NZ202107A

NZ202107A - Phenoxyphenyl azolylmethyl ketones and carbinols;fungicides

Info

Publication number: NZ202107A
Application number: NZ202107A
Authority: NZ
Inventors: H-L Elbe; K H Buchel; W Brandes; P-E Frohberger; V Paul
Original assignee: Bayer Ag
Priority date: 1981-10-10
Filing date: 1982-10-07
Publication date: 1985-07-12
Also published as: AU8922382A; GR77014B; ZA827370B; JPS5872568A; EP0077479A2; ES516368A0; PL238571A1; PT75638A; CS235964B2; IL66942A0; PT75638B; DK447082A; DE3140276A1; DD206728A5; CA1187084A; EP0077479A3; BR8205929A; ES8307004A1; PL134646B1

Description

New Zealand Paient Spedficaiion for Paient Number £02107 N.Z.No.

NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION L--70 cr fens.®/ "PHENOXYPHENYL AZOLYLMETHYL KETONES AND CARBINOLS, PROCESSES FOR THEIR PREPARATION, AND THEIR USE AS FUNGICIDES AND AS INTERMEDIATE PRODUCTS" We, BAYER AKTIENGESELLSCHAFT, company registered under the laws of the Federal Republic of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement : - _ 1 _ (followed by 1A) J C>7 1A- Type lb The present invention relates to certain new phenoxyphenyl azolylmethyl ketones and carbinols, to a process for their-preparation and to their use as fungicides and as intermediate products for the synthesis of further plant protection agents.

It has already been disclosed that phenyl azolylmethyl ketones and carbinols possess fungicidal properties (see Great Britain "Patent Specification No.1,464,224.

However, the action of these azolyl derivatives is not always completely satisfactory in many areas of indication, in particular when small amounts and low concentrations are used.

The present invention now provides, as new compounds, the phenoxyphenyl azolylmethyl ketones and carbinols of the general formula Az represents 1, 2, 4-1riazo1-1 -y1 or -4-yl or imidazol-1-y1, A represents the keto group or the -CH(OH)- or -C(0H)R grouping, R represents alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted phenyl or optionally substituted phenalkyl, 1 R represents alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, ha 1ogenoa1ky1, alkoxyalkyl, halogenoa1koxya 1ky1 , a 1ky11hioalky1 , balogeno-alky11hioa1ky1 , dia 1kylaminoaIky 1 or optionally A — CH — R1 Az (I) V2 in which 202 1! 0 7 substituted phenalky 1 or 1 R may represent hydrogen, provided that at the same time X does not represent unsubstituted 12 3 phenyl and Y , Y and Y do not represent hydrogen, 5 or provided ttiat R does not represent alkyl, cycloalkyl or cycloalkylalkyl, X represents phenyl which optionally carries one or more substituents selected independently, and 12 3 Y , Y and Y are selected independently and each 10 represent hydrogen, halogen or alkyl, and their plant-tolerated acid addition salts and metal salt complexes.

The compounds of the formula (I) may possess two asymmetric carbon atoms; they can then be present as the 15 two geometrical isomers (threo form and erythro form), which can occur in varying proportions. In both cases, they are present as optical isomers.

The present invention also provides a process for. the preparation of a phenoxyphenyl azolylmethyl ketone or 20 carbinol of the formula (I), in which (a) a halogenoketone of the general formula (II) , in which Hal represents halogen, preferably chlorine or bromine, and 12 3 X, Y , Y and Y have the meanings given above, is reacted with an azole of the general formula 30 H - Az (III), in which Az has the meaning given above, in the presence of a diluent and in the presence of an acid-binding agent; or 35 (b) an azolyl ketone of the general formula x - 0 -<£5}— C0 " CH2 - Az (la), in which 12 3 Az, X, Y , Y and Y have the meanings given above, is reacted with an alkylating agent of the general formula R1 - Z (IV), in which 1 R has the meaning given above and Z represents an electron-attracting leaving grouping, in the presence of a base and in the presence of an organic diluent, or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst; or (c) an azolyl ketone of the general formula X - 0 ~ (Q) —CO - CH - R2 (lb) , Az in which . _ Y1 Y2 Y3 12 3 Az , X, Y , Y and Y have the meanings given above and 2 11 R represents hydrogen or R , where R has the meaning given above, is reduced by reaction with a complex hydride or aluminium isopropylate in the presence of a diluent, or is reacted with an organometallic compound of the general formula M - R (V) , in which R has the meaning given above and M represents an alkali metal or the radical Hal'-Mg, wherein Hal' represents chlorine, bromine or iodine, in the presence of a diluent.

An acid or a metal salt can then be added onto the compound of the formula (I) obtained by process variant (a), (b)'or '(c), if appropriate. In some cases it proves to be advantageous to obtain the compounds of the formula (I) in pure form via their salts.

The phenoxyphenyl azolylmethyl ketones and carbinols of the formula (I) and their derivatives possess powerful fungicidal properties. Surprisingly, the compounds according to the invention exhibit a better fungicidal action than the phenyl azolylmethyl ketones and 15 carbinols which are known from the state of the art and are chemically similar compounds with a similar action .

In addition, the phenoxyphenyl azolylmethyl ketones and carbinols of the formula (I) are interesting inter-20 mediate products for the preparation of further plant protection agents. In the keto derivatives, the keto group can be reduced.to a -CH(OH) group or to a -CR(OH) group (see process variant (c)). Furthermore, functional derivatives of the keto group, for example oximes, oxime 25 ethers, hydrazones and ketals, can be obtained by appropriate reactions. The carbinol derivatives can be converted into the corresponding ethers in the customary manner, at the hydroxyl group. Furthermore, acyl or carbamoyl derivatives of the compounds of the formula (I) 30 can be obtained by reaction with, for example, acyl halides or carbamoyl chlorides in a manner which is known in principle.

The substances according to the invention thus represent a valuable enrichment of the art.

Formula (I) gives a general definition of the phenoxyphenyl azolylmethyl ketones and carbinols according to the invention. Preferred compounds are those of the general formula ■ 1 ■ ^ ^ . r 1 0 - Y1 Y (IA) in which Az represents 1,2,4-triazol-1-yl or -4-yl or imidazol-1-yl , A represents the keto group, or the -CH(OH) or 10 -C(0H)R grouping, R represents straight-chain or branched alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 2 carbon atoms in the alkyl part, alkenyl or alkynyl each having 2 to 6 carbon atoms, optionally substituted phenyl or optionally substituted phen-alkyl having 1 to 4 carbon atoms in the alkyl part, preferred substituents on the phenyl in 20 either case being halogen and alkyl having 1 to 4 carbon atoms , 1 R represents straight-chain or branched alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkyl-alkyl having 3 to 7 25 carbon atoms in the cycloalkyl part and 1 to 2 carbon atoms in the alkyl part, alkenyl or alkynyl, each having 2 to 6 carbon atoms, alkoxyalkyl or alkylthioalkyl , each having 1 to 2 carbon atoms in each alkyl part, halogenoalkyl 30 having 1 to 8 carbon atoms and 1 to 5 halogen Lu illi D1 J08 202107 atoms (preferably fluorine atoms and chlorine atoms), halogenoalkoxyalkyl or halogenoalkyl-thioalkyl, each having 1 to 4 carbon atoms in each alkyl part and 1 to 5 halogen atoms (preferably fluorine atoms and chlorine atoms), dialkylaminoalkyl having 1 to 4 carbon atoms in each alkyl' part, or optionally substituted pnenylalkyl having 1 to 4 carbon atoms in the 1 alkyl part, the radicals mentioned for X being suitable phenyl substituents, 1 or R may represent hydrogen provided that at the same time X^ , X^, X3, y\ and Y^ do not represent hydrogen, or provided that R does not represent alkyl, cycloalkyl or cycloalkylalkyl, 1 X represents hydrogen, halogen, alkyl having 1 to 4- carbon atoms, halogenoalkyl, halogenoalkoxy or halogenoalkylthio, each having 1 to 4 carbon atoms and 1 to 5 halogen atoms (preferably fluorine atoms and chlorine atoms), alkoxy or alkylthio, each having 1 to 4 carbon atoms, amino, alkyl-amino or dialkylamino , each having 1 to 4 carbon atoms in each alkyl part, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl part, nitro or cyano, 2 X represents hydrogen, halogen or alkyl or alkoxy, each having 1 to 4 carbon atoms, or 1 2 X and X together, in the o-position to one another, represent methylenedioxo, X3 represents hydrogen, halogen .or alkyl qT alkoxy, each having 1 to 4 carbon atoms, 1 Y represents hydrogen, halogen or alkyl having 1 to 4 carbon atoms, Y represents hydrogen or halogen, and Y3 represents hydrogen. ?107 1 o Particularly preferred compounds are those of the formula (IA ) , in which A and Az have the meanings given above, R represents "straight-chain or branched alkyl having 1 to 4 carbon atoms, cycloalkyl or cyclo-alkylmethyl, each having 5 or 6 carbon atoms in the cycloalkyl part , alkenyl or alkynyl, each having 2 to 4 carbon atoms, or optionally substituted phenyl or benzyl, the following being mentioned as possible substituents : fluorine, chlorine, bromine and methyl, 1 R represents straight-chain or branched alkyl having 1 to 8 carbon atoms, cycloalkyl or cycloid alkylmethyl, each having 5 or 6 carbon atoms in the cycloalkyl part, alkenyl having 2 to 6 carbon atoms, alkynyl having 2 to 4 carbon atoms, alkoxy-alkyl or alkylthioalkyl, each having 1 to 2 carbon atoms in each alkyl part, halogenoalkyl having 20 1 to 4 carbon atoms and 1 to 5 halogen atoms (especially fluorine atoms and chlorine atoms), halogenoalkoxyalkyl or halogenoalkylthioalkyl, each having 1 to 2 carbon atoms in each alkyl part and 1 to 5 halogen atoms (especially fluorine atoms 25 and chlorine atoms), dialkylaminoalkyl having 1 to 2 carbon atoms 'in each alkyl part, or optionally -1 substituted benzyl, the radicals mentioned for X being suitable phenyl substituents, i or R may represent hydrogen provided that at the same time , X^, X3, y'' , Y^ and Y3 do not. represent hydrogen, or provided that R does not represent alkyl, cycloalkyl or cycloalkylalkyl, X represents hydrogen, fluorine, chlorine, 1 0 bromine, methyl, trifluoromethyl, trifluoro-methoxy, trifluoromethylthio, methoxy, methyl-thio, amino, dimethylamino, methoxycarbonyl , nitro or cyano , 2 X represents hydrogen, fluorine, chlorine, methyl or methoxy, or X^ and X^ together, in the o-position to one another, represent methylenedioxo, X3 represents hydrogen, fluorine, chlorine, methyl or methoxy, 1 Y represents hydrogen, fluorine, chlorine or methyl, 2 Y represents hydrogen, fluorine or chlorine, and Y3 represents hydrogen. in addition to the compounds mentioned in the preparative examples,, the following compounds of the general formula (IA) may be mentioned individually (Az representing 1,2,4-triazol-1-yl or imidazol-1-yl): (IA) 202107 x1 x2 x3 y1 y2 9 -y3 a r1 u-ci h h h h h -C(OH)-® h 4-C1 h h h h h -C(0H)-CH2^g> h 4-C1 h h h h h -c(0h)-ch2ch=chch3 h 4-c1 h h h h h -c(ok) -ch2-c=ch h 4-f h h h h h -C(OH)H^) h 4-f h h h h h -C(0H)-CH2-^^ h 4-f H h H H H -c(0h)-ch2ch=chch3 h 4-f H H h H H -c(0h)-ch2-c = ch h 4-f H H- H H H -co- ch3 4-f H H H H h -co- c2hs a-f h h h h h -co- c3h7 4-f h h h h h -co- c^ha 6-f h h h h h -cd- csh11 4-f h h h h h -co- 6-F h h h H h -ch(oh)- ch3 4-f h h h h h -ch(oh)— c2h5 i-F h h H h h -ch(oh)- 0 3h7 4-f H H H H H -ch(oh)- Cl.H3 t-F H K H H hi -ch(oh C5H',i ——r H H H H H -CH(OH)- 1-C3H7 Mo > r <202 10 • x1 x2 x3 v1 y2 y3 A S1 4-n(ch3)2 h h h h h -c0- C3H7 -o-ch2-o- h h h h -co- O3H7 4-ch3 h h h h h -co- c3h7 • 3-OCH3 ' 4-OCH3 -0ch3 h h h -co- O3H7 4-co-OCH3 h h h h h -cd- C3H7 4-SCF3 h h h h h -co- C3H7 4-n02 H H H H H -co- C3H7 • 4-cn H H H h h -co- O3H7 4-8r H H H H H -co- c3h7 4-OCF3 H H H H H -co- c3h7 4-n(ch3)2 H h H h h -ch(oh)- O3H7 -0-ch2-0- H H H H -ch(oh)- O3H7 4-CH3 H H H H H -ch(oh)- C3H7 • 3-OCH3 4-OCH3 : -och3 H H H -ch(oh)- O3H7 4-co-OCH3 H H H H H -ch(oh)- C3H7 4-SCF3 H H H H H -ch(oh)- o3h7 • 4-n02 H H H H H -CH(OH)- C3H7 4-cn H H H H H -CH(OH)- C3H7 • 4-0r H H H H H —ch(oh )- C3H7 4-OCF3 H H H H H -ch(oh)- C3H7 4-F .

H H H H H -CO- -ch2ch20ch3 • 4-F H H H H H -CO- -ch2ch2sch3 4-F H H H H H -CO- -ch2ch2n(CH3)2 ^■OpfC X1 X2 X3 Y1 Y2 y3 A R1 4-F H H H H H —ch(oh )- -ch2ch-20ch3, 4-F H H •H- H H -ch(oh)- -ch2ch2sch3 4-F H H H H H -ch(oh)- -ch2ch2n(CH3)2 4-Cl H H H H H -ch(oh)- -ch2ch2och3 4-Cl H H H H H -ch(oh)- -ch2ch2sch3 4-Cl H H H H H —ch(oh )- -ch2ch2n(ch3)2 4-Cl H H H H H -co- -ch2ch2och3 4-Cl H H H H H -co- -ch2ch2sch3 4-Cl H H H H H -CQ- -ch2ch2n(ch3)2 4-Cl h h 3-C1 H H -co- C3H7 4-Cl H H 3-C1 H H -ch(oh)- 03h7 4-Cl H H 3-CH3 H H -co- C3H7 4-Cl H h 3-CH3 h h -ch(oh)- ^3H7 4-Cl H h h H H -c(oh)ch3 ^3H7 4-Cl H h H H H -c(oh) —c3h7 • c3h7 4-Cl h H H H H -co- -ch2^h) 4-Cl H H H H H -ch(oh)- -CH2^) .

If, for example, U-chloro-4-(4 '-chlorophenoxy ) - acetophenone and 1,2,4-triazole are used as starting materials in process variant (a), the course of the reaction can be represented by the following equation: If, for example, 4 —(4'-chlorophenoxy) - U-(1 ,2,4-triazo1-1 -y1)-acetophenone and 4-chlorobenzyl chloride are used as starting materials in process variant (b) the course of the reaction can be represented by the following equation: triazol-1 -yl)-acetophenone and sodium borohydride are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation: If, for example, 1 -(4-chloropheny1)-3-[4-(4 ' -chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3 If, for example, 4-( 4 '-c h 1 orop henox y ) - u) - (1 , 2 , 4- -0210 7 one and methyl-magnesium b.romide are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation: Cl~<^)-0-<^)-C0-CH-CH2-^)-C1 + CH3MgBr > N U - J H i ,<^N Formula (II) gives a general definition of the halogenoketones required as starting materials for carry- 1 ing out process variant (a). In this formula, X, Y , 2 3 Y and Y preferably have the meanings given in the preferred definition of the invention.

The halogenoketones of the formula (II) have not hitherto been disclosed in the literature; however, they can be prepared in a generally known manner by reacting, for example, diphenyl ethers of general formula x - ° - Y1 y 2 Y 3 inwhich —• 12 3 X, Y , Y and Y have the meaning given above, with chloro(bromo)acetyl chloride (bromide) under the conditions of a Friedel-Crafts acylation (see also the preparative examples).

Formula (III) gives a general definition of the azoles additionally to be used as starting materials for process variant (a). In this formula Az has the meanings given in the definition of the invention . 2021C.

The azoles of the formula (III) are generally known compounds af organic chemistry.

Formula (la) gives a general definition of the azolyl ketones to be used as starting materials for 5 carrying out process variant (b). The compounds of the formula (la) are themselves compounds according to the invention: they are prepared by process variant (a).

Formula (IV) gives a general definition of the alkylating agents additionally to be used as starting 10 materials for process variant (b) according to the 1 invention. In this formula, R preferably has the meanings given in the preferred definition of the invention. Z preferably represents an electron-attracting leaving grouping, such as, for example, halogen, p-methylphenyl-15 sulphonyloxy or the grouping -O-SO^-OR1 or -NR^,whereas R1 represents, for example, alkyl with 1 to 4 carbon atoms.

The alkylating agents of the formula (IV) are generally known compounds of organic chemistry.

Formula (lb) gives a general definition of the 20 azolyl ketones to be used as starting materials for carrying out process variant (c). The compounds of the formula (lb) are themselves compounds according to the invention: they are prepared by process variant (a) or (b ) .

Formula (V) gives a general definition of the organometallic compounds additionally to be used, inter alia, as starting materials for process variant (c). In this formula, R preferably has the meanings given in the preferred definition of the invention. 30 M preferably represents lithium, sodium or the so-called Grignard grouping Hal'-Mg, wherein Hal' represents chlorine, bromine or iodine.

The organometallic compounds of the formula (V) are generally known compounds of organic chemistry.

Suitable diluents for process variant (a) are inert organic solvents. These include, as preferences ketones, such as diethyl ketone or, in particular, acetone or methyl.ethyl ketone; nitriles, such as pro-5 pionitrile or, in particular, acetonitrile; alcohols, such as ethanol or isopropanol; ethers, such as tetra-hydrofuran or dioxan ; aromatic hydrocarbons, such as toluene, benzene or chlorobenzene ; formamides, such as, in particular, dimethyIformamide ; and halogenated hydro-1o carbons .

Process variant (a) is carried out in the presence of an acid-binding agent. Any of the inorganic or organic acid-binding agents which can customarily be used can be added, such as alkali metal carbonates', for example 15 sodium carbonate, potassium carbonate or sodium bicarbonate, or such as lower tertiary alkylamines, cycloalkyl-amines or aralkylamines, for example triethylamine , N,N-dimethylcyclohexylamine , dicyclohexylamine and N,N-dimethylbenzylamine , and furthermore pyridine or 20 diazabicyclooctane. An appropriate excess of azole is preferably employed.

In process variant (a), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at between20° and 150°C, 25 preferably at 60° to 120°C. In the presence of a solvent, the reaction is advantageously carried out at the boiling point of the particular solvent.

In carrying out process variant (a), 2 to 4 moles of azole and 1 to 4 moles of acid-binding agent are 30 preferably employed per mole of the compound of the formula (II). To isolate the compounds of the formula (I), the solvent is distilled off and the residue is worked up in the customary manner. £02107 Suitable diluents for process variant (b) 0f the invention are inert organic solvents. These include, as preferences, aromatic hydrocarbons, such as benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, "carbon tetrachloride, chloroform or chlorobenzene; esters, such as ethyl acetate; form-amides, such as dimethyIformamide ; and dimethylsulphoxide.

Process variant (b) is carried out in the presence of a base. In this process, any of the customary organic and in particular inorganic bases can be employed, especially alkali metal hydroxides or alkali metal carbonates, sodium hydroxide and potassium hydroxide being mentioned as examples.

In carrying out process variant.(b), the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at between 0° and 100°C, preferably between 20° and 100°C.

In carrying out the process variant (b), 1 to 1.2 moles of alkylating agent are preferably employed per mole of the compound of the formula (la). The isolation of the end products of the formula (I) can be effected in a generally customary manner.

Process variant (b) can alternatively be carried out in a two-phase system, for example aqueous sodium hydroxide solution or potassium hydroxide solution/toluene or methylene chloride, if appropriate with the addition of 0.1 to 1 mol of a phase-transfer catalyst, for example an ammonium or phosphonium compound, benzyl-dodecyl-dimethyl-ammonium chloride and triethyl-benzyl-ammonium chloride being mentioned as examples.

The reduction according to process variant (c), can be effected in a customary manner.

If the reaction is carried out using a complex hydride, suitable diluents -for the reaction are polar organic solvents.. These include, as preferences, alcohols, such as methanol, ethanol, butanol or isopropanol, and ethers, such as diethyl ether or tetra hydrofuran. The re-action is carried out in general at 0° to 30°C, preferably at 0° to 20°C. In this reaction about 1 reaction equivalent of a complex hydride, such as sodium borohydride or lithium alanate, is employed per mole of the ketone of the formula (lb). To isolate the resultant compound of the formula (I), the residue is taken up in dilute hydrochloric acid, and the solution is then rendered alkaline and is extracted with an organic solvent. Further working-up may be effected in the customary manner.

If the reaction is carried out using aluminium isopropylate, preferred diluents for the reaction according to the invention are alcohols, such as isopropanol, or inert hydrocarbons, such as benzene.

Once again, the reaction temperatures can be varied within a relatively wide range; in general the reaction is carried out at between 20° and 120°C, preferably at 50° to 100°C. To carry out the reaction, about 1 to 2 moles of aluminium isopropylate are employ ed per mole of the ketone of the formula (lb). To isolate the .resultant compound of the formula (I), the excess solvent is removed by distillation in. vacuo, and the resulting aluminium compound is decomposed with dilute sulphuric acid or sodium hydroxide solution. Further working-up may be effected in the customary manner.

If the reaction is carried out using an organometallic compound, preferred diluents are anhydrous ethers, such as diethyl ether, dibutyl ether or tetra- hydrofuran. The reaction is carried out in general at 0° to 80°C, preferably at the boiling point of the /■> T? i J // solvent used. In this reaction, about 1 to 3 moles of the organometallic compound of the formula (V) are employed per mole of the compound of the formula (lb). Working-up of the mixtures obtained by organometallic reactions can be effected in a customary and generally known manner.

The following acids are preferably used for the preparation of physiologically tolerated acid addition salts of the compounds of the formula (I): hydrogen halide acids (for example hydrobromic acid and, in particular, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acetic acid, maleic acid, succinic acid, fumaric 1^ acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid) and. sulphonic acids (for example p-toluenesulphonic acid and naphthalene-1 , 5-disulphonic acid). The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by custom 20 ary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and can be isolated in a known manner, for example by filtra tion, and if appropriate purified by washing with an 25 inert organic solvent.

Salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII are preferably used for the preparation of metal salt complexes of the compounds of the formula (I), copper, zinc, manganese, magnesium, tin, iron and nickel being mentioned as examples of such metals. Preferred anions of the salts are those which are derived from the following acids: hydrogen halide acids (for example hydrochloric acid 1 0 207 f, n* and hydrobromic acid), phosphoric acid, nitric acid and sulphuric acid. The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (I). The metal salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystallisation.

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

Fungicidal agents in plant protection are emp loyed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes , Zygomycetes, Ascomycetes, Basidiomy-cetes and Deuteromycetes .

Bactericidal agents are employed in plant protec-20 tion for combating Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycet-aceae.

The good toleration, by plants, of the active compounds, at the concentrations required for combating 25 plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil .

As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating those fungi which cause powdery mildew diseases, hence for combating Erysiphe species, such as the powdery mildew of barley or powdery mildew of cereal causative organism (Erysiphe graminis), ' ') ^ V. J - for combating Venturis species, for example the apple scab causative organism (Venturis inaequalis), or for combating rice diseases, for example Pyricularia oryzae and Pellicularia sasakii. It should be emphasised that 5 the substances according to the invention also possess good bactericidal properties.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, 10 foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations 15 used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in known manner, for example by mixing the active compounds with extenders, 20 that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents 25 can, for example, also be used as auxiliary solvents.

As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, 30 such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well ? 07 as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo-hexanone, or strongly polar solvents, such as dimethyl-formamide and dimethylsulphoxide , as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for 15 granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust," coconut shells, maize cobs and tobacco stalks 20 As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as 25 well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

It is possible to use colorants such as inorganic 1 0 7 0/ pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dye-stuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.

The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure. 15 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, emulsionssuspensions , powders, pastes and granules. They may be 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.

Especially in the treatment of parts of plants, 25 the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0 . 0 0 01 ?o by weight, preferably between 0.5 and 0.001?S.

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

For the treatment of soil, active compound concentrations of in general 0.00001 to 0.1 % by weight, 20ii preferably 0.0001 to 0.2^ by weight, are required at the place of action.

The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present invention alone or in the form of a composition contain ing as active ingredient a compound of the present invention in admixture with a diluent or carrier.

The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.

The preparative process is illustrated by the following Examples.

Preparative Examples Example 1 ci^^co-cna-Q (1) 24 ? r> d n 0 7 .. W . 3 J V ' Process variant (a) 100 g (0.36 mol) of oJ-chloro-4-(41-chlorophenoxy)- acetophenone, 31.1 g (0.45 mol) of 1 , 2,4-triazole and 124 g (0.9 mol) of. ground potassium carbonate were heated under reflux for 20 hours, while stirring. Thereafter, the mixture was allowed to cool, the inorganic salts were filtered off under suction, and the filtrate was concentrated. The residue was stirred in methylene chloride, and dilute hydrochloric acid was added. The resulting hydrochloride was separated off, washed with methylene chloride and converted into the free base in the customary manner by the addition of alkalis and subsequent extraction. 41.5 g ( 3 6 . 8 ?o of theory) of 4 -(4'-chlorophenoxy)-t»J - (1 ,2,4-triazol-1-yl)-acetophenone of melting point 148-150°0 were obtained.

Preparation of the starting material added dropwise to 150 g (0.73 mol) of 4-chlorobiphenyl ether and 117 g (0.88 mol) of aluminium trichloride in 1,000 ml of methylene chloride at room temperature. The reaction solution was stirred for a further hour, and was then introduced onto 3 litres of ice-water. The organic phase was separated off, washed with water, dried over sodium sulphate and concentrated. The residue was triturated with petroleum ether, filtered off under suction and dried. 168.7 g (82.3% of theory) of W-chloro-4-(4'-chlorophenoxy)-acetophenone of melting point 5 9-610 C were obtained.

Example 2 86.6 g (0.77 mol) of chloroacetyl chloride were JJ (2) N ?, a 0 7 Process variant (b) 31.4 g (0.1 mol) of 4-(4 '-ch lorop henox y ) - (J - (1 , 2 , 4-triazol-1-yl)-acetophenone (Example 1), 16.1 g of 4-chlorobenzyl chloride and 5.6 g (0.1 mol) of potassium hydroxide in 200 ml of dimethylsulphoxide were stirred for 20 hours at 40°C. The reaction mixture was then introduced onto 700 ml of water and extracted with ethyl acetate. The organic phase was washed with water, dried over sodium sulphate and concentrated. The residue was purified by boiling it with isopropyl ether. 26.1 g (59.6% of theory) of 1-(4-chlorophenyl)-3-[4-(4'-chloro-phenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-one of melting point 132°C were obtained.

Example 3 OH CH-CH^d (3) cHm Process variant (c) 7 g (0.016 mol) of 1 -(4-chlorophenyl)-3-[4-(4 1 -chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-one (Example 2) and 4.8 g (0.04 mol) of methyl-magnesium bromide, dissolved in 50 ml of ether, were stirred under reflux in 100 ml of tetrahydrofuran for 1 hour. The mixture was allowed to cool, and dilute hydrochloric acid was added. The organic phase was separated off, washed with water, dried over sodium sulphate and concentrated. The residue was stirred in diisopropyl ether, filtered off under suction and dried. 5.3 g (13% of theory) of 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1 , 2,4-triazo1-1-y1)-butan-3-o1 of melting point 159°C were obtained. 7 Example 4 oh ci h-ch-ch2- "n II if N" H -CI (4) Process variant (c) 0.38 g (0.01 mol) of sodium borohydride, dissolved 5 in 10 ml of water, was added to 14 g (0.032 mol) of 1-(4-chlorophenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2 , 4-triazol-1-yl)-propan-3-one (Example'2) in 400 ml of methanol. The mixture was stirred for 2 hours at 25°C, and the pH value was then adjusted to 6-7 by the addition of dilute hydrochloric acid. The reaction solution was concentrated and the residue was taken up with methylene chloride/water. The organic phase was separated off, dried over sodium sulphate and concentrated. The solid residue was recrystallised from diiso-15 propyl ether. 10.5 g (75?o of theory) of 1-(4-chloro- phenyl)-3-[4-(4'-chlorophenoxy)-phenyl]-2-(1,2,4-triazol-1-yl)-propan-3-ol of melting point 112°C were obtained.

The compounds of the general formula ( IA) which are listed in the table below were obtained in a manner analogous to those described in the above Examples and by means of the processes according to the invention. in this table, the references to "A form" and "B form" relate to the two possible geometrical isomers.

Ex- X1 ample No . x2 x3 y1 y2 a 2 r1 m*p-( °c) ' or n20 H H H H H -CQ- 6 4-Cl H H H H H -C0- 7 4-Cl H H H H H -C0- H H ; H H H -C0- 9 4-Cl H H H H H -C0- 4-Cl H H H H H -C0- 11 4-Cl H H H H H -C0- 12 4-Cl H H H H - H -C0- 13 4-Cl H H H H H -CO- 14 4-Cl H H H H H -CO- 4-Cl H H H H H -CO- 16 4-Cl H H H H H -CO- 17 4-Cl H H H H H -CO- 18 4-Cl H H H H H -CQ- 19 . 4-Cl H H H H H -CO- 2-C1 4-Cl H H H H -CO- /l=j -N I \=n -u /N=j -N | ~^=N /N--N_ /N--N \^n' /N- -N \=N /n~ -N \=N /N=? -N \=isi -N /N — -N -N /Nq -N I \_ n /N- -N /N = -N \=|sj /n--n _ V_N /*=\ -N \=*l 1 n-C3H7 n-C3H7 -C2H5 ~c2h5 -ch3 n -Ci+Hg n -c5H-i i i-C3H7 66—68 64-66 91-92 62-63 1,6061 88 126 64 92-93 -CH2C=CH 116 -CH2CH=CH2 87 -C7H-15 67 -CH2CH=CHCH3 87 -CH2CH20CH3 1,5940 -CH=CHC3H7 ' 1,5840 -C3H7 106 Example X no. - 28 X2 X3 Y1 Y2 Y3 A Az R1 or n m .d j( °c) '20 21 2-CH3 6-C1 H H H H -C0- 22 2-Cl 4-Cl H H H- H -CO- 23 4-Br H H H H H -CO- 24 4-Cl H H H H H -CO- 4-Cl H H H H H -CO -n \=* /N=] -n \=*l "\ 1 \=N -N I VzN -N I \=N 26 4-Cl H H H H H -CO- -N 27 4-Cl H H ■ H H H -CO- -N —N 28 4-Cl H H " H H H -CO -N — N 29 4-Cl H H H H H -CO- -N^J /N^t 4-Cl H H H H. H -CH(OH)- -N | \=N 31 4-Cl H H H H H -CH(OH)- -N j \=N N-tt 32. 4-Cl H H H H H -CH(OH)- 33 4-Cl H H H H H -CH(OH)- 34 4-Cl H H H H H -CH(OH)- -N -N I /N=T ■N | :N ,N~ 4-Cl H H H H H -(CH(OH)- -N N N^t 36 4-CL H- H H H H -CH(OH)- -N /*=! -c2h5 n-c3h7 -ch3 n-C^Hg i-c3h7 H -C2H5 -c2h5 n-C3H7 n-c3h7 n-C^H9 n-C^Hg . ~ch3 93-97 100 150 1,6092 1,6040 1,5990 1,5959 114-116 212 (xCuCl2) (A-Form) 161-62 (B-F orm) 150(A-Form) 106-07 (B-Form) 90(A-Form) 116 (B-Form) 90-100- Example no. 37 H 38 H 39 H 40 H 49 4-Cl 1 5 50 4-Cl 52 4-Cl 53 4-Cl X2 X3. Y1 Y2 Y3 A Az R1 m.p.( °C) or n20 /N=» )- -N \=lJ /N- H H H H H -CH(OH)- -N \=fl /N=l H H H H' H -CH(OH)- -N \=N /N-j H H H H H -CH(OH)- -N I /n— H H H H H -CH( OH)- -N 45 4-Cl H H , H H H -CH(OH)- 46 4-Cl H H H H H -CH(OH)- 41 4-Cl H H H H H -CH(OH)- -N N n—i ,n=1 H H H H H -CH(OH)- -N 42 H 43 H H H H H H -CH(OH)- -N | \=N ,N=] 44 4-Cl H H H H H -CH(OH)- -N \=.^ JM=- /' -N —N N= A- 47 4-Cl • H H H H H -CH(OH)- -N \=N /N-| N I /N- H H H H H —CH(OH)- -N 48 4-Cl H H H H H -CH(OH)- -N H H H H H -CH(OH)- -N 51 4-Cl H H H H H -CH(OH)- -N /N~ H H H H H -CH(OH)- -N -N /J=- H H H H H -CH(OH)- -N :N yn—. -ch3 n-C3H7 n-C3H7 i-C3H7 -c2h5 -c2h5 n -CsH-n n -c5h-1 -| i -C3H7 i-c3h7 i-C^Hg i -C^Hg i-C^Hg i-C3H7 1,5842 96(A-Form) 102 (B-F orm) 114-117 158 121 (A-F orm) 120 (B-Form) 84 (A-F orm) 102 (B-F orm) 161-63 (A-Form) 74-76 (B-Form) 110-14 107 (A-Form) 151 (B-F orm) 160-62 \=N -CH2C=CH 90 -CH2CH=CH2 107 Ex ample X1 No.

X2 X3 Y1 Y2 Az R1 m. p.( °C) or n20 54 4-Cl H H H H 55 4-Cl H H H H 56 4-Cl H H H H Z'-! H -CH(OH)- -N I n-C7H15 \=N A=1 74 57 4-Cl H H H H H -CH(OH)- -N 58 2-Cl 4-Cl H H H / —I H -CH(OH)- -N I -CH2CH=CHCH3 109 \=N /l=j H -CH(OH)- -N /N- -CH2CH20CH3 95-100 -CH=CHC3H7 1,5608 59 2-Cl 4-Cl H H H 60 4-Cl H H H H 61 4-Cl H H H H -ch- H -CH(OH)- -N | n-C3H7 ,N=t H -CH(OH)- -N N=n H -C (OH) -N I n-C3H7 H -C(0H)CH3 -N | n /' 62 4-Cl H H H H H -C(0H)CH3 -N 63 4-Cl H H H H 64 4-Cl H H H H H -(j(0H) / -N n= CHa^ci \=|V c3h7 ch3 ch3 H -C(OH) -N n-C3H7 1 ^=N CH->-CH=CH? :h2-ch=ch2 65 2-CH3 6-Cl H H H H -CH(OH)- -N .n = 66 2-Cl 4-Cl H H H •1 5 67 4-Cl H H H H 68 4-Br H H H H H -CH(OH)- -N I \=N ,N=j H -CH(OH)- -N N ,N=i H -CH(OH)- -N viscous oil 200(xHCl ) oil 145 128 142 128 125-26 viscous oil 114 106 0 210 7 Example X1 X2 X3 Y1 Y2 Y3" A Az R1 m.p.(°C) N|o. or n20 69 H H H H H H -CH(OH)- -N | n-C3H7 1,5600 -N 70 h h h h h h -ch(oh)- -n 71 4-Cl H H H H H -CH(OH)- -N i-C3H7 128 -C2H5 48-52 72 4-Cl H H H H H -CH(OH)- -N -CH3 viscous oil 73 4-Cl H H H H H -CH(OH)- -l/^ n-C^Hg 120-30 ~N 74 4-Cl H H H H H -CH(OH)- -N | i-C3H7 50-55 75 4-Cl H H H H H -CH(OH)- -N | n-C3H7 44-48 1 0 32 202107 Use Examples The fungicidal activity of the compounds of this invention is illustrated by the following biotest Examples.

In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example.

The known comparison compounds are identified as follows: /=N (A) = ^ C 0 -C H 2-N CE~3 /N= (B) = CH3-(O)-C0-CH2-N (C) = CF, ,N— C0-CH2-N (D)= CI -<c> OH ! CH- iN ■CH2 -N nn- Example A Venturia test (apple) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed 33 202 1 with the stated amounts of-solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.

To test for protective activity, young plants 5 were sprayed with't-he preparation of active compound until dripping wet. After the spray coating had dried on, the plants were inoculated with an aqueous conidia suspension of the apple scab causative organism (Venturia inaequalis) and were then left in an incub-ation cabin at 20°C and 10 0% relative atmospheric humidity for 1 day.

The plants were then placed in a greenhouse at 2 0 0 C and a relative atmospheric humidity of about 70%.

Evaluation was carried out 12 days after the 1^ inoculation.

In this test, a clearly superior activity compared with the prior art was shown, for example, by the compounds (9), (10), (41), (5), (7), (6), (8), (40) and (13).' Example B Erysiphe test (barley)/protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl poly- compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration. were sprayed with the preparation of active compound until dew-moist. After the spray coating had dried on, the plants were dusted with spores of Erysiphe graminis glycol eth'er To produce a suitable preparation of active To test for protective activity, young plants 202H Q7 f.sp.hordei.

The plants Were placed in a greenhouse at a temperature of about 20°C and a relative atmospheric humidity of about 80%, in order to promote the develop-5 ment of powdery mildew pustules.

Evaluation was carried out 7 days after the inoculation.

In this test, a clearly superior activity compared with the prior art was shown, for example, by the com-10 pounds (69), (9), (10), (36), (41), (4), (37), (5), (7), (6), (8), (40) and (13).

Example C Pyricularia test (rice) / protective Solvent: 12.5 parts by weight of ace-tone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a Suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, and the concentrate ? D was diluted with water and the stated amount of emulsifier, to the desired concentration.

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

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

In this test, a clearly superior activity compared with the prior art was shown, for example, by the compounds (36), (7) and (74). 202107 Example D Pellicularia test (rice) Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, and the concentrate was diluted with water and the stated amount of emulsifier, to the desired concentration.

To test for activity, young rice plants in the 3 to 4 leaf stage were sprayed until dripping wet. The plants remained in a greenhouse until they had dried off. The plants were then inoculated with Pellicularia sasakii and were kept at 25°C and 100% relative atmospheric humidity.

The evaluation of the disease infestation was carried out 5 to 8 days after the inoculation.

In this test, a clearly superior activity compared with the prior art was shown, for example, by the compounds (36), (7) and (74). u k. i u 7

Claims

WHAT WE CLAIM IS:

1. Phenoxyphenyl azolylmethyl ketones and carbinols of the general formula X " 0 ' ((Si) A — CH — L Y2 (I) 10 in which ~" Az represents 1 , 2 , 4-triazol-1-yl or -4-yl or imidazol-1-yl , A represents the keto group or the -CH(OH)- or -C(0H)R— grouping, R represents alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted phenyl or optionally substituted phenalkyl, 1 R represents alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, halogenoalky1, alkoxyalkyl, halogenoalkoxyalkyl, alkylthioalkyl, halogeno-15 alkylthioalkyl, dialkylaminoalky1 or optionally substituted phenalkyl, or 1 R may alternatively represent hydrogen provided that at the same time X does not represent un- 12 3 substituted phenyl and Y , Y and Y do not 20 represent hydrogen, or provided that R does not represent alkyl, cycloalkyl or cycloalkylalkyl, X represents phenyl which optionally carries one or more substituents that are selected independently, and 25 Y^, Y^ and Y^ are selected independently and each represent hydrogen, halogen or alkyl, and their plant-tolerated acid addition salts and metal salt complexes. L ^r- - v> / • 202 1 C"7 - 37 -

2. Compounds according to claim 1, characterised in that X represents a group of the general formula X1 x2 10 X3 R represents straight-chain or branched alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 or 2 carbon atoms in the alkyl part, alkenyl or alkynyl each having 2 to 6 carbon atoms, optionally substituted phenyl °r optionally substituted phenalkyl having 1 to 4 carbon atoms in the alkyl part, each phenyl substituent in either case being selected independently from halogen and alkyl 15 having 1 to 4 carbon atoms, 1 R represents straight-chain or branched alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 or 2 20 carbon atoms in the alkyl part, alkenyl or alkyn yl, each having 2 to 6 carbon atoms, alkoxyalkyl or alkylthioalkyl, each having 1 or 2 carbon atoms in each alkyl part, halogenoalkyl having 1 to 8 carbon atoms and 1 to 5 halogen atoms, halogeno-25 alkoxyalkyl or halogenoalkylthioalkyl , each having 1 to 4 carbon atoms in each alkyl part and 1 to 5 halogen atoms, dialky1 aminoalky1 having 1 to 4 carbon atoms in each alkyl part, or optionally substituted phenalkyl having 1 to 4 carbon atoms in - 0 2 1 0 7 the alkyl part, each phenyl substituent being selected independently- from the radicals mentioned i below for X , or i R may alternatively represent hydrogen provided that at the same time x'' , X2, X3, , Y2 and Y3 do not represent' hydrogen, or provided that R does not represent alkyl, cycloalkyl or cycloalkylalkyl, 1 X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms, halogenoalky1 , halogenoalkoxy or halogenoalkylthio, each having 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy or alkylthio, each having 1 to 4 carbon atoms, amino, alkylamino or dialkylamino, each having 1 to 4 carbon atoms in each alkyl part, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl part, nitro or cyano, 2 X represents hydrogen, halogen, or alkyl or alkoxy, each having 1 to 4 carbon atoms, or 1 2 X and X together, in the o-position to one another, represent methylenedioxo, X3 represents hydrogen, halogen, or alkyl or alkoxy, each having 1 to 4 carbon atoms, 1 Y represents hydrogen, halogen or alkyl having 1 to 4 carbon atoms, 2 Y represents hydrogen or halogen, and Y"5 represents hydrogen. Compounds according to claim 2, characterised in that R represents straight-chain or branched alkyl having 1 to 4 carbon atoms, cycloalkyl or cycloalkyl-methyl, each having 5 or 6 carbon atoms in the cycloalkyl part, alkenyl or alkynyl, each having 2 to 4 carbon atoms, or phenyl or benzyl, either of which may optionally carry one or more substituents each selected independently from 202107 " * - 39 - fluorine, chlorine, b-romine and methyl, R represents straight-chain or branched alkyl having 1 to B carbon atoms, cycloalkyl or cyclo-alkylmethyl, each having 5 or 6 carbon atoms in 5 the cycloalkyl part, alkenyl having 2 to 6 carbon atoms, alkynyl having 2 to 4 carbon atoms, alkoxyalkyl or alkylthioalkyl, each having 1 or 2 carbon atoms in each alkyl part, halogenoalkyl having 1 to b carbon atoms and 1 to 5 halogen atoms, 10 halogenoalkoxyalkyl or halogenoalkylthioalkyl, each having 1 or 2 carbon atoms in each alkyl part and 1 to 5 halogen atoms, dialkylaminoalkyl having 1 or 2 carbon atoms in each alkyl part, or optionally substituted benzyl, each phenyl 15 substituent being selected independently from the 1 radicals mentioned below for X , or R ' may alternatively, represent hydrogen provided that at the same time X^ , X2, X

3, Y^, V2 and do not represent hydrogen, or provided that R 20 does not represent alkyl, cycloalkyl or cycloalkyl alkyl , 1 X represents hydrogen, fluorine, chlorine, bromine, methyl, trifluoro methyl, trifluoromethoxy, trifluoromethylthio, methoxy, methylthio, amino, 25 dimethylamino, methoxycarbonyl, nitro or cyano, 2 X represents hydrogen, fluorine, chlorine, methyl or methoxy, or 1 2 X and X together, in the o-position to one another, represent methylened'ioxo, 30 X3 represents hydrogen, fluorine, chlorine, methyl or methox y, 1 Y represents hydrogen, fluorine, chlorine or methyl, ■i > ': - - , #"? • i - 40 - 2 Y represents hydrogen, fluorine or chlorine, and Y3 represents hydrogen.

4. Compounds according to claim 1, 2 or 3, character-5 ised in that they are in the form of salts of an acid selected from hydrogen halide acids, phosphoric acid, sulphuric acid, nitric acid, sulphonic acids and mono-functional or difunctional carboxylic and hydroxy-carboxylic acids, or in the form of complexes of a 1A metal salt, the metal of which is selected from copper, zinc, manganese, magnesium, tin, iron and nickel and the anion of which is selected from halide, phosphate, sulphate and nitrate.

5. Any one of the compounds according to claim 1 15 that are hereinbefore specifically disclosed.

6. A process for the preparation of a compound according to claim 1, characterised in that tn produce a compound wherein A is -rp-C a J/a hSiogenoketone of the general formula 20 -3 - n„A (n)> 25 in which Hal represents halogen,-and 12 3 X, Y , Y and Y have the meanings given in claim 1 , is reacted with an azole of the general formula H - Az (III) , in which Az has the meaning given in claim 1, Jl >1 «> f - 41 - tj,' (■-» in the presence of a diluent and in the presence of an acid-binding agent; or , , . , • „ nr. to produce a compound wherein A is -lu- (b) /an azolyl ketone of the general formula (la) , 5 in which 12 3 Az , X, V , V and Y have the meanings given in claim 1, is reacted with an alkylating agent of the general formula 10 R1 - Z (IV), in which 1 R has the meaning given in claim 1 and Z represents an electron-attracting leaving grouping , 15 in the presence of a base and in the presence of an organic diluent, or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst; qr to produce a compound wherein A is^£HlQHj -or-£iOiLLR-(c) /an azolyl ketone oT the general formula X - 0 - —CO - CH - R2 | (lb), Y1 Y2 Y3 Az 20 in which 12 3 Az , X, Y , Y and Y have the meanings given in claim 1 and 2 11 R represents hydrogen or R , where R has the :« v - 42 - <& .jl U r'l 10 meaning given in claim 1, is reduced by reaction with a complex hydride or aluminium isopropylate in the presence of a diluent, or is reacted with an organometallic compound of the general formula (V), in which R has the meaning given in claim 1 and M represents an alkali metal or the radical Hal ' -Mg, wherein Hal1 represents chlorine, bromine or iodine, in the presence of a diluent, and (d), if required, an acid or a metal salt is added onto the compound of the formula (I) obtained by process var-iant (a), (b) or (c).

7. A process according to claim 6(a )•characterised , in that the diluent is an inert organic solvent selected from ketones, nitriles, alcohols, ethers, aromatic hydrocarbons, formamides and halogenated hydrocarbons.

8. A process according to claim 6(a) or 7, characterised in that the acid-binding agent is an alkali metal carbonate, an alkali metal bicarbonate, a tertiary alkyl-amine, a cycloalkylamine, an aralkylamine, pyridine, a diazabicyclooctane or an excess of the azole.

9. A process according to claim 6(a), 7 or 8, characterised in that the reaction is effected at from 20° to 150°C.

10. A process according to claim 6(a), 7, 8 or 9, characterised in that to 4 moles of azole and 1 to 4 moles of acid-binding agent are employed per mole of 20 25 30 the compound (II). "-'202107 -» i). - 43 - 1 0 1 5

11. A process according to any one of claims 6(a) and 7 to 10, characterised in that a compound (II) is employed wherein Hal represents chlorine or bromine.

12. A process according to claim 6(b), characterised in that the diluent is an inert organic solvent selected from aromatic hydrocarbons, halogenated hydrocarbons, esters, formamides and dimethylsulphoxide.

13. A process according to claim 6(b) or 12, characterised in that the base is an alkali metal hydroxide or an alkali metal carbonate.

14. A process according to claim 6(b), characterised in that the reaction is effected in a two-phase system comprising aqueous sodium hydroxide or potassium hydroxide solution and toluene or methylene chloride, in the presence of a phase-transfer catalyst selected from ammonium and phosphonium compounds.

15. A process according to claim 6(b), 12, 1.3 or 14, characterised in that the reaction is effected at from 0° to 100°C.

16. A process according to any one of claims 6(b) and 12 to 15, characterised in that from 1 to 1.2 moles of alkylating agent are employed per mole of a compound (la).

17. A process according to any one of claims 6(b) and 12 to 16, characterised in that an alkylating agent (IV) is employed wherein Z represents halogen, p-methylphenyl-sulphonyloxy or a grouping of the formula -0- SO^-OR or -NR^ wherein R is an organic radical.

18. A process according to claim 6(c), characterised in that the reduction is effected using a complex hydride in the presence of a polar organic solvent at a temperature of from 0° to 30°C.

19. A process according to claim 6(c) or 18,characterised in that the reduction is effected using one reaction equivalent of a complex hydride per mole of the ketone (lb) 20 30 *LL ill Oil 7 Q0 ''J' * V, '' ■ 1 .S . J i J •l« V - 44 -

20. A process according to claim 6{c), 18 or 19, characterised in that the reduction is effected using sodium borohydride or lithium alanate.

21. A process according to claim 6(c), characterised 5 in that the reduction is effected using aluminium isopropylate in the presence, as a diluent, of an alcohol or an inert hydrocarbon and at a temperature of from 20° to 120°C.

22. A process according to claim 6(c) or 21, character-^0 ised in that the reduction is effected using 1 to 2 moles of aluminium isopropylate per mole of the ketone (lb).

23. A process according to claim 6(c), characterised in that the reaction with the organometallic compound (V) is effected in an anhydrous ether at a temperature ^5 of from 0° to 80°C.

24. A process according to claim 6(c) or 23, characterised in that 1 to 3 moles of organometallic compound (V) are employed per mole of the ketone (lb).

25. A process for the preparation of a compound 20 according to claim 1, substantially as described in any one of Examples 1 to 75.

26. A compound according to claim 1, characterised in that it is prepared by a process according to any one of claims 6 to 25. 25

27. A fungicidal composition, characterised in that it contains as active ingredient a compound according to any of claims 1 to 5 and 26 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

28. A composition according to claim 27, characterised in that it contains from 0.1 to 95% of the active compound, by weight.

29. A method of combating fungi, characterised in that 35 there is applied to the fungi, or to a habitat thereof, 11 I 9 IP r/< o Tj/j W 2o2i<>l V X 1 - 45 - a c 0 mpound according to any-of claims 1 to 5 and 26 al o n e or in the form of a composition cont aining as act i ve ingredient a compound according to any of claims 1 t 0 5 and 26, in admixture with a dil uent or carrier.

30. A method according to claim 29, cha racterised in tha t a composition is used containing from 0.0001 to 1?o 0 f the active compound, by weight.

31 . A method according to claim 30, cha racterised in tha t a composition is used containing from 0.001 to 0.5?,; o f the active compound, by weight.

32. A method according to claim 29, cha racterised in tha t the active compound is applied to soi 1 in an amount of 0.00001 to 0.1 percent active aarpound by weight of cartposition.

33. A method according to claim 32, characterised in that the active compound is applied to soil in an amount of 0.0001 to 0.02 percent active compound by weight of composition.

34. A method according to claim 29, characterised in that the active compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

35. A method according to claim 34, characterised in that the active compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

36. A compound according to any one of claims 1 to 5 and 26 when in contact with a crop and/or crop growing area optionally in admixture with a diluent or carrier. BAYER AKT1ENGSELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By: •X :