CA1254574A - Hydroxyalkyl-azolyl derivatives substituted by heterocyclic substituents - Google Patents

Abstract

ABSTRACT

The invention relates to a heterocyclyl-hydroxyalkyl-azolyl deri-vative of the formula

Description

The present invention relates to new hydroxyalkylazolyl derivatives substituted by heterocyclic substltuents, several processes for their preparation and their use as funglcides.
This application is divided out of copending parent application serial No. 441,096 filed November 14, 1983.
It has already been disclosed that certain hydroxyethyl-azolyl derivatives, such as, for example, 3,3-dimethyl-1-phenoxy-2-(1,2,4-triazol- 1-yl-methyl)-2-butanol or 1-(2-chloro-4-fluorophenoxyj-3,3-dimethyl-1-(1,2,4-triazol-l-yl-methyl)-2-butanol or 1-(4-cblorophenoxy)-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-2-propanol, have fungicidal properties (compare DE-OS
[German Published Specification] 3,018,866 [Le A 20 330]). However, the activity of these compounds is not always completely satisfactory, especially when low amounts and concentrations are applied.
According to one aspect of the invention of the parent application there is provided a heterocyclyl-hydroxyalkylazolyl derivative of the formula f-R CH3 R-C ~ C ) _ Het (Id) CH2 CH3 n Az in which Az represents 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl or imidazol-l-yl, Het represents dioxolan-2-yl or 1,3-dioxanyl, each of which is optionally monosubstituted or polysubstituted by identical or different substituents selected from the group consisting of alkyl with 1 to 4 carbon atoms, and phenyl and phenoxyalkyl with 1 to 4 carbon atoms in the alkyl part, each of which is optionally monosubstituted or polysubstituted by identical or different substituents, substituents on the phenyl being selected from the `~

~,5~5~
~ 2 --group consisting of halogen, alkyl with 1 to 4 car`bon atorns, alkoxy and alkylthio with in each case 1 or 2 carbon atoms and halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms;
R represents straight-chain or branched alkyl with 1 to 7 carbon atoms, or phenyl, phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenoxy- or phenylthio-alkyl with in each case 1 to 4 carbon atoms in the alkyl part or phenylethenyl, each of which is optionally monosubstituted or polysubstituted by identical or different substituents, substituents on the phenyl groups being selected from the group consisti.ng of halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, nitro, halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, hydroximinoalkyl with 1 to 4 carbon atoms, alkoximinoalkyl with 1 to 4 carbon atoms in each alky] part, and phenyl, phenoxy, benzyl and benzyloxy, each of which is optionally substituted by halogen or alkyl with 1 or 2 carbon atoms; or R represents cycloalkyl with 5 to 7 carbon atoms, which is in each case optionally monosubstituted or polysubstituted by identical or different alkyl radicals with 1 to 4 carbon atoms, or cycloalkyl-methyl or -ethyl with 5 to 7 carbon atoms in the cycloalkyl part, or cyclohexylethenyl, or, alkenyl with 2 to 6 carbon atoms, 2-furyl, naphthyloxy-methyl, 1,2,4-triazol-l-yl-methyl, 1,2,4-triazol-4-yl-methyl, imidazol-l-yl methyl or pyrazol-l-yl-methyl, and R' represents hydrogen, alkyl which has 1 to 4 carbon atoms and is optionally substituted by phenyl, it being possible for the phenyl radical to be substituted by the substituents on phenyl mentioned under R, or alkenyl a~

- 2a -with 2 to 4 carbon atoms, and n is l, or a rlon-phytotox:ic addition product thereof with an acid or metal sa:1t wherein sclld ac:id is selected from the group consisting of hydrogen halide ac:ids, phosphorlc acid, nitric acid, monofunctional and bifunctional carboxylic acids, hydroxycarboxylic acids and sulphonic acids and said metal is selected from the group consisting of metals of main groups II to IV and of sub-groups I and II and IV to VIII.
According to other aspects of the invention of the parent application there is provided a process for preparing compounds of formula Id above (which process is set forth below) and a method of combatting fungi using a compound of formula Id.
According to one aspect of the invention of the present divisional application there is provided a heterocyclyl-hydroxyalkyl-azolyl derivative of the formula 10-R' R-C-Het (Ie) lz in which Az represents l,2,4-triazol-l-yl, l,2,4-triazol-4-yl or imidazol-l-yl, Het represents l,3-dioxan-5-yl unsubstituted or substituted by identical or different substituents selected from the group consisting of alkyl with l to 4 carbon atoms, and phenyl and phenoxyalkyl with l to 4 carbon atoms in the alkyl part, each of which is optionally monosubstituted or polysubstituted by identical or different substituents, substituents on the phenyl being selected from the group consisting of halogen, alkyl with l to 4 carbon atoms, alkoxy and alkylthio with in each case l or 2 carbon atoms and halogenoalkyl, halogenoalkoxy and halogenoalkylthio with ln each case l or

2 carbon atoms and l to 5 identical or different halogen atoms;

~Z,~S~

- 2b -R represents straight-chain or branched alkyl w:Lth 1 to 7 carbon atoms, or phenyl, phenylalkyl w:Lth 1 to 4 carbon atorn., in the alkyl part, phenoxy- or phenylthio-alkyl wlth ln each case 1 to 4 carbon atoms in the alkyl part or phenylethenyl, each of which ls optlonally monosubstltuted or polysubstituted by identlcal or dlfferent substltuents, substituents on the phenyl groups belng selected from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, nitro, halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, hydroximinoalkyl wlth 1 to 4 carbon atoms, alkoximinoalkyl with 1 to 4 carbon atoms ln each alkyl part, and phenyl, phenoxy, benzyl and benzyloxy, each of which is optionally substituted by halogen or alkyl with 1 or 2 carbon atoms; or R represents cycloalkyl with 5 to 7 carbon atoms, which is in each case optionally monosubstituted or polysubstituted by identical or different alkyl radicals with 1 to 4 carbon atoms, or cycloalkyl-methyl or -ethyl with 5 to 7 carbon atoms in the cycloalkyl part, or cyclohexylethenyl, or, alkenyl with 2 to 6 carbon atoms, 2-furyl, naphthyloxy-methyl, 1,2,4-triazol-l-yl-methyl, 1,2,4-triazol-4-yl-methyl, imidazol-l-yl-methyl or pyrazol-l-yl-methyl, and R' represents hydrogen, alkyl which has 1 to 4 carbon atoms andis optionally substituted by phenyl, it being possible for the phenyl radical to be substituted by the substituents on phenyl mentioned under R, or alkenyl with 2 to 4 carbon atoms, or a non-phytoto~ic addition product thereof with an acld or met~l salt wherein said acid is selected from the group conslsting of hydrogen halide acids, phosphoric acld9 nltric acld, monofunctional and blfunctlonal carboxyllc acids, hydroxycarboxylic acids and sulphonlc aclds and sald metal ls selected r~

- 2c -from the group consisting of metals of main groups IL to IV and of sub-groups I and II and IV to VIII.
According to other aspects of the invention of this divisional application there is provided a process for preparing compounds of formula Ie and a method of combatting fungi using a compound of formula Ie.
In the following text, where a passage relates equally to compounds of formula Id or Ie, depending only on the values of the symbols in the above general formulae, these two groups of compounds will be referred to collectively as compounds of formula I.
In some cases, the compounds of the formula (I) have an asymmetric carbon atom, and they can therefore be obtained in the two optical isomer forms.
It has furthermore been found that the hydroxyalkyl-azolyl derivatives substituted by heterocyclic substituents, of the formula (I), are obtained by a process in which a) oxiranes of the formula (II) R - C ~ C ) -Het (II) H2 CH3 n in which Het, R and n have the abovementioned meaning, are reacted with azoles of the formula (III) M-Az (III) . in which Az has the abovementioned meaning and M represents hydrogen or an alkali metal salt, in the presence of a diluent and, if appropriate, in the presence of a base, or - 2d -b) azolo-ketones of the formul~ (IV) Itl3 Az-cH2-co- ( C ) -fl~t (IV) CH3 n ;n wh;ch Az, Het and n have the abovement;oned mean;ng, are reacted w;th an organomagnes;um compound of the for-mula (V) R-Mg-X ~V~

in wh;ch R has the abovement;oned meaning and X represents chlorine, bromine or iod;ne~
in the presence of a d;luent, or c) azolo-oxiranes of the formula (VI) Az CHz C ~C ~ -Het (VI) ~ CHz~CH3 Jn in which Az, Het and n have the abovementioned meaning, are reacted with optionally substituted phenols and thio-phenols and with organometallic compounds of the formula( V I I ) R-Me (VII) in which R has the abovementioned meaning and Me represents an alkali metal or -Mg-X, wherein X has the abovementioned meaning, in the presence of a diluent and if appropr;ate ;n the presence of a base, and subsequently, ;f appropr;ate, d) the hydroxy compounds (where;n R' ;n formula (I) rep-resents hydrogen) obtained according to process a), b) or c) is converted into the alkali metal alcoholate in the presence of a diluent, and this product is reacted Le A 22 013 . . .

~,sa~7~

with a halide to give the corresponding ether derivatives (wherein R' in forrnula (I) represents an optionally substituted alkyl group or an alkenyl group).
If desired, an acid or a metal salt can then be added on to the com-pounds of the formula (I) thus obtained.
The new hydroxyalkyl-azolyl derivatives substituted by heterocyclic substituents, of the formula (I), have powerful fungicidal properties. Sur-prisingly, the compounds according to the invention exhibit a more powerful action than the hydroxyethyl-azolyl derivatives 3,3-dimethyl-1-phenoxy-2-(1,2,4-triazol-1-yl-methyl)-2-butanol, 1-(2-chloro-4-fluorophenoxy)-3,3-di-methyl-2-(1,2,4-triazol-1-yl-methyl)-2-butanol or 1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-2-propanol, which are known from the prior art and are closely related compounds structurally and from the point of view of their action. The substances according to the invention thus represent an enrichment of the art.
In formulae Id and Ie, within the scope of the definitions given above, Az represents 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl or imidazol---l-yl;
Het represents dioxolan 2-yl or 1,3-dioxanyl, each of which is optionally monosubstituted or polysubstituted by identical or dif-ferent substituents, examples of substituents which may be mentioned being: alkyl with 1 to 4 carbon atoms, and phenyl and phenoxyalkyl with 1 to 4 carbon atoms in the alkyl part, each of which is op-tionally monosubstituted or polysubstituted by ldentical or dif-ferent substituents, examples of substituents on the phenyl which may be mentioned being: halogen, alkyl with 1 to 4 carbon ~J~

_ S _ atoms, alkoxy and aLkylthio with in each case 1 or 2 carbon atoms and halogenoalkyl~ halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as, preferably, fluorine and chlor;ne atoms;
R represents straight-chain or branched alkyl with 1 to 7 carbon atoms, or phenyl, phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phen-oxy- or phenylthio-alkyl with in each case 1 to 4 carbon atoms in the alkyl part or phenyl-etheny~, each of which is opt;onally monosub-stituted or polysubstituted by identical or different substituents, examples of substituents on the phenyl groups which may be mentioned being:
halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, nitro, halogenoalkyl~ halogenoalkoxy and halogenoalkylth;o with in each case 1 or Z car-bon atoms and 1 to 5 identical or different halo-gen atoms, such as, preferably, fluorine and chlorine atoms, hydroximinoalkyl with 1 to 4 carbon atoms, alkoximinoalkyl with 1 to 4 carbon ato~s in each alkyl part, and phenyl, phenoxy, benzyl and benzyloxy, each of which is optionally substituted by halogen or alkyl with 1 or 2 car-bon atoms; or, preferably, R repreSents cyclo-alkyl with 5 to 7 carbon atoms, which is in each case optionally monosubstituted or polysubsti~
tuted by identical or different alkyl radicals with 1 to 4 carbon atoms, or cycloalkyl-methyl or -ethyl with 5 to 7 carbon atoms in the cyclo-alkyl part~ or cyclohexylethenyl; or, prefer-ably, R represents alkenyl with 2 to 6 carbon atoms, 2-furyl, naphthyloxymethyl, 1,2,4-tr;azol-1-yl-methyl, 1,Z,4-triazol-4-yl~methyl, imidazol-Le A 22 013 l-yl-methyl or pyrazol-l-yl-methyl;
R' represents hydrogen, alkyl whlch has 1 to 4 carbon atoms and i8 optionally substituted by phenyl, Lt belng possl.ble :eor the phenyl radical to be substituted by the 3ubstituents on phenyl mentioned under R, or alkenyl with 2 to 4 carbon atoms; and the index n represents the number 0 or 1.
Preferred compounds are those in which Az represents 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl or imidazol-l-yl;
Het represents dioxolan-2-yl, 1,3-dioxan-4-yl or 1,3-dioxan-2-yl, each of which is optionally mono-, di- or tri-substituted by identical or different substituents, examples of substituents which may be mentioned being: methyl, ethyl, n-propyl, isopropyl and phenyl and phenoxymethyl, each of which is optionally mono-, di- or tri-substituted by identical or different substituents from the group comprising fluorine, chlorine, methyl, trifluoromethyl and trifluoro-methoxy;
R represents tert.-butyl, trimethyl-propyl or tetramethyl-propyl, or phenyl, benzyl, phenethyl, phenoxymethyl, phenylthiomethyl or phen-ethenyl, each of which is optionally mono-, di- or tri-substituted by identical or different substituents, examples of substituents on the phenyl which may be mentioned being: fluorine, chlorine, methyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, hydroximino-methyl, l-hydroximinoethyl, methoximinomethyl and l-methoxlmino-ethyl, and phenyl, phenoxy, benzyl and benzyloxy, each of which is optionally substituted by chlorine and/or methyl; or R represents cyclohexyl, cyclohexylmethyl, cyclohexylethyl or cyclohexylethenyl, each of which ls optionally rnono- or dl-substituted by identical or dlfferent substituents from the group comprlsing methy:l, ethyl and isopropyl; or R represents allyl, dimethylpropenyl, 2-~uryl, naphthy-loxymethyl, 1,2,4-triazol-1-yl-methyl, 1,2,4-triazol-4-yl-methyl, imidazol-l-yl-methyl or pyrazol-l-yl-methyl;
R' represents hydrogen, methyl, 4-chlorobenzyl or allyl; and the index n represents the number 0 or 1.
Non-phytotoxic addition products of acids and those hydroxyalkyl-azolyl derivatives substituted by heterocyclic substituents, of the formula (I), in which the substituents Az, Het, R and R' and the index n have the meanings which have already been mentioned as preferred for these substituents and the index are also preferred compounds.
Acids which can be added on are hydrogen, halide acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, and furthermore phosphoric acid, nitric acid, mono-functional and bi-functional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, rnaleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and sulphonic acids, such as, for example, p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid.
Addition products of salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII and those hydroxyalkyl-azolyl derivatives substituted by heterocyclic substituents, of the formula (I), in which the substituents Het~ R and R' and the index n have the meanings which have already been mentioned as preferred for these substituents and the index are also preferred compounds.
Salts of copper, zinc, manganese, l~gnesium, tin, iron and nickel ~L~154~7~

are particularly preferred here. Possible anlons of these salt~s are those which are derived from aclds which lead to physLologLcaLly acceptable addLtion products. In this connectLon, partlcu:larLy preferred acicls of thls type are the hydrogen halide acids, such as, for exaTnple, hydrochloric acid and hydro-bromic acid 7 and furthermore phosphoric acid, nitric acid and sulphuric acid.
The following compounds of the formula (Ia) which includes compounds of formulae Id and le may be mentioned specifically, in addition to the com-pounds mentioned in the preparation examples:

OH ~ CH3 ~
R-Cj `~ C J ~ Het (Ia) CIH2 ~ 3 Az R__ Az _ n Het __ ~ -N ~ 1 -b~

N ~ N
L N-CH

Cl ~ CH=CH- -N

Cl- ~ CH2-CH - -N I O

Cl- ~ 2 N ~

7~

_ 9 _ R Az n Het CI~CH=CH- -N\~--1 ~ol C2H$

Cl~CH2 CH2- -N~ ol CzH5 C l~0-CH2- ~N ~
\~N 0 CzH5 N ~ /N _ 0 C l ~-CHz- -N
--N \~N 0 1 ~CHz-O~Cl N~ ~N-- 0--N- C H z - - N
~N/ ~N ~Ol~Cl Cl~S-CH2- -N~ ¦ 1 ~<

C l ~c H 2 - ~N ~< 0 Cl~ CH

CH

~3CH=CH- ~N~ l \~ N 0 CzH5 Le A 22 013 q~r-~ ~Y7 R Az n Het ~3CH2-CHZ- - 1 --<olc2H5 H3C CH3 /N- ~ 0 -H3C CH3 -N 1 1 0 l C~2_0 ~ Cl H2C=HC-C- ~N - l ~ 0 1 CH3 ~:N CH2-0-~ ~ Cl CH=CH~ N ~ O x CH3 _ I \ r CH3 CH2~CH2--N 0 -C

Cl ~=:N 1 ~ CH3 Cl ~ ~=: N ~ l C2H5 ~ -N~ J , ~ ~

H3CON=CH ~ o-CH2- -N ~ ~ ~

H3CON-C ~ (~-CH2~ O ~

Le A 22 013 . .

s7a,r Az n Het Cl Cl ~ol CzH5 C ~ ol c 2H 5 Le A 22 013

3~a", If, for example, 2-C2-(1,3-dioxolan-2-yl)-prop-2-y~J-2-(4-fluoro-phenoxyrnethyl)-oxirane and 1,2,4-triazol are used as starting s~bstances~ the course of process (a) can be represented by the followlng equation:

F ~ O - CH2 C~ ~ 1 + H-F ~ O-CH2 - C - C

~ ~N

If, for example, 2-(1,3-dioxolan-2-yl)-prop-2-yl, 1,2,4--triazol-1-yl-methyl ketone and 4-chlorobenzyl-magnesium chloride are used as starting substances~ the courSe of process (b) Can be represented by the following equation:

CH
L N - CH2-Co-0 ~ ~ + Cl ~ H2MgCl -OH CH
Cl ~ CH2 C~13 D

N ~

If~ for example~ 2-[2-(1,3-dioxolan-2-yl)-prop-2-yl]-2-(1,2,4-triazol-l-yl-methyl)-oxirane and 4-fluorophenol are used as starting substances, the course of process (c) can be represented by the following equation:

r-~ ~7~

~ 13 -I_ /N CH2 / \ l~oJ ~ F ~ OH - >

F ~ O-CH2-C C
CH3 C~3 `N
N ~
Formula (II) provldes a general definition oE the oxiranes to be used as starting substances for carrying out process (a~. In this formula, Het, R and the index n preferably have the meanings which have already been mentioned as preferred for these substituents and for the index n in connection with the description of the substances of the formula (I).
The oxiranes of the formula (II) are not yet known. flowever, they can be obtained in a generally known manner, by reacting ketones of the formula (VIII) ~ ICH3 R - CO - ~ C ) -Het (VIII) 3 n in which Het, R and n have the abovementioned meaning, either ~) with dimethyloxosulphonium methylide of the formula (IX) ( 3)2SOCH2 (IX) in the presence of a diluent, or ~.~5~

~) with trimethylsul.phonlum me~hyl-sulphate of the formula (X) ~CH3)3s ~ C~L3S4 (X) in the presence of an inert organic solvent and in the presence of a base.
The ketones of the formul.a (VIII), in which n = 1, required as starting substances in the preparation of the oxiranes of the formula (II) are known in some cases (compare, for example, J. Org.
Chem. 32, 404 (1967)), or they can be obtained in a known manner, by reacting l-(N-morpholino)-isobutene of the ~ormula (XI) o N-C7rL5C(CH3)2 (XI) with chlorides of the formula (XII) R-CO-Cl (XII) in which R has the abovementioned meaning, in the presence of a solvent, such as, for example, diethyl ether, at temperatures between 20C and 120C, and forming derivatives of the resulting keto derivatives of the formula (XIII) C~13 R-CO-C~CHO ~XIII) CH~
in wh;ch R has the abovementioned meaning, on the aldehyde group with corresponding diols in the customary manner in the presence of an inert organic solvent, such as, for example, toluene, and in the pre-sence of a strong acid, as the catalyst, such as, for example, p-toluenesulphonic acid, at ternperatures between 80C and 110C.
The ketones of the formula (VIII), in which n = O, required as starting substances in tha preparation of the oxiranes of the formula (II) are known in soms cases (compare, for example, EP-OS ~European Offenlegungs-schrift] 0,043,923), or they can be obtained in a known manner~ by reacting aldehyde-ketones (compare~ for ex-ample, Houben-Weyl, Methoden der organischen Chem;e CMeth-ods of Organic Chemistry], volume 7/1. Page 185) of the formula (XIV~

R-CO-CHO (XIV) in which R has the abovementioned meaning, or acetals or ketals thereof, of the formula R-C(OCH3)2-CHO
(for their preparation compare Bull.Soc.Chim.France, 1971, page 2598) on the aldehyde group with correspond-;ng d;ols ;n the customary manner in the presence of an ;nert organ;c solvent, such as, for example, toluene, and in the presence of a strong acid, such as, for ex-ample, p-toluenesulphon;c ac;d, at temperatures between 4ûC and 110C.
Ketones of the formula (VIII) in wh;ch R = op-tionally substituted phenethenyl or cyclohexylethenyl Le A 22 013 .

can also be obtained by subjectiny correspond;ng benz-aldehydes or cyclohexyLcarbaldehydes to an aldol conden-sat;on with corresponding methyl ketones ;n the customary manner. If appropriate, the resulting ketones of the formula (VIII) in which R = optionally substituted phen-ethenyl or cyclohexylethenyl can be hydrogenated in the customary manner to give ketones o~ the formula (VIII) in which R = optionally substituted phenethyl or cyclo-hexylethyl (compare also the preparation exampLes).
The dimethyloxosulphonium methylide of the formula (IX) required in process variant ~) is known (compare J-Amer.Chem.Soc. 87, 1363-1364 (1965)). In the above reaction, it is processed in the freshly prepared state by being produced in situ by reaction of trimethlyoxosul-phonium iodide with sodium hydride, sodium amide or po-tassium tert.-butylate in the presence of a diluent.
The trimethylsulphonium methyl-sulphate of the formula (X) required in process variant (~) is also known (compare Heterocycles 8, 397 (1977)). It ;s l;kew;se employed in the above reaction in the freshly prepared state, by be;ng produced ;n situ by react;on of dimethyl sulph;de with dimethyl sulphate.
A poss;ble d;luent ;n var;ant (~) of the process for the preparat;on of the ox;ranes of the formula (II) ;s, preferably, dimethylsulphoxide.
The react;on temperatures can be var;ed within a substantial range in process var;ant (~) descr;bed above.
In general, the reaction is carried out at temperatures between 20C and 80C.
The process for the preparation of the oxiranes of the formula (II) by variant (~) and the working up of the react;on m;xture obtained ;n th;s synthesis are carried out by customary methods tcompare J.Amer~Chem.Soc.
87, 1363-1364 ~1965)).
A possible inert organic solvent in variant (l~ ) for the preparation of the oxiranes of the formula ~II) Le A 22 013 7a~

is preferably, acetonitrile.
Bases which can be used in process variant (~) are strong inorganic or organic bases. Sodium methylate i9 preferably used.
The reaction temperatures can be varied within a certain range in process variant (~) described above. In general, the reaction is carried out at temperatures between 0C and 60C, preferably at room temperature.
The process for the preparation of the oxiranes of the formula (II) by variant (~) and the working up of the reaction product obtained in this synthesis are carried out by customary method (compare Heterocycles 8, 397 (1977)).
In the process, if appropriate, the oxiranes of the formula (II) can be further reacted directly, without isolation.
Formula (III) provides a general definition of the azoles also to be used as starting substances for process (a). In this formula, Az preferably has those meanings which have already been mentioned for these substituents. M preferably represents hydrogen, sodium or potassium.
The azoles of the formula (III) are generally known compounds of organic chemistry.
Formula (IV) provides a general definition of the azolo ketones to be used as starting substances in carrying out process ('~). In this formula Az, Het and the index n preferably have the meanings which have already been mentioned as preferred for these substituents or for the index n in connection with the description of the substances of the formula (I).
Some of the azolo-ketones of the formula (IV) are known (compare, for example, EP-OS [European Published Specification] 0,043,923).

7~

The azolo-ketones of the formula (IV) can be ol,ta:Lned ln a gerlerally known manner, by reacting halogenomethyl ketones of the formula (XV) Hal-cH2-co ( C ) --Het (XV) 3 n in which Het and n have the abovementioned meaning and Hal represents chlorine or bromine, with 1,2,4-triazole or imidazole in the presence of an inert organic solvent, such as, for example, acetone, and in the presence of an acid-binding agent, such as, for example, potassium carbonate, at temperatures between 20C and 150C in the customary manner.
The halogenomethyl ketones of the formula (XV) in which n = 1 which are required as starting substances in the preparation of the azolo-ketones of the formula (IV) are not yet known. They can be obtained by the preparation described above for the ketones of the formula (VIII) in which n is 1.
Some of the halogenomethyl ketones of the formula (XV) in which n = O re~uired as starting substances in the preparation of the azolo-ketones of the formula (IV) are known (compare, for example, EP-OS LEuropean Published Specification] 0,043,923); they can be obtained in a known manner by halogenation, such as, for example, with " ~5~i7~

-- lg-N-bromosuccinamide, of corresponding ketone.s o:f the formula (VIII).
Formula (V) provldes a general defln:itlon of t~e organomagneslum compounds also to be used as starting substances for process (b). In this formula, R preferably has the meanings which have already been mentioned for this substituent in connection with the description of the substances of the formula (I).
The organomagnesium compounds of the formula (V) are generally known compounds of organic chemistry (so-called "Grignard compounds"); or they are obtained in a generally known manner.
Formula (VI) provides a general definition of the azolo-oxiranes to be used as starting substances in carrying out process (c).
In this formula, Az, Het and the index n preferably have the meanlngs which have already been mentioned as preferred for these substituents and for the index n in connection with the description of the substances of the formula (I).
The azolo-oxiranes of the formula (VI) are not yet known;
however, they can be obtained in a generally known manner by epoxidising azolo-ketones of the formula (IV) in accordance with the abovementioned process variants (~) and (~).
The phenols and thiophenols also used as starting substances for process (c) are given by the preferred definition of the radical R
in the substances of the formula (I).
Formula (VII) provides a general definition of the organometallic compounds also to be used as starting substances for process (c). In this formula, R preferably has the meanings which have already been mentioned for this substituent in connection with the description of the substances ~

of the formula (I). Me preferably represents lith:Lutn, sodLuM, potassium or the grouping -Mg-X, in which X represents chlorine, bromine or iodine.
The phenols and thiophenols and the organometallic compounds of the formula (VII) are generally known compounds of organic chemistry.
Possible diluents for process (a) are organ:ic solvents which are inert under the reaction conditions. Preferred solvents include alcohols, such as, for example, ethanol, methoxyethanol or propanol; ketones, such as for example, 2-butanone; nitriles, such as, for example, acetonitrile; esters, such as, for example, ethyl acetate; ethers, such as, for example, dioxane;
aromatic hydrocarbons, such as, for example, benzene and toluene; and amides, such as, for example, dimethylformamide.
Possible bases for process (a) are all the inorganic and organic bases which can customarily be used. Preferred bases include alkali metal carbonates, such as, for example, sodium and potassium carbonate; alkali metal hydroxides, such as, for example, sodium hydroxide; alkali metal alcoholates, such as, for example, sodium and potassium methylate and ethylate; alkali metal hydrides, such as, for example, sodium hydride; and lower tertiary alylamines, cycloalkylamines and aralkylamines, such as, in particular, triethylamine.
The reaction temperatures can be varied within a subskantial range in carrying out process (a). In general, the reaction is carried out at temperatures between 0C and 200C, preferably between 60C
and 150C.
In carrying out process (a) 1 to 2 mols of a~ole and, if appropriate, 1 to 2 mols of base are preferably employed per mol oE oxirane of the formula (II). The end producta are isolated in the generally customary manner.
Possible diluents Eor process (b) are all the solvents customary for a Grignard reaction. Preferred solvents include ethers, such as diethyl ether or tetrahydrofuran, and mixtures with other organlc solvents, such as, for example, benzene.
The reaction temperatures can be varied within a substantial range in carrying out process (b). in general, the reaction is carried out between about 20C and 120C, preferably between about 30C and about 80C.
In carrying out process (b), an excess of 3 to 5 mols of an organometallic compound of the formula (V) is preferably employed per mol of azo~ketone of the formula (IV). The end products are isolated in the generally customary manner.
Possible diluents for process (c) are organic solvents which are inert under the reaction conditions. Preferred solvents include alcohols, such as, for example, ethanol, methoxyethanol or propanol;
ketones, such as, for example, 2-butanone; nitriles, such as, for example, acetonitrile; esters, such as, for example, ethyl acetate;
ethers, such as, for example, dioxane; aromatic hydrocarbons, such as, for example, benzene and toluene; and amides, such as, for example, dimethylformamide.
Possible bases for process (c) are all the inorganic and organic bases which can customarily be used. Preferred bases include the compounds which have already been mentioned for process (a).
The reaction temperatures can be varied within a substantial range in carrying out process (c). In general, the reaction is carried out at temperatures between 0C and 200C, preferably ~ h between 60C and 150C.
In carrying out process (c) 1 to 2 mols of ~thLo)phenol and, if appropriate, 1 to 2 mols of base, ar.d 1 to 3 mols o~ the organometallic compounds of the formula (VII) are ernployed per mol of azolo-oxirane of the formula (VI). The end products are in each case isolated in the generally customary manner.
The preparation of the ether compounds of the formula (I) by process d) is advantageously carried out by convert:ing compounds of the formula (I) into the alkali metal alcoholate by means of an alkali metal hydride or amide in a suitable inert organic solvent, and reacting the alcoholate immediately without isolation, with a corresponding halide, such as, in particular, an alkyl halide, in a temperature range between 0 and 80C, the ethers of the compounds of the formula (I) being obtained in one operation, with elimination of alkali metal halide.
In a preferred embodiment, the preparation of the alcoholates and further reaction thereof with a halide are advantagesouly carried out in a two-phase system, such as, for example, aqueous sodium hydroxide solution or potassium hydroxide solution/toluene or methylene chloride, with addition of 0.01 to 1 mol of a phase transfer catalyst, such as, for example, ammonium or phosphonium compounds, the alcoholates being formed in the organic phase or at the phase boundary and reacting with the halides in the organic phase, The hydroxy compounds (in which, in formula (I), R' represents hydrogen) obtainable by processes a), b) and c) can also be converted into the corresponding esters.
The compounds are thus interesting intermediates.
The preparation of the esters is advantageously carried out by reacting the hydroxy compounds with, for example, acid halides in the presence of an inert organic solvent, such as, for exampLe, ethyl acetate, at tempera-tures between 0C and 100C; or react;ng the hydroxy com-pounds w;th ac;d anhydr;des ;n the presence of an inert organ;c solvent, such as, for example, methylene chlor;de or an excess of acid anhydr;de, and ;n the presence of a catalyst, such as, for example, sod;um acetate, at tem-peratures between 0C and 15ûC.
The compounds of the formula (I) can also be con-verted ;nto ac;d add;t;on salts or metal salt complexes.
The ac;d add;tion salts of the compounds of the formula (I) can be obta;ned ;n a s;mple manner by custom-ary salt format;on methods, for example by dissolv;ng a compound of the formula (I) ;n a su;table ;nert solvent and add;ng the ac;d, for example hydrochlor;c ac;d, and they can be ;solated ;n a known manner, for example by f;ltrat;on, and ;f appropr;ate pur;f;ed by wash;ng w;th an ;nert organic solvent.
The metal complexes of compounds of the formula (I) can be obta;ned in a simple manner by customary pro-20 cesses, thus, for example by dissolv;ng the metal salts;n alcohol, for example ethanol, and add;ng the solution to the compound of the formula (I). The metal salt com-plexes can be purified in a known manner, for example by filtration, isolation and, ;f necessary, by recrystal-25 lisation.
The active compounds according to the inventionexhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organ;sms. The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant protection are employed for combat;ng Plasmodiophoromycetes, Oomycetes, Chytridio-mycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration, by plants, of the active compounds, at the concentrations required for combating Le A 22 013 ~5~7a~

plant diseases, perm;ts treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil~
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating Puccinia species, such as against the brown rust of wheat causative organism (Puccinia recondita), and Botrytis species, such as against grey mould ~Botrytis cinerea), and also for combating mildew, Leptosphaeria nodorum, Cochliobolus sativus and Pyreno-phora teres on cereals, and aga;nst Pyr;cularia and Pelli-cularia on r;cev When used in appropriate amounts, the substances according to the invention also exhibit a growth-regulating action.
The active compounds can be converted to the cus-tomary formulations, such as solutions, emulsions, sus-pensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active Z0 compound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist formulations.
These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents~ that is, emulsifying agents and/or dis-persing agents, andtor foam-forming agents. In the case of the use of water as an extender, organic solvents can, for exampley also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, Le A 22 013 aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as buta-nol or glycol as well as the;r ethers and esters, ke~ones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water; by llquefied gaseous extenders or carr;ers are meant those l;qu;ds wh;ch are gaseous at normal temperature and under normal pressure, for example aerosol propellant, 1û such as halogenated hydrocarbons as well as butane, pro-pane, n;trogen and carbon d;ox;de; as sol;d carriers there are suitable: for example ground natural minerals, such as kaolins~ clays, talc, chalk, quartz, attapulgite, montmorillonite or d;atomaceous earth, and ground synthetic m;nerals, such as highly-d;spersed s;l;c;c ac;d, alumina and silicates; as sol;d carriers for granules there are su;table: for example crushed and fract;onated natural rocks such as calc;te~ marble, pum;ce, sep;ol;te and dolo-m;te, as well as synthet;c granules of ;norgan;c and organ;c meals, and granules of organ;c mater;al such as sawclust, coconut shells, ma;ze cobs and tobacco stalks;
as emuls;fy;ng and~or foam-forming agents there are su;t-able: for example non-;onic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethyl-ene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphon-ates as well as albumin hydrolysat;on products; as dis-pers;ng agents there are su;table: for example lignin-sulph;te waste l;quors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural,and synthetic polymers in the form of powders, granules or latices~ such as gum arab;c, polyvinyl alco-hol and polyv;nyl acetate, can be used ;n the formulat;ons.
It is poss;ble to use colorants such as inorgan;c p;gments, for example iron oxide, t;tanium oxide and Pruss;an Blue, and organic dyestuffs, such as alizarin Le A 22 013 dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, horon, copper, cobalt, molybdenum and zinc.
The formulations in general contain between O~l and 95% by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules.
They are used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
In the treatment of parLs of plants, the active compound concentrations in the use forms can be varied within a substantial range.
They are, in general, between l and 0.0001% by weight, preferably between 0.5 and 0.001%.
In the treatment of seed, amounts of active compound of 0.00l to 50 g per kilogram of seed, preferably O.Ol to lO g, are generally required.
For the treatment of soil, active compound concentrations of O.OOOOl to 0.1% by weight, preferably O.OOOl to 0.02%, are required at the place of action.
The following examples relate to both compounds of formula Id and Ie.

~,5 ~S 7 Preparation examples:
Example 1:

F~O- C H 2- C C~

~`N
N

(Process a) A solution of 17.6 g (0.0623 mol) of Z-C2-(1,3-d;oxolan-2-yl)-prop-Z-yl~-2-(4-fluorophenoxymethyl)-oxi-rane in 30 ml of n-propanol are added dropwise to a sol-ution of 4.~3 g (0.0715 mol) of 1,204-triazole and 0.36 9 (0.0065 mol) of potassium hydroxide in 30 ml of n-propanol at room temperature. The react;on mixture is heated under reflux for 2 days and is then concentrated. The residue is taken up in ethyl acetate and the mixture is washed twice with.water and once with saturated sodium chloride solution, dr;ed over sodium sulphate and concentrated.
The residue is purified by column chromatography (dichloro-methane/ethyl acetate = 3:1) and recrystallised from alittle ether.
10.Z g (47% of theory) of 3-(1,3-dioxolan-2-yl)-1-(4-fluorophenoxy)-3-m~thyl-2-(1,2,4-triazol-1-yl-methyl)-2-butanol of melting point 102C to 104C are obtained.
Preparation of the starting substance~
._ _ ~)- C H 2--~C - - C
CHz CH3 8.4 g (0.0748 mol) of potassium tert.-butylate are added to a suspension of 16.47 9 (0.0748 mol) of tri-methylsulphoxonium iodide in 20 ml of absolute dimethyl-Le A Z2 013 -5~7~

-- 2~ --sulphoxide at room temperature1 The m;xture ;s subse-quently stirred for 30 rninutes and a solution of 3-~1,3-dioxolan-2-yl)-1-(4-fluorophenoxy)-3-methyl~2-butanone in 20 ml of absolute toluene is then added dropwise.
5 The reaction mixture is stirred overnight at room tempera-ture and is then heated at 50C for 2 hours and cooled, and water and toluene are added. The toluene phase is separated off, washed twice with water and once with saturated sodium chloride solution, dried over sodium 10 sulphate and concentrated.
17.6 9 (91% of theory) of 2-C2-(1,3-dioxolan-2-yl)-prop-2-yl]-2~(4-fluorophenoxymethyl)-oxirane are ob-tained as an oil, which is further reacted directly.

F ~ O-CH2-CO-C--( ~

-A mixture of 16.7 9 (0.15 mol) of 4-fluorophenol, 29 9 (0~15 mol) of 1-chloro-3-(1,3-dioxolan-2-yl)-3-methyl-2-butanone and Z3.4 9 (0 17 mol) of powdered potassium carbonate in 300 ml of methyl ethyl ketone is heated under reflux for 16 hours. It is allowed to cool and is fil-20 tered. The filtrate is concentrated, the residue is taken up in dichloromethane, the m;xture is washed once with 5% strength sodium hydroxide solution and once with water, dried over sodium sulphate and concentrated and the resi-due is distilled. 29 9 (72% of theory) of 3-(1,3-dioxo-25 lan-2-yl)-1-(4-fluorophenoxy)-3-methyl-2-butanone of boiling point 143C to 145C/0.1 mbar are obtained.

Cl-CH2-CO-C--~ 1 Le A 22 013 204 g (1.38 mols) of 4-chloro-2,2-dimethyl-3-keto-butanal are heated with 93 g (1~5 mols) of ethylene 0lycol and 0.7 9 of p-toluenesulphonic acid in 400 ml of methyl-ene chloride for 3 hours, using a water separator. The organic phase is extracted with 150 ml of 5~ strength sodium hydroxide solution and then ~00 ml of water. The solvent is dist;lled of-f and the residue is d;stilled under a water pump vacuum.
211 9 (79.8% of theory) of 1-chloro-3-(dioxo'an-2 yl-3-methyl-2-butanone of boiling point 127C to 128C/
14 mbar are obtained.

CH~
Cl-CHz-CO-C CH0 210 g (1.5 mols) of 1-(N-morpholino)-isobutene are added dropw;se, at 5C, to 169 g (1.5 mols) of chloro-acetyl chloride dissolved in 350 ml of diethyl ether,;n the course of one hour. ~hen the add;t;on has ended, the mixture is stirred for a further 3 hours, while cool-ing under reflux. The solution is poured onto 100 9 of ice, the pH is brought to 5 with aqueous sodium bicarbon-ate solution and the ether phase is separated off. The aqueous phase is extracted with 100 ml of diethyl ether, the organic phases are combined and dried over sodium sulphate, the solvent is d;st;lled off and the res;due is distilled under a water pump vacuum~
136.4 9 (61% of theory) of 4-chloro-2,2-dimethyl-3-keto-butanal of bo;ling point 95C to 98C/14 mbarare obtained.

Le A 22 013 ~5~7a,, Example 2 and 3:
-OH CH3 0 a~ CH3 Cl ~ C - C ~ ~ Cl ~ C - C

~N~ ~N~N
N _ N N__~
(Example 2) (Example 3) (Process a) A solution of 26.8 9 (0.1 mol) of 2-~4-chloro-phenyl)-2-C2~(1,3-d;oxolan-2-yl)-prop-2-yl~-ox;rane, 7.6g (0.11 mol) of 1,2,4-tr;azole and 0.5 g of potass;um hy-drox;de ;n 200 ml of absolute butanol ;s heated under reflux for 18 hours~ The m;xture ;s allowed to cool to room temperature, and 800 ml of water are added. The organic phase ;s separated off, dr;ed over sod;um sulphate and concentrated. The res;due ;s stirred with 200 ml of ;sopropyl e~her/ethyl acetate (10:1).
The sol;d wh;ch prec;p;tates is filtered off and dr;ed~ 4~5 g (13.3% of theory) of 3-(i,3-d;oxolan-2-yl)-2-(4-chlorophenyl)-3-methyl-1-(1,2,4-tr;azol-4-yl)-2-butanol (Example 2) of melt;ng po;nt 180C to 1~2C are obta;ned.
The filtrate is concentrated and the residue ;s f;rst taken up ;n 350 ml of acetone, and 8 g of 1,5-naph-thalened;sulphon;c ac;d ;n 30 ml of acetone are then added~The m;xture ;s st;rred at 0C for 6 hours, the sol;d is filtered off with suction and saturated, aqueous sodium b;carbonate/methylene chlorid solution is added. The or~anic phase is separated off, dried over sodium sulphate and concentrated.
19 9 (56.2% of theory) of 3-(1,3-dioxolan-2-yl)-2-(4-chlorophenyl)-3-methyl-1-(1,2,4-triazol-1-yl)-2-butanol (Example 3) are obta;ned as an oil.
Le A 22 013 ~7.,~

Preparation of the starting substance:

Cl~C~

29.5 9 (0~208 mol) of methyl iodide are added dropwise to 13.7 9 (0.22 mol~ of dimethyl sulphide in 130 ml of absolute dimethylsulphoxide and 120 ml of ab-solute tetrahydrofuran, whereupon the temperature rises to about 30C. The mixture is subsequen~ly stirred for 5 hours and a solution of 33 9 (0~13 mol) of 4~chloro-~ phenyl 2-C2-(1,3-dioxolan-2-yl)-prop-2 yl] ketone in 100ml of absolute toluene is then added. 9.5 g of sodium methyl~
ate are then added in portions in the course of one hour.
The reaction mixture is subsequently stirred for 3 hours and a further 5.6 9 of sodium methylate are added in two portions in the course of 30 minutes. The reaction mix-ture is stirred overnight and poured onto 700 ml of ice-water~ The organic phase is separated off and the aqueous phase is extracted by shaking with 200 ml of toluene.
The combined organic phases are washed with two 1,000 ml portions of water, dried over sodium sulphate and concen-trated~ The oily residue is degassed in vacuo.
26.8 9 of 2-(4-chlorophenyl)-2-C2-(1,3-dioxolan-2-yl~-prop-2-yl~-oxirane are obtained as an oil, which is further reacted directly.
Example 4:
Cl CH3 Cl ~ CH=CH c~

(Process a) Le A 22 013 ~5~

13.6 9 (0.2 mol) of imidazole are added in por-tions to 6 9 of sodium hydride (80% strength, 0.2 mol) in 200 ml of absolute dimethylformam;de, ~Ihereupon the temperature r;ses to about 45C. The m;xture ;s subse quently stirred for 30 m;nutes and 34 g (0 10~ mol) of 2-(2,4-d;chlorophenethenyl)-2-(5-methyl~1,3-d;oxan-5-yl)-ox;rane ;n 50 ml of absolute d;methylformamide are then added. The reaction mixture is st;rred at 80C for

4 hours. It ;s allowed to cool and ;s poured onto 800 ml of ;ce-water/600 ml of methylene chlor;de. The m;xture ;s subsequently st;rred for 45 m;nutes and the methylene chlor;de phase ;s separated off, washed twice w;th water, dr;ed over sod;um sulphate and concentrated~ The res;due is recrystall;sed from ether.
10.5 9 (25n4% of theory) of 1-(2,4-d;chlorophenyl) 4-(;m;dazol-1-yl)-3-(~,-methyl-1,3~d;oxan-5-yl)-1-buten-3-ol of melting po;nt 142C to 144C are obta;ned.
Preparation of the starting substance:
_ .

C l ~ c ~1- C H--~C~ C~ o~

56.8 9 (0.4 mol) of methyl iodide are added drop-wise to 26.4 g (0~425 mol) of d;methyl sulph;de ;n 180 ml of absolute d;methylsulphox;de and 175 ml of absolute tetrahydrofuran, whereupon the temperature rises to about 35C~ The mixture is subsequently st;rred for 16 hours 25 and a solut;on of 75.2 g ~0.25 mol) of 2~4-dichlorophen-ethenyl 5-methyl-1,3-d;oxan-5-yl ketone ;n 200 ml of abso-lute toluene ;s then added~ 17.4 g ~0.3 mol) of sodium methylate are ;ntroduced ;n port;ons at 0C. The m;xture is subsequently stirred for 3 hours, a further 10.~ g ~0.2 mol) of sodium methylate are added and the m;xture ;s stirred overn;ght. 250 ml of water are added to the Le A 22 013 57~

~ 33 -reaction mixture, the toluene phase ;s separated off and the aqueous phase is extracted w;th -two 150 ml portions of toluene. The combined toluene phases are washed with three 700 ml por~ions of water, dried over sod;um suLphate and concentrateda The oiLy residue is degassed in vacuo.
69 g of Z-tZ,4-dichLorophenethenyL)-2-(5~methyl-1,3-d;oxan-5-yl)-oxirane are obtained as an oil, which is further reacted directly.

Cl~CH=CH-CO Cr~

35 ml of 10% strength sodium hydroxide soLution are added dropwise to 70 g (0.4 moL) of 2,4-dichLorobenz-aldehyde and 57.5 9 of methyL 5-methyl-1,3-d;oxan-5-yl) ketone (85% strength, 0.4 moL) in 140 ml of ethanol and 50 ml of water. The reaction mixture is subsequently stirred at room temperature for 8 hours and is then poured onto 400 ml of methylene chloride. The organic phase is separated off~ washed with water, dried over sodium sulphate and concentrated. The oiLy residue crystallises after trituration with ether.
80 g of 2,4-dichlorophenethenyL 5-methyl-1,3-di-oxan-5-yl ketone of melting point 100C to 102C are obtained.

CH3-C0-C ~ >

360 g (5 mols) of methyl ethyl ketone and 225 g (2.5 moLs) of trioxane are heated under refLux in 1,000 mL
of chloroform, with addition of 40 mL of concentrated sulphuric acid, for 2 hours. The mixture is alLowed to cool, 2 litres of water are added and the mixture is sub-sequently stirred for 10 minutes. The organic phase is Le A 22 01_ separated off and stirred into saturated, aqueous sodium bicarbonate solution and the mixture ;s aga;n subsequently stirred for 10 m;nutes. The organic phase ;s separa~ed off, dr;ed over sodium sulphate and concentrated. The res;due ;s distilled in vacuo.
199 9 of methyl 5-methyL-1,3-dioxan-5-yl ketone of boiling point 50C to 5ZC/0.08 mbar are obta;ned.
Example 5:
Cl OH CH3 03H

CH2 C ~ x 1~2 ~N~N S~3H
N ~
(Process a / salt formation) 13.8 g (0~2 mol) of 1,2,4-triazole are added in portions to a suspension of 6 9 of sod;um hydr;de (80%
strength, û42 mol) in 330 ml of absolute dimethylformamide.
The mixture is subsequently stirred for 30 minutes and 45~(0,13~ mol) 2-(2,4-dichlorophenylethyl)-2~C2(1,3-d;oxolan-2-yl)-pro-2-yl]-oxirane in 80 ml of dimethylforam;de ;s then added.
The react;on m;xture is s-tirred at 80C for 4 hours. It is then allowed to cool and is poured onto 600 ml of ice-water/800 ml of methylene chlor;de. The methylene chlor-;de phase is separated off, washed with two 1,500 ml por t;ons of water, dried over sod;um sulphate and concen-trated. The oily res;due ;s taken up in 400 ml of acetone, and 14.4 9 of 1,5-naphthalenedisulphonic acid ;n 40 ml of acetone are added at 0C. The mixture is subsequently stirred for 5 hours and the prec;p;tate formed ;s f;ltered off w;th suction.
43.1 g (29~1% of theory) of 1-(2,4-dichlorophenyl)-4-(1,3-dioxolan-2-yl)-4-methyl-3-(1,2,4-triazol-1-yl-methyl)-3-pentanol 1,5-naphthalenedisulphonate of melting point 183C are obtained.

Le A 22_013 ~S~ a Preparat;on of the starting substance:
~ _ _ _ ._ _ _ _ _ _ _ _ _ _ C l ~ C H 2 - C H --C ~--< ~

90 g of 2-(2,4-dichlorophenylethyl)-2-~Z (1,3-dioxolan-2-yl)-prop-2-yl]-oxirane are obtained as an oil, S which ;s further reacted directly, by react;on of 83 g tO.262 mol) of 2,4-d;chlorophenylethyl 2-(1,3-dioxolan-2-yl~-prop-2-yl ketone with 28.2 g (0~455 mol) of dimethyl-sulph;de/60 g of methyl ;od;de accord;ng to Example 3.

c l ~ C H 2 C H 2 C o t~ 3 100 g of 2,4-dichlorophenylethenyl 2-(1,3-dioxolan-2-yl)-pro-2-yl) ketone are heated to 25C under a press-ure of 55 bar with 10 g of Raney nickel ;n 600 ml of tetrahydrofuran for 25 m;nutes. The react;on m1xture is then concentrated and the residue is dist;lled in vacuo.
83 g of Z,4-dichlorophenylethyl 2-(1,3-dioxolan-2-yl)-prop-2-yl ketone of boiling point 148C/0.1 mbar are obtained.

Cl ~ CH=CH-C0-C ~ ~

95 nl of 10% strength sodium hydroxide solution are added dropwise to 196 g (1.12 mol) of 2,4-d;chloro-Le A 22 013 d benzaldehyde and 178 g (1.125 mol) of methyl 2-(1,3-di-oxolan-2-yl)-prop-2-yl ketone in ltOO ml of ethanol and 140 ml of water. The reaction m;xture ;s subsequently stirred for 10 hours and the solid formed is filtered off with suct;on and washed w1th ethanol~
309 g of 2,4-dichlorophenylethenyl Z-(1,3-dioxolan-2-yl)-pro-2-yl ketone of melting point 92C to 93C are obtained.
Example 6:

CL~CH2-CH2-C--C~ 1 CHz CH3 ~N~
N__~
(Process d / ether formation) 1.4 9 (n.046 mol) of sodium hydride are added to 18 q (0~045 mol) of 1-(2,4-dichlorophenyl)-4-(1,3-d;oxan-2-yl)-4-methyl-3-(1,2,4-triazol-1-yl-methyl)-3-pentanol in 150 ml of absolute dioxane. The mixture is subsequently stirred at room temperature for 5 hours and 7.1 9 (0.05 mol) of methyl iodide are added. The mixture is then stirred overnight, and 0.7 g (O.OZ3 mol) of sodium hydride and 3.5 9 (0.025 mol) of methyl iodide are again added. After subsequently stirring for a further period, the inorganic salts are filtered off with suction. The filtrate is concentrated, the oily residue is taken up in methylene chloride and the mixture is rinsed with two 600 ml portions of water~ dried over sodium sulphate and concentrated. The residue is recrystallised from iso-propyl ether.
12 9 (64.4~ of theory) of 1-~2,4-dichlorophenyl)-4-(1,3-dioxan-2-yl)-3-methoxy-4-methyl-3-~1,Z,4-triazol-1-yl-methyl)-pentane of melting point 130C to 13ZC are obtained.
Le A 22 013 ;~s~5~a~

The following compounds of the general formula (IQ) are obtained in an analogous manner and by the abo-ve proces~
descriptions:

OH~CH3~ (Ia) CH 2~ CH 3 )n Az Melting point ( C) Exarnple R Az n Het or nZD

7 Cl~CH2-CH2- N~ N ~(O~ 179 (x 1/2 NDS) 8 Cl~CH2-CH2~ ~ > 119 - 121 9 C l~CH2-CH2- -N~ O ~ ) 125 ~ 1 Z7 C l~CH=CH--N ~ 116 - 118 Cl 11 Cl ~ CH=CH N ~ N -<O

Le A 22 013 -3 - ~

~5~5~7~

Melting point (C) Example R Az n H~t n2a No. D

12 Cl~CH=CM- -N I 0 ~ > 182 - 184 Cl N_ CH
13 Cl~CH=CH--N 1 0 ~C ~ 171 173 14 ~0-CHz-N~ N ~0~ 106 107 15 Cl~0-CH~-~N ~(01 105 ~ 107 ~ ~ N ~? -/Cl CH3 17 Cl~O-CH2-/N~ JCo) 1'7 - 122 18 Cl~O-CH2--N ¦ 0 ~C ~ 220 - 225 19 Cl~CH2-CH2- -N~ 93 20 Cl~CH2-CH2- N~N ~~0l 140-143 (x 1/2 NûS) 21 Cl~CH2-CH2- -N/~l o Ç~) 122 - 12 Le A 22 013 -~-,5~;7~

Melting point ~C) Exa ple R Az n Het or n2Do .

22 Cl ~ -CH2-CH2- -N ~ 0 ~ ) 68 - 73 23 Cl ~ CH=CH- ~ N 0 24 Cl ~ CH=CH- -N ~ 12Z - 1Z5 Cl ~ H=CH- N 9 0 ~ ) 19Z - 195 26 Cl ~ 0-CHz- -N 9 0 ~ ) 141 144 Cl CH3 ~7 Cl ~ 0-CH2- N ~ 0 N ~ /N _ 1 0 ~
28 L ,N-CH2 ~ N ol 1,5240 29 @~o-cHz- -N ~ ~ 89-92 3G Cl ~ 0-CH2- -N ~ 129-30 31 ~ ~ 0-CH2- N ~ N ~ o ~ 138-39 NDS = 1, 5-napthalene~disulphonic acid Le A 22 013 ;~ a~
- 40 ~

M.p. ( C) Example R Az n Het or 20 No. n~
, . .

32~ O-CH2- -N ~ 1 ~CL_/~ 149 33Cl- ~ -CH=CH- ~ N ~ ~ 147-49 34Cl- ~ -CH=CH- -N ~ O J 152-55 35 Cl ~ -CH2-CH2- ' ~ 1 ~ ] v~scous 36 Cl- ~ -CH2-CH2 -N ~ C2H5 37 Cl ~ -O-CH2- -N ~ 169-72 C2H5 (x1 NDS) 38 Cl- ~ -O-CH2- -N ~ ~ ~ v~scous C2H, Le A 22 013 .

M.p. (C) Example R Az n Het 20 No~ or nD

3 9 C 1~ _o -CH 2 - -N,~ 1 < ~ v i s c o u s o i l Cl-~)-CH2~cH2~ 110-12 41 Cl -<~-CH2 -CH2 - -N~ 1 1 7 -19 42 ~ --CH -- ~ N ~2~

43 Cl~I=CH- N~ ~ lC2~5 80 44 Cl~--CH- ~3N lC H 88--90 Cl~_S_CH2~ v i s c ous o i l O

Le A 22 013

5~

E x a m p l e R Az n Het ; n.2 0 46 ~-(~2 \~_N ol C2H5 105 ~Cl /~ \{ ~3v i s c ou s o i l 48 Cl-~-CH=CH- \~ { ~3 49 ~ vi s cous oi l~l- -N 1 -<b ~ 100 N--I O--5~ cl-~) CH2~rI2 ~7 O ~--C3H7 v i s c ou s o i l 52 Cl-~2CH2- -N ~ 115 <~Cl ~ OolC3H 7 54 C~ 2CH2- ~ ol C~13 Le A 22 013 7~

M.p. ( C) N o . ~ A2 n He t D -C~ H2CH - -N~ 1 ol CH3 v i s c ou s o i l 56 Cl-~CH2- \=N olcH3 vi scous oi l 57 Cl-(~ ~}CH2- -N~ 1 ~O~ 123 5~ Cl ~{~CH - ~~ O~ 81 59 ~)~I=CH- -N/~ 1 ~ ) 146 N .~ O
~ CH=CH- ~~ 170 61 ~ ~) CH2CH2 ~ N CH~ o 98 62 (~) ~ -CH2CH2-- -N/~ 0 ~ > 131 63 C~ (l ~/i scous Oi ~ A 22 013 5~

Exampl~ M.p. ( C) N o . R Az n He t 64Cl~i2 -N~ 2 5 65Cl~ CHCH2_ -/1 =~ 1 ~l viscous oi l 66~ ~}CH2- -N~ 126 67Cl~CH - N/~~
2 ~N v i s c o u s o i l /~ ~O~ visCouS oi l 68Cl~)- -N ¦ 1 0 1 C EI_ CH~, ~ 1 2 ~ Vi SCOUS 0i l 70C14~ CHCH2_ / N l ~ H v i s c ou s o i l 3 /~= ~ 1 viscous oi l 71Cl~CH2- -N ¦ 1 \~N C3H7 Le A 22 013 ~5~57f~, Example R Az n Het M~p. (C) _ _ or Z

72 ~ 0-CH2- -N 1 1 ~ 0~ viscous oil 13 ~ -0-CH2 \_ rl ~O > 96-98 74 ~ 0-CH2- -N ¦ O ~ O> 148-51 75 ~ ~ -0-CH2- _~ 1 0 ~ 0~ 113-15 70 ~ -0-CH2 N ~ O ~ ~ > 169-71 77 ~ ~ -CH=CH~ viscous oil 78 ~ -CH=CH- -N ~ `'C2H5 79 ~ ~ -CH2-CH2- - ~ ~ viscous-oil 80 ~ CH2-CH2- ~ viscous oil 81 Cl ~ ~~ ~ viscous oil ~2 ~ ~ ~ C2~15 Le A 22 Ol3 - 4~ -Example R A~ n Het ?~I,P. 20C) No. or n[~

83Cl~0-CH2- /~ ] ~ 1 viscous oil 84Cl~HcH2_ ~_ N 1 \0 _~ viscous oil 8 5~ CH3 _~ 1I C H5 8 6~CH3 ~ \0 ~ viscous oil 8 7Cl-~- -N ~ ~ ~ viscous oil 88 Cl~ N ~ 0--- 138 I`~~ 1 viscous oil 89(CH3)3C4~ rl~l~ \0-90(cH3)3c~ _N~ 0--- 164-66 Le A 22 013 ~,54~

Use exa~ples:
The substances shown below are employed as com-parison compounds in the use exampLes which folLow:

OH
(A) ~ O-CH7-C - C(CH3)3 `N
N
OH C~
(B) Cl ~ O-CH~-C ~ Cl CH, ~Cl OH
(C) F ~ O-CH7-C C(CH3)3 N

Le A 22 013 _.

- ~8 -Ex~le A
-Pucc;n;a test (wheat) t protective Solvent- 100 parts by we;ght of dimethylformamide Emuls;fier: 0.25 parts by we;ght of alkylaryl poly-glycol ether To produce a su;table preparation of act;ve com-pound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the con-centrate ;s diluted w;th water to the desired concentration.
To test for protective activity, young plants are inoculated with a spore suspension of Pucc;n;a recondita ;n a 0.1% strength aqueous agar solution. After the spore suspension has dried on, the plants are sprayed with the preparation of active compound unt;l dew-mo;st. The plants remain in an incubation cabin at 20C and 100%
relat;ve atmospheric hum;d;ty for 24 hours.
The plants are placed ;n a greenhouse at a tempera-ture of about 20C and a relative atmospheric humidity of about 80~ in order to promote the development of rust pustules.
Evaluation is carried out 10 days after the inoculation.
In this test, a clearly superior activity com~
pared with the prior art is shown, for example, by the compounds according to the following preparation examples:
12, 13, 25, 10~ 23, 8, 11, 21, 24, 7, 19, 9, 22, 5, 20 and 14.

Le A 22 013 7aR
~9 _ Example 8 sotryt;s test ~beans)/protect;ve Solvent: ~.7 parts by we;ght of acetone Emuls;f;er: 0.3 parts by we;ght of alkylaryL polyglycol ether To produce a su;table preparat;on of act;ve com-pound~ 1 part by we;ght of active compound is m1xed with the stated amounts of solvent and emulsifier, and the concentrate ;s d;luted w;th water to the des;red concen-tration.
To test for protect;ve act;v;ty, young plants are sprayed w;th the preparat;on of act;ve compound unt;l dripping wet. After the spray coating has dried on, Z
small p;eces of agar covered w;th 8Otrytis cinerea are placed on each leaf~ The ;noculated plants are placed in a darkened humidity chamber at 20C. 3 days after the inoculation, the size of the ;nfected spots on the leaves ;s evaluated~
In th;s test, a clearly super;or act;v;ty com-pared w;th the pr;or art ;s shown, for example, by the compounds accord;ng to the following preparation examples:
11, Z1, Z4, 7, 19 and 5.

Le A Z2 013

Claims (15)

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

1. A heterocyclyl-hydroxyalkyl-azolyl derivative of the formula (Ie) in which Az represents 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl or imidazol-1-yl, Het represents 1,3-dioxan-5-yl unsubstituted or substituted by identical or different substituents selected from the group con-sisting of alkyl with 1 to 4 carbon atoms, and phenyl and phenoxy-alkyl with 1 to 4 carbon atoms in the alkyl part, each of which is optionally monosubstituted or polysubstituted by identical or dif-ferent substituents, substituents on the phenyl being selected from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms and halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms;
R represents straight-chain or branched alkyl with 1 to 7 carbon atoms, or phenyl, phenylalkyl with 1 to 4 carbon atoms in the alkyl part, phenoxy- or phenylthio-alkyl with in each case 1 to 4 carbon atoms in the alkyl part or phenylethenyl, each of which is optionally monosubstituted or polysubstituted by identical or dif-ferent substituents, substituents on the phenyl groups being selected from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with in each case 1 or 2 carbon atoms, nitro, halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or dif-ferent halogen atoms, hydroximinoalkyl with 1 to 4 carbon atoms, alkoximinoalkyl with 1 to 4 carbon atoms in each alkyl part, and phenyl, phenoxy, benzyl and benzyloxy, each of which is optionally substituted by halogen or alkyl with 1 or 2 carbon atoms; or R represents cycloalkyl with 5 to 7 carbon atoms, which is in each case optionally monosubstituted or polysubstituted by identi-cal or different alkyl radicals with 1 to 4 carbon atoms, or cycloalkyl-methyl or -ethyl with 5 to 7 carbon atoms in the cyclo-alkyl part, or cyclohexylethenyl, or, alkenyl with 2 to 6 carbon atoms, 2-furyl, naphthyloxy-methyl, 1,2,4-triazol-1-yl-methyl, 1,2,4-triazol-4-yl-methyl, imidazol-1-yl-methyl or pyrazol-1-yl-methyl, and R' represents hydrogen, alkyl which has 1 to 4 carbon atoms and is optionally substituted by phenyl, it being possible for the phenyl radical to be substituted by the substituents on phenyl men-tioned under R, or alkenyl with 2 to 4 carbon atoms, or a non-phytotoxic addition product thereof with an acid or metal salt wherein said acid is selected from the group consisting of hydrogen halide acids, phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids, hydroxycarboxylic acids and sul-phonic acids and said metal is selected from the group consisting of metals of main groups II to IV and of sub-groups I and II and IV to VIII.

2. A compound according to Claim 1, wherein Het represents 1,3-dioxan-5-yl, which is optionally mono-, di-or tri-substituted by identical or different substituents selected from the group consisting of methyl, ethyl, n-propyl, isopropyl and phenyl and phenoxymethyl, each of which is optionally mono-, di- or tri-substituted by identical or different substituents from the group comprising fluorine, chlorine, methyl, trifluoromethyl and trifluoromethoxy;
R represents tert.-butyl, trimethyl-propyl or tetramethyl-propyl, or phenyl, benzyl, phenethyl, phenoxymethyl, phenylthio-methyl or phenethenyl each of which is optionally mono-, di- or tri-substituted by identical or different substituents selected from the group consisting of fluorine, chlorine, methyl, trifluoro-methyl, trifluoromethoxy, trifluoromethylthio, hydroximinomethyl, 1-hydroximinoethyl, methoximinomethyl, 1-methoximinoethyl, and phenyl, phenoxy, benzyl and benzyloxy, each of which is optionally substituted by chlorine and/or methyl; or R represents cyclohexyl, cyclohexylmethyl, cyclohexylethyl or cyclohexylethenyl each of which is optionally mono-, or di-substituted by identical or different substituents from the group comprising methyl, ethyl and isopropyl; or R represents allyl, dimethylpropenyl, 2-furyl, naphthyloxy-methyl, 1,2,4-triazol-1-yl-methyl, 1,2,4-triazol-4-yl-methyl, imidazol-1-yl-methyl or pyrazol-1-yl-methyl; and R' represents hydrogen, methyl, 4-chlorobenzyl or allyl, and said acid is selected from the group consisting of hydrochloric, hydrobromic, phosphoric, nitric and sulphuric acids and said metal is selected from the group consisting of copper, zinc, manganese, magnesium, tin, iron and nickel.

3. A compound according to Claim 1 or 2 wherein R is 4-chlorophenethyl.

4. 1-(4-Chlorophenyl)-4-(1,2,4-triazol-1-yl)-3-(5-methyl-1,3-dioxan-5-yl)-3-butanol of the formula

5. 1-(4-Chlorophenyl)-4-(imidazol-1-yl)-3-(5-methyl-1,3-dioxan-5-yl)-3-butanol of the formula

6. A method of combating fungi which comprises applying to a fungus or a fungus habitat a fungicidally effective amount of a compound according to Claim 1.

7. A method according to Claim 6 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable carrier or diluent.

8. A method according to Claim 7 wherein the active ingre-dient concentration in said composition is between 0.0001 to 1% by weight.

9. A method according to Claim 7 wherein the active ingre-dient concentration in said composition is between 0.001 to 0.5%
by weight.

10. A method according to Claim 6, 7 or 9 wherein the com-pound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

11. A method according to Claim 6, 7 or 9 wherein the com-pound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

12. A method according to Claim 6, 7 or 9 wherein the com-pound is applied to soil in an amount to give a soil concentration of 0.00001 to 0.1% by weight at the place of action.

13. A method according to Claim 6, 7 or 9 wherein the com-pound is applied to soil in an amount to give a soil concentration of 0.0001 to 0.02% by weight at the place of action.

14. A method according to Claim 9, 10 or 12 wherein such com-pound is 1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-3-(5-methyl-1,3-dioxan-5-yl)-3-butanol.

15. A method according to Claim 9, 10 or 12 wherein such com-pound is 1-(4-chlorophenyl)-4-(imidazol-1-yl)-3-(5-methyl-1,3-dioxan-5-yl)-3-butanol.