4-OC6H4C1(4) /C\ H

.lO ICH3(2) H ~ CH O OC~I3 4.11CH3(2) H ,H5C20 C2H5 H

4.12 H H 4-OC6H5 1 -C- CH3 4.13 H H 6 I CH30 OCH3 CH3 4.14 H H H5C20 OC2H5 CH3 4.15ICH3(2) H 4-OC6H5 C\ CH3 4.16 CH3(2) I H H5C20 C2H5 CH3 4.17 CH3(2 H 4-OC6H4Cl(4) -C- ,C H

4.18 CH3(2) j H ~4-OC6H4Br(4) ¦ /C\ ~C2H5 I ~

~Z~374 Table 4_ continuation R~ __ _ A R~

4.19 ~CH3(2) H 4-OC6H4F(4) 0/ \0 C3H7~n 4.20 CH3(2) H 4-OC6H4C1(43 /C~ C(CH3)3 n~H7C3 OC3H7-n 4.21 CH3(2) H 4-OC6H4~r(4) CH30 OCH3 C3H7-i 4.22 C1(2)Cl(6) 4-OC6H5 . - ~ CH3 4.23 CH3(2) H 4-OC6H4cl(4) /C\ CH3 4.24 iCl(2) H 4-OC6H4C1(4) CH3 ~ \OCH3 H

4.25 H H 4-OC6H4cl(4) H5C20 C2H5 H

4.26 ¦ H I H 4-OC6H4cl(4) H5C20 C2H5 H

4) 0/ \0 H
i' .

Table 4: continuation . poond Rl R2 R4 . ~ . _ 4.28 H H 4-OC6H4cl(4)/C\ H

4.29 CH3(2) H 4-OC6H4cl~4~/C\ H

4.30 CH3(2) H 4-OC6H5 lo/c\~ H

4.31 CH3(2) H 4-OC6H4cl(4)/C~ H

4.32 Cl(2 ~ 1~3C q. - ~-C~3 4.33 H H 4-OC6H4C1(4)ol ! H

\-/ \CH3 4.34 CH3(2) H 4~0C6H4Cl(4) O./C\O! H

\-/ \CH3 4.35 Cl(2) H 4-OC6H4cl(4) /C\ H

CH3 _ 121~i374 Table 4: continuation Com- Rl R2 R
pound 4.36C1(2) H 4-OC H3C12(2,4) -C- H

4.37CH3 (2) H 4-C6H4cl(4) ~ C2H5 H

4.38CH~(2) H 4-C6H4C1(4) O~ ~O H

4.39CH3 (2) H 4-OC6H4cl(4) -C- H

4.40CH3 (2) H 4-OC6H4cl(4) ~ / \CH CH3 4. 41Cl(2) H 4-OC6H4cl(4) ~ _ 1-CH20CH3 CH3 4.42CH3(2) H 3-C6H4C1(4) CH30 OCH3 H

4.43CH3(4) H 3-C6H4C1(4) CH30 OCH3 H

4.44Cl (2) H 3-OC6H4cl(4) 0l l H

-- so --Table 4: continuation Com- Rl R2 R A R

4.45 CH3(2) H 3-OC6H4CH3(4) ~ -C2H5 H

4.46 CH3(2) H 3-OC6H4cl(4) o/ \o H

4.47 CH3(4)5-Cl 2-OC6H5 /C\ H

4.48 Cl(2) H 3-OC6H4cl(4) \ / \CH H

4.49 CH3(2) H 3-0 6H4Cl(4) , q 4.50 CH3(2) H 3-OC H4C1(4) ~ !-CH20CH3 H

4.51 Cl(2) H 3-OC6H4cl(4) ~ -CH20CH3 H

~;~i5374 Fonmulation 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 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 ~

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

F2. Solutions a) b) c) d) a compound of tables 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) ~~ 94 ~ ~

These solutions are suitable for application in the form of micro-drops.

F3. Granulates a) b) a compound of tables 5 ~ 10 kaolin 94 %
highly dispersed silicic acid 1 ~ -attapulgite - 90 ~2~5374 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and`the solvent is subsequent-ly evaporated off in vacuo.

F4. Dusts a) b) a compound of tables 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 active ingredients of the formula I
(throughout, percentages are by weight) F5. Wettable powders a) b) c) a compound of tables 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) - Z %
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.

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

12~5374 castor oil polyglycol ether ~36 moles of ethylene oxide) 4 cyclohexanone 30 xylene mixture 50 ~

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

F7. Dusts a) b) a compound of tables 5 ~ 8 talcum 95 %
kaolin - 92 ~

~eady-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 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 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.

lZ1537~

F10. Suspension concentrate a compound of tables 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 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 20 C and then stood in a greenhouse at about 22C. Evaluation or rust pustule development is made 12 days ~21537~:

after infection. Compounds of Tables 1 to 3 are very effective against Puccinia fungi. Puccinia attack is lO0 % on untreated and infected control plants. Compounds l.l, 1.2, 1.5 to l.9, 1.24, 1.27, 2.1, 2.5, 2.6, 2.25, 5.1 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 sp~ayed 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 to 3 is substantially reduced. In this test, compounds 1.1, 1.2, 1.5 to 1.9, 1.24, 1.27, 2.1, 2.5, 2.6 and 2.25 inhibit the occurrence of specks almost completely (0-10~).

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 infes~ation is evaluated after 10 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 test compound formulated as wettable powder. Care is taken that the spra~
mixture does not come in contact with the parts of the plants above ~215374 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 l.l, 1.2, 1.5 to 1.9, 1.24, 1.26, 1.27, 2.5 and 5.1 and other compounds of Tables l to 3 inhibit fungus attack on barley to 0 to 5~.

Example B4: Residual-protective action against Venturia inaequalis on apple shoots Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.006 %) 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 i5 evaluated 15 days after infection.

Compounds l.l, 1.2, 1.5, 1.6, 1.8, 1.26, 2.1 and 2.6 and others inhibit attack to less than 20~. Venturia attack is 100~ on untreated and infected shoots.

Example B5: Action 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 20C. Fungicidal action is evaluated by examining the fruit for the presence of rot and the size of the ~æ~5374 i injury sites attacked by rot. After treatment with compounds of Tables 1 to 3, e.g. compounds 1.1, 1.2, 1.7, 1.8, 1.9, 1.24, 1.26, 1.27, 2.6 and 2.25 , no or almost no injury sites attacked by rot are observed, (0-5 % attack).

Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula I

(I) wherein R1 and R2 are each independently hydrogen, halogen C1-C4alkyl or CF3, and Rn denotes one to three alkyl, alkoxy, haloalkoxy, halo-alkyl, halogen and/or cyano groups, R4 is hydrogen, C1-C10alkyl, C3-C6cycloalkyl, phenyl, or sub-stituted phenyl, wherein the substituents are chosen independently from C1-C4alkyl, C1-C4alkoxy, C1-C3haloalkyl, halogen, and cyano, X is -CH= or -N=, R5 is hydrogen, C1-C12alkyl, C2-C4alkenyl, C2-C4alkynyl, benzyl, or substituted benzyl wherein the substituents are chosen independently from C1-C4alkyl, C1-C4alkoxy, C1-C3haloalkyl, halog-en, and cyano; and A is the radical wherein - 58a -R6 and R7 are each independently C1-C12alkyl, phenyl, or substituted phenyl wherein the substituents are chosen independently from C1-C4alkyl, C1-C4alkoxy, C1-C3haloalkyl, halogen, and cyano or both together form a C2-C4alkylene bridge which is unsubstituted or substituted by one or more identical or different members selected from the group consisting of C1-C4alkyl, C2-C4alkenyloxymethyl or C1-C3alkoxymethyl; 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 and R2 are each independently hydrogen, halogen, C1-C3alkyl or CF3; Rn is hydrogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C3halo-alkyl, halogen and/or cyano; A is one of the molecular fragments - 59a -wherein when a substituted phenyl group is present then the substitutents are chosen independently from C1-C4alkyl, C1-C4alkoxy, C1-C3haloalkyl, halogen, and cyano; R4 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl, phenyl or phenyl substituted by C1-C4alkyl, C1-C4alkoxy, C1-C3haloalkyl, 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, quaternary azolium salt or metal complex thereof.

3. A compound of the formula I according to claim I wherein each of R1 and R2 independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl or CF3; Rn is hydrogen, chlorine, dichloro, fluorine, bromine, methyl, difluoro, CF3 or OCF3; A is one of the molecular fragments R4 is hydrogen, C1-C4alkyl, C3-C6cycloalkyl, phenyl or phenyl substituted by methyl, methoxy, CF3, F, Cl, Br or CN; R5 is hydrogen, C1-C6alkyl, 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, quaternary azolium salt or 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, 3-F, 3-Cl, 3-Br, 3-CF3, 2-CH3, 4-Cl, 4-Br, 4-F, 4-CF3, 5-Cl, 5-Br, 5-F or 5-CF3; R2 is hydrogen; Rn is hydrogen, 4-chloro, 2,4-dichloro, 4-fluoro, 2,4-difluoro, 4-bromo, 4-methyl, 4-CF3 or 4-OCF3; A is one of the molecular fragments 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-dihalobenzyl; and X is -N=; or an acid addition salt, quaternary azolium salt or metal complex thereof.

5. A compound of the formula I according to claim 4, wherein R1 is 2-H, 2-F,2-Cl, 2-Br or 2-CH3; R2 is hydrogen; Rn in a para-positioned phenyl group is hydrogen, 4-chloro, 2,4-dichloro, 4-fluoro, 2,4-difluoro, 4-bromo, 4-methyl, 4-CF3 or 4-OCF3; A is one of the molecular fragments R4 is hydrogen; R5 is hydrogen; and X is -N=; or an acid addition salt, quaternary azolium salt or metal complex thereof.

6. A compound of the formula I according to claim 1, selected from the group consisting of 1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl]-3,3-di-methoxypropan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl]-2-(1,3-dioxolan-2-yl)-ethan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl]-2-(4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-bromophenoxy)phenyl]-3,3-di-methoxypropan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-bromophenoxy)phenyl]-2-(4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)-2-methylphenyl]-3,3-dimethoxy-propan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)-2-methylphenyl]-2-(1,3-dioxolan-2-yl)-ethan-2-ol;

1-(1H-imidazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl]-3,3-dimethoxy-propan-2-ol;

1-(1H-imidazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl]-2-(4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol;

1-(1H-imidazol-1'-yl)-2-[p-(4-bromophenoxy)phenyl]-3,3-dimethoxy-propan-2-ol;

1-(1H-imidazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl]-3,3-diethoxy-propan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)-2-chlorophenyl]-3,3-dimethoxypropan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(2,4-dichlorophenoxy)phenyl]-3,3-dimethoxypropan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(2,4-dichlorophenoxy)phenyl]-2-(4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)phenyl]-2-(2-methyl-1,3-dioxolan-2-yl)-ethan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)-2-methylphenyl]-2-(4-methyl-1,3-dioxolan-2-yl)-ethan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(4-chlorophenoxy)-2-methylphenyl]-2-(1,3-dioxan-2-yl)-ethan-2-ol;

1-(1H-1,2,4-triazol-1'-yl)-2-[p-(phenoxy)phenyl]-2-(2-phenyl-4 ethyl-1,3-dioxolan-2-yl)-ethan-2-ol;

1-(1H-imidazol-1'-yl)-2-[p-(phenoxy)phenyl]-2-(2-phenyl-4-ethyl-1,3-dioxolan-2-yl)-ethan-2-ol.

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

(II) with an azole of the formula III

(III) to give first a compound of the formula [a (Ia) and, if desired, converting the alcohol [a, 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 and V
above the substituents R1, R2, R , R4, R5, A and X are as defined for formula I in claim 1, M is hydrogen or a metal atom, and W is OH or a leaving group.

8. A process for controlling phytopathogenic microorganisms or for protecting cultivated plants from attack by said microorganisms, and/or of controlling plant growth, which method comprises applying to said plants or the locus thereof an effective amount of a compound of the formula I as defined in claims 1, 2 or 3.
FO 7.5 HL/eg*