IE51829B1 - Azolylalkyl-2,3-dihydrobenzofurans,fungicides containing these,and their preparations - Google Patents

Abstract

1. Claims for the Contracting States : BE, CH, DE, FR, GB, IT, LI, LU, NL, SE An azolylalkyl-2,3-dihydrobenzofuran of the formula see diagramm : EP0056089,P14,F2 where R is hydrogen or alkyl of 1 to 4 carbon atoms, X is hydrogen, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 3 carbon atoms, alkenyl of 2 or 3 carbon atoms, phenyl or phenoxy, and m is an integer from 1 to 4, and the individual groups X are identical or different if m is greater than 1, Y is N or CH and Z is -CO- or -CR**1 OR**2 -, where R**1 is hydrogen or alkyl of 1 to 4 carbon atoms, and R**2 is hydrogen, or is alkyl of 1 to 6 carbon atoms which is unsubstituted or substituted by chlorine, or is alkenyl of 3 to 5 carbon atoms which is unsubstituted or substituted by chlorine, or is alkynyl of 3 or 4 carbon atoms, or is benzyl, which may be substituted by fluorine, chlorine, bromine, nitro, trifluoromethyl or alkyl of 1 to 4 carbon atoms, or is -CO-R**3 -, where R**3 is alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by halogen, alkoxy of 1 to 2 carbon atoms, oxo (=O) or carboxyalkyl of 2 to 5 carbon atoms, or an acid addition salt or metal salt complex thereof. 1. Claims for the Contracting State : AT A fungicide containing an azolylalkyl-2,3-dihydrobenzofuran of the formula see diagramm : EP0056089,P15,F3 where R is hydrogen or alkyl of 1 to 4 carbon atoms, X is hydrogen, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 3 carbon atoms, alkenyl of 2 or 3 carbon atoms, phenyl or phenoxy, and m is an integer from 1 to 4, and the individual groups X are identical or different if m is greater than 1, Y is N or CH and Z is -CO- or -CR**1 OR**2 -, where R**1 is hydrogen or alkyl of 1 to 4 carbon atoms, and R**2 is hydrogen, or is alkyl of 1 to 6 carbon atoms which is unsubstituted or substituted by chlorine, or is alkenyl of 3 to 5 carbon atoms which is unsubstituted or substituted by chlorine, or is alkynyl of 3 or 4 carbon atoms, or is benzyl, which may be substituted by fluorine, chlorine, bromine, nitro, trifluoromethyl or alkyl of 1 to 4 carbon atoms, or is -CO-R**3 -, where R**3 is alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by halogen, alkoxy of 1 to 2 carbon atoms, oxo (=O) or carboxyalkyl of 2 to 5 carbon atoms, or an acid addition salt or metal salt complex thereof.

Description

The present invention relates to novel azolylalkyl-2 , 3-dihydrobenzofurans , processes for their preparation, fungicidal agents which contain these compounds, methods of controlling phytopathogenic fungi with the novel substances, and the preparation of fungicides using the novel substances.

It is known that imidazole derivatives, for example 1-(2-(21,4'-dichlorophenyl)-2-(prop-2'-en-l,-yloxy) ethyl)-lH-imidazole (German Laid-Open Application DOS 2,063,857) and triazole derivatives, for example 2,2dimethyl-4-(1,2,4-triazol-l-yl)-2-phenylpentan-3-one (German Laid-Open Application DOS 2,638,470) display a good fungicidal activity. However, the action is not always satisfactory when low amounts are applied. Fur15 thermore, the fungitoxic action is combined with a high phytotoxicity, so that important crops are also damaged, or their growth is greatly inhibited, when these compounds are used in the concentrations necessary for the control of phytopathogenic fungi, for example for the control of pow dery mildew or rust fungi. For these reasons, they cannot always be used as agents for controlling phytopathogenic fungi and are not suitable for all species of plants.

We have now found compounds which have a very good fungicidal activity coupled with excellent toleration by plants.

The invention relates to novel azolylalkyl-2,351829 dihydrobenzofurans of the formula I where R is hydrogen or alkyl of 1 to 4 carbon atoms, X is hydrogen, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 3 carbon atoms, alkenyl of 2 or 3 carbon atoms, phenyl or phenoxy and m is an integer from 1 to 4, and the individual groups X are identical or different if m is greater than 1, Y is N or CH and Z is -CO- or -CR^COR^)-, where R1 is hydrogen or alkyl of 1 to 4 carbon atoms and p R is hydrogen, or is alkyl of 1 to 6 carbon atoms which is unsubstituted or substituted by chlorine, or is alkenyl of 3 to 5 carbon atoms which is unsubstituted or substituted by chlorine, or is alkynyl of 3 or 4 carbon atoms, or is benzyl, which may be substituted by fluorine, chlorine, bromine, nitro, trifluoromethyl or alkyl 3 of 1 to 4 carbon atoms, or is -CO-R , where R is alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by halogen, alkoxy of 1 to 2 carbon atoms, oxo (=0) or carboxyalkyl of 2 to 5 carbon atoms, and acid addition salts and metal salt complexes thereof.

The novel compounds of the formula I contain chirality centers and are generally obtained in the form of racemates or as diastereomer mixtures. The diaster51829 eomers can be separated, for example, by column chromatography or isolated in the pure form on the basis of solubility differences. Pure enantiomers can be obtained from pure diastereomers in a conventional manner. The present invention also relates to these forms. The compounds according to the invention can be used as fungicides both in the form of the pure diastereomers or enantiomers and in the form of the mixtures thereof obtained during synthesis. The mixtures are preferably used.

X is, for example, 5-fluoro, 5-fluoro, 5-chloro, 6-chloro, 5-bromo, 6-bromo, 5-methyl, 7-methyl, 5-methoxy, 6-methoxy, 5-trifluoromethyl, 6-trifluoromethyl, 5tert.-butyl, 6-tert.-butyl, 5-nitro, 6-nitro, 4,6-dichloro, 5,7-dichloro, 5,6-dichloro, 5-bromo-7-chloro, 5chloro-7-bromo, 5-chloro-7-methyl, 5-methyl-7-chloro, 4,5,7-trichloro, 5,7-dimethyl, 4,6-dimethyl, 5-ethoxy, -n-butoxy or 5-phenoxy.

R and R1 are, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl or n-butyl. o R is, for example, hydrogen, methyl, ethyl, npropyl, n-butyl, 4-chlorobutyl, n-pentyl, n-hexyl, allyl, l-buten-2-yl, propargyl, benzyl, 4-fluorobenzyl, 4-chlorobenzyl, 4-bromobenzyl, 2,4-dichlorobenzyl or 4-trifluoro3 methylbenzyl. R is preferably methyl, ethyl, n-propyl, isopropyl, chloromethyl, chloropropyl, methoxymethyl, acetonyl (CHjCOCHj), vinyl or propenyl.

Examples of suitable acid addition salts are the bromides, chlorides, sulfates, nitrates, phosphates, ox51829 alates and dodecylsulfonates. The activity of the salts is attributable to the cation; consequently any anion can be chosen, provided it is tolerated by plants. Examples of the metal complex salts are the complexes with copper sulfate, cobalt sulfate, nickel chloride or iron chloride.

The present invention also relates to a process for the preparation of the compounds of the formula I according to the invention, wherein a 2,3-dihydrobenzo10 furan-2-ylmethyl halide of the formula II R CK2-Hal (ii) in which R, X and m have the above meanings and Hal is chlorine, bromine or iodine, is reacted with a ketone of the formula III CH2-CO-C(CH ) A Vn (III) in which Y has the above meaning, or with an alkali metal enolate thereof, and the compound thus obtained is then, if necessary, treated with a Grignard reagent or reduced, and, if desired, the product is then etherified or esteri20 fied.

The process for the preparation of the ketones of the formula I in which Z is -CO- comprises a procedure in which a known ketone of the formula III (German Laid-Open Application DOS 2,638,479) or an alkali metal enolate thereof, is alkylated with a 2,3-dihydrobenzofuran-2-ylmethyl halide II (cf. Toyoshima and coworkers, Yakugaku Zasshi. 88 (1968) 503), in the pres5 ence or absence of a strong inorganic or organic base,and in the presence or absence of a solvent or diluent which forms a one-phase or two-phase system, with on without the addition of a reaction accelerator and/or phase transfer catalyst, for example in accordance with the following equation: (ID (III) For this process, the ketone III can first be metallized to give the alkali metal enolates by reacting it with from 1 to 4 equivalents, preferably 1.0 equivalent, of a metallizing reagent, such as sodium hydride, lithium diisopropylamide, calcium hydride or potassium tert.-butoxide at from -10 to 100°C, preferably at from to 70°C, preferably in the presence of a polar aprotic solvent, such as dimethylformamide, dimethylacetamide, acetonitrile, sulfolane, tetrahydrofuran or dimethoxyethane. After subsequent addition of from 0.8 to 2.0, preferably 1.0, equivalents of the particular benzofuran1-ylmethyl halide II and, if necessary, a reaction accelerator, such as sodium borohydride, sodium iodide, potassium bromide, potassium iodide or a crown ether, such as 14-crown-5, 18-crown-6 or dibenzo-18-crown-6, the ketone of the formula I is obtained at from 0 to 100’C, preferably at from 3 to 60°C.

If necessary, a ketone of the formula I (Z = -CO-) according to the invention can be reduced in the presence of a solvent or diluent, at from -20 to 150°C, under atmospheric pressure or under superatmospheric pressure, with hydrogen in the presence of a hydrogenation catalyst, with an alkali metal hydride or complex boron or aluminum hydrides, with aluminum isopropoxide and isopropanol, with sodium dithionite or electrochemically, to give the secondary alcohol of the formula I in which Z is the group -CH-. When X is an alkenyl radical t the reduction is carried out with the above reducing agents excluding hydrogen in the presence of a hydrogenation catalyst.

Examples of suitable solvents or diluents for this reaction are water, methanol, ethanol, isopropanol, acetic acid, diethyl ether, tetrahydrofuran, dioxane, ethyl acetate, toluene and dimethylformamide, and mixtures of these.

Platinum or palladium catalysts on inert supports are used for the catalytic hydrogenation, which is carried out under pressures of from 20 to 100 bar until no further hydrogen is taken up.

Examples of hydrides which can be used as the re51829 ducing agents are sodium hydride and lithium aluminum hydride .

Finally, a ketone of the formula I (Z = -CO-) according to the invention can be alkylated with a Grig5 nard compound of the formula R1MgHal (IV) where R1 is alkyl of 1 to 4 carbon atoms and Hal is chlor ine, bromine or iodine, in the presence or absence of a solvent or diluent and in the presence or absence of a magnesium or tetraalkyl-ammonium halide, at from 0 to 100°C, to give the tertiary alcohol of the formula I where Z is the group OH -CR1 Preferred solvents are ethers, such as diethyl ether, di-n-propyl ether, methyl tert.-butyl ether, tetra hydrofuran, dimethoxyethane and anisole, as well as tertiary amines, such as Ν,Ν-dimethylaniline, 1,2-bis(dimethylamino)-ethane and phosphoric acid tris—(dimethylamide); where relevant, the reaction can also be carried out in mixtures of these solvents with aliphatic or aromatic hydrocarbons, such as n-pentane, n-hexane, cyclohexane, benzene or toluene. Suitable salts which increase the yield and suppress the usual side reactions are, in particular, anhydrous magnesium halides, such as anhy25 drous magnesium bromide, or anhydrous tetraalkyl-ammonium halides, for example tetra-n-butyl-ammonium chloride.

The reaction can be carried out at from 0 to 100°C, depending on the solvent, preferably at from 0 to 60°C.

The magnesium alcoholate thereby first formed is then converted into the alcohol by hydrolysis with a dilute aqueous acid, such as hydrochloric acid, sulfuric acid or, preferably, acetic acid, or, particularly preferably, with aqueous ammonium chloride solution, and, if desired, after removing the aqueous phase, these alochols are purified in a conventional manner by extraction, recrystallization or chromatography.

The alcohols of the formula I (Z = -CHOH- or -C-) il thus obtained can be etherified with alkylating agents of the formula V R2-Hal (V) o where R and Hal have the above meanings, in the presence or absence of a solvent or diluent which forms a onephase or two-phase system, with or without the addition of an inorganic base and with or without the addition of a reaction accelerator and/or a phase transfer catalyst, to give the corresponding compounds in which Z is -CH(OR2)- or -Cr1(0R2)-.

The following are examples of suitable solvents or diluents: diethyl ether, tetrahydrofuran, dioxane, n-pentane, monohalohydrocarbons of 2 to 6 carbon atoms, for example chloroethane, bromoethane, 1-chloropropane, 1-bromopropane, 1-chlorobutane, 1-bromobutane, 1-chloropentane, 1-bromopentane, 1-chlorohexane and 1-bromohexane, cyclohexane, methylene chloride, chloroform, toluene, chlorobenzene, xylene or dimethylformamide .

Examples of inorganic bases which may be used are: alkali metal and alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide, alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium carbonate and barium carbonate, and alkali metal and alkaline earth metal alcoholates, such as sodium methylate, sodium ethylate, magnesium methylate, sodium isopropylate and potassium tert.-butylate.

Examples of suitable reaction accelerators are metal halides, such as sodium bromide, sodium iodide, potassium bromide and potassium iodide, and crown ethers, such as 14-crown-5, 18-crown-6, dibenzo-18-crown-6 and dicyclohexano-18-crown-6.

Phase transfer catalysts which can be used are, preferably, quaternary ammonium salts, such as tetrabutyl ammonium chloride, bromide, iodide or bisulfate, benzyltriethylammonium chloride and methyl-trioctylammonium chloride or bromide, and phosphonium salts, such as tetrabutylphosphonium bromide or iodide.

I The alcohols of the formula I (Z = -CHOH- or -C-) Al can be esterified with acid chlorides or anhydrides of the formula R3-CO-C1 (VI) or (R3-CO)2O (VII) in the presence or absence of a solvent or diluent, with or without the addition of an acid acceptor and with or without the addition of a reaction accelerator. Bases which are η suitable for this reaction are the same as those for the etherification. In addition, tertiary amines, such as trimethylamine, triethylamine, N,N-dimethylaniline, Ν,Νdimethylcyclohexylamine, N-methylpiperidine and pyridine can be used as bases and imidazole, N-methylimidazole, 1.2.4- triazole, 4-dimethylaminopyridine and 4-pyrrolldonopyridine can be used as reaction accelerators.

The alcohols can also initially be converted to their alcoholate salts in a first reaction with suitable bases, for example an alkali metal hydride, such as sodium hydride, or an alkali metal or alkaline earth metal alcoholate, such as sodium methylate, and these salts can then be reacted.

The compounds of the formula I thus obtained, where Z is -CH(O-CO-R3)- or -R^tO-CO-ll3)-, are isolated purified if necessary, and, if desired, reacted with acids or metal salts to give salts or metal complex salts, these operations being carried out in a conventional manner.

Specific examples of the novel compounds of the formula I according to the invention are: l-(2',3'-dihydrobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4-dime thylpentan-3-one, 1-(2’,3'-dihydrobenzofuran-2'-yl)-2(1,2,4-triazol-l-yl) -4,4-dimethylpentan-3-ol, 1-(2',31 dihydrobenzofuran-21-yl)-2-(1,2,4-triazol-l-yl)-3-methoxy-4,4-dimethylpentane, 1-(2',3'-dihydrobenzofuran-2'-yl)2-(1,2,3-triazol-l-yl)-3-(1-propoxy)-4,4-dimethylpentane, 1-(2',3'-dihydrobenzofuran-2'-yl)-2-(l,2,4-triazol-l-yl)3.4.4- trimethylpentan-3-ol, 1-(21,3'-dihydrobenzofuran51829 2'-yl)-2-(1,2,4-triazol-l-yl)-3-methoxy-3,4,4-trimethylpentane , 1-(21,31-dihydrobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-3-allyloxy-4,4-dimethylpentane, 1-(2',3'-dihydrobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-3-(4-chloro1-butoxy)-4,4-dime thylpen tane, 1-(2',3'-dihydrobenzofuran2'-yl)-2-(1,2,4-triazol-l-yl)-3-(1-pentyloxy)-4,4-dimethylpentane , 1-(21,3'-dihydrobenzofuran-2'-yl)-2(1,2,4-triazol-l-yl)-3-benzyloxy-4,4-dimethylpentane, 1-(2',3'-dihydrobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)3-(4-chlorobenzyloxy)-4,4-dimethylpentane, 1-(2',3'-dihydrobenzofuran-2 '-yl)-2-(1,2,4-triazol-l-yl)-3-(4-nitrobenzyloxy)-4,4-dimethylpentane, 1-(21,3'-dihydrobenzofuran-2 '-yl)-2-(1,2,4-triazol-l-yl)-3-(4-trifluoromethylbenzyloxy)-4,4-dimethylpentane, 1-(21,3'-dihydrobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-3-(propoxy)-4,4-dime thylpentane, 1-(2',3'-dihydrobenzofuran-2'-yl)-2(1,2,4-triazol-l-yl)-3-ace toxy-4,4-dime thylpentane, 1(21,3'-dihydrobenzofuran-21-yl)-2-(1,2,4-triazol-l-yl)3-acetoxy-3,4,4-tri methylpentane, 1-(2',3'-dihydrobenzofuran-2 '-yl)-2-(1,2,4-triazol-l-yl)-3-propionyloxy-4,4dimethylpentane, 1-(2',3'-dihydrobenzofuran-2'-yl)-2(1,2,4-triazol-l-yl)-3-chloroacetoxy-4,4-dime thylpentane, 1- (2',3'-dihydrobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)3-bromoacetoxy-4,4-dimethylpentane, 1-(2',3'-dihydrobenzofuran-2 '-yl)-2-(1,2,4-triazol-l-yl)-3-methoxyacetyl4,4-dimethylpentane, 1-(2',3'-dihydrobenzofuran-2'-yl)2- (1,2,4-triazol-l-yl)-3-acetoacetoxy-4,4-dimethylpentane , 1-(2',3'-dihydro-3'-methylbenzofuran-2'-yl)-2(l,2,4-triazol-l-yl)-4,4-dimethylpentan-3-one, 1-(2',3'51829 dihydro-3'-methylbenzofuran-2'-yl)-2-(1,2,4-triazol-lyl )-4, 4-dimethylpentan-3-ol, 1-(21,3'-dihydro-3'-methylbenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-3-me thoxy-4,4dimethylpentane, 1-(2',3'-dihydro-31-methylbenzofuran21-yl)-2-(1,2,4-triazol-l-yl)-3-acetoxy-4,4-dime thylpentane, 1-(2',3'-dihydro-3'-methylbenzofuran-2'-yl)-2(1,2,4-triazol-l-yl)-3-propionyloxy-4,4-dimethylpentane, 1- (21,3'-dihydro-51-fluorobenzofuran-2'-yl)-2-(1,2,4triazol-l-yl)-4,4-dimethylpentan-3-one, 1-(21,3'-dihydro-5'-methylbenzofuran-21-yl)-(1,2,4-triazol-l-yl)4.4- dimethylpentan-3-one, 1-(21,3'-dihydro-5'-methylbenzofuran-2 '-yl)-(1,2,4-triazol-l-yl)-4,4-dime thylpentan-3-ol, 1-(2',3'-dihydro-5'-methylbenzofuran-2'-yl)(1,2,4-triazol-l-yl)-3-acetoxy-4,4-dimethylpentane, 1(2',3'-dihydro-5'-methylbenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-3-propionyloxy-4,4-dimethylpentane, 1-(21,3'dihydro-5'-tert.-butylbenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4-dime thylpentan-3-one, 1-(2',3'-dihydro5'-tert.-butylbenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)4.4- dimethylpentan-3-ol, l-(2',3'-dihydro-5'-tert.butylbenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-3,4,4-trimethylpentan-3-ol, 1-(21,3'-dihydro-5',7'-dimethylbenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpentan3-one, 1-(2',3'-dihydro-5',7'-dimethylbenzofuran-2'-yl)2- (l,2,4-triazol-l-yl)-4,4-dimethylpentan-3-ol, 1-(2',3'dihydro-5',7'-dichlorobenzofuran-2'-yl)-2-(1,2,4-triazoll-yl)-4,4-dimethylpentan-3-one, 1-(21,3'-dihydro-5',7'dichlorobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-ol, l-(2',3'-dihydro-5',7’-dichlorobenzo51829 furan-2 1-yl)-2-(1,2,4-triazol-l-yl)-3,4,4-trimethylpentan-3-ol, 1-(2',3'-dihydro-5 1,7'-dichlorobenzofuran-2'yl)-2-(1,2,4-triazo1-1-yl)-3-methoxy-4,4-dimethylpentane, 1-(21,3'-dihydro-5',7'-dichlorobenzofuran-2'-yl)-25 (1,2,4-triazol-l-yl)-3-(1-propoxy)-4,4-dime thylpentane, 1- (21,31-dihydro-51,7'-dichlorobenzofuran-2'-yl)-2(1,2,4-triazol-l-yl)-3-allyloxy-4,4-dimethylpentane, 1(2',3'-dihydro-5',7'-dichlorobenzofuran-2'-yl)-2-(1,2,4triazol-l-yl)-3-(2,4-dichlorobenzyloxy)-4,4-dimethylpen10 tane, 1-(2',31-dihydro-51,71-dichlorobenzofuran-2'-yl)2- (1,2,4-triazol-l-yl)-3-(4-fluorobenzyloxy)-4,4-dime thylpentane , 1-(21,3'-dihydro-5',7’-dichlorobenzofuran2'-yl)-2-(1,2,4-triazol-l-yl)-3-(4-methylbenzyloxy)-4,4dimethylpentane, 1-(2',3'-dihydro-5',71-dichlorobenzo15 furan-2 1-yl)-2-(1,2,4-triazol-l-yl)-3-acetoxy-4,4-dime thylpen tane , 1-(2',3'-dihydro-3'-methyl-5',7'-dichlorobenzofuran-21-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-one, 1 — (2',3'-dihydro-3'-methyl-5',7'-dichlorobenzofuran-2 1-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpen20 tan-3-ol, 1-(2',3'-dihydro-3'-methyl-5',7'-dichlorobenzofuran-21-yl)-2-(1,2,4-triazol-l-yl)-3,4,4-trimethylpentan-3-ol, 1-(2',3'-dihydro-31-methyl-5',7'-dichlorobenzofuran-2 '-yl)-2-(1,2,4-triazol-l-yl)-3-methoxy-4,4-dimethylpentane, 1-(2',3'-dihydro-4',6'-dichlorobenzofuran25 21-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-one, 1-(21,31-dihydro-4',6'-dichlorobenzofuran-2'-yl)-2(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-ol, 1-(21,3'dihydro-4',6'-dichlorobenzofuran-2'-yl)-2-( 1,2,4-triazoll-yl )-3-methoxy-4,4-dimethylpentane, 1-(2',3'-dihydro5182θ 4',6'-dichlorobenzofuran-21-yl)-2-(1,2,4-triazol-l-yl)3-(l-butoxy)-4,4-dimethylpentane, 1-(21,3'-dihydro-4',6'dichlorobenzofuran-21-yl)-2-(1,2,4-triazol-l-yl)-3-aeetoxy-4,4-dime thylpentane, 1-(21,31-dihydro-5'-bromo-7'chlorobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4-dime thylpentan-3-one, 1-(21,31-dihydro-5'-bromo-7'-chlorobenzofuran-2 '-yl)-2-(1,2,4-triazol-l-yl)-4,4-dlmethylpentan-3-ol, 1-(2',31-dihydro-5'-bromo-7'-chlorobenzofuran21-yl)-2-(1,2,4-triazol-l-yl)-3-methoxy-4,4-dimethylpentane , 1-(2',3'-dihydro-5'-ohloro-7'-methylbenzofuran-2'yl)-2-(1,2,4-triazol-l-yl)-4,4-dime thylpen tan-3-one, 1(2',31-dihydro-5'-ehloro-7'-methylbenzofuran-21-yl)-2(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-ol, 1-(2',31 dihydro-5'-chloro-71-methylbenzofuran-21-yl)-2-(1,2,4triazol-l-yl)-3-propionyloxy-4,4-dimethylpentane, 1(21,31-dihydro-51-nitrobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl )-4,4-dimethylpentan-3-one, 1-(2',3'-dihydro-5'nitrobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-ol, 1-(21,31-dihydro-5'-ethoxybenzofuran21-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-one, 1-(21,3'-dihydro-5'-ethoxybenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-ol, 1-(21,3'-dihydro-51 trifluoromethylbenzofuran-21-yl)-2-(l,2,4-triazol-l-yl)4,4-dimethylpentan-3-one, X—(21,S'-dihydro-S'-trifluorome thylbenzofuran-2 '-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-o1, 1-(21,3'-dihydro-4',5',7'-trichlorobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethylpentan-3-ol and l-(2',3'-dihydro-4,,5')7'-trichlorobenzofuran-2’-yl)-2-(l,2,4-triazol-l-yl)-4,4-dimethylpentan-351829 one.

The examples which follow illustrate the preparation of the compounds of the formula I according to,the invention.

EXAMPLE 1 A solution of 66.7 g (0.4 mole) of 2,2-dimethyl4-(1,2,4-triazol-l-yl)-butan-3-one (cf. German Laid-Open Application DOS 2,638,470) in 80 ml of dimethylformamide (DMF) is added dropwise to a stirred suspension of 9.6 g (0.4 mole) of sodium hydride in 120 ml of dry DMF at from 20 to 25°C under a dry nitrogen atmosphere. After the mixture has been stirred for three hours, a solution of 99 g (0.4 mole) of 2,3-dihydro-2-bromomethyl-5-chloro15 benzofuran (cf. S. Toshima and co-workers, Yakugaku Zasshi., 88 (1968), 503) in 80 ml of DMF is added drog.wise at and the reaction mixture is subsequently stirred for a further 48 hours. 50 ml of ice-water are carefully added dropwise and the mixture is concentrated under re20 duced pressure. The residue is partitioned between 500 ml of methylene chloride and 200 ml of water and the organic phase is washed twice with 200 ml of water each time, dried over NajSO^ and concentrated. The residue is stirred with 50 ml of petroleum ether at 10°C for 1 25 hour and the precipitate is filtered off with suction. 55.4 g (41.5% of theory) of 1-(21,3'-dihydro-5'-chlorobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4-dime thylpentan-3-one are obtained as white crystals of melting point 131-134°C (active ingredient No. 1).

EXAMPLE 2 c(ch3)3 4.6 g (0.12 mole) of sodium borohydride are added a little at a time to a solution of 35.3 g (0.105 mole) of 1-(2',3'-dihydro-5'-chlorodibenzofuran-2'-yl)-2-(1,2,41° triazol-l-yl)-4,4-dimethylpentan-3-one in 250 ml of methanol at from 0 to +5°C. After the mixture has been stirred at 20°C for 12 hours, it is concentrated. The residue is stirred with 150 ml of 20% strength by weight of potassium hydroxide solution and with 400 ml of methylene chloride for 1 hour. The organic phase is washed twice with 70 ml of water each time, dried over sodium sulfate and concentrated. After addition of ml of petroleum ether, the residue crystallizes at 10°C. 33.9 g (96.2% of theory) of 1-(2',3’-dihydro20 5'-chlorobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-4,4dimethylpentan-3-ol are isolated as colorless crystals of melting point 63-66’C (active ingredient No. 2).

EXAMPLE 3 CO - CH.

Cl A mixture of 12.5 g (0.0375 mole) of l-(2',3'dihydro-51-chlorobenzofuran-2 1-y1)-2-(1,2,4-triazol-l5 yl)-4,4-dimethylpentan-3-ol, 4,6 g (0,0375 mole) of 4dimethylaminopyridine and 100 ml of acetic anhydride is stirred at 60°C for 12 hours and is then concentrated under reduced pressure. The residue is stirred with 300 ml of ether and 100 ml of 6% strength sodium bicarlo bonate solution for 1½ hours and the organic phase is separated off, dried over sodium sulfate and concentrated. The solid, colorless residue is stirred with n-pentane and the product is filtered off with suction. .5 g (74.2% of theory) of 1-(21,31-dihydro-5'15 chlorobenzofuran-21-yl)-2-(1,2,4-triazol-l-yl)-3-acetoxy4,4-dimethylpentane of melting point 98-99°C are obtained (active ingredient No. 3).

EXAMPLE 4 Cl c(ch3)3 Vn A mixture of 12.5 g (0.0375 mole) of 1-(2',3'dihydro-5'-chlorobenzofuran-2'-yl)-2-(1,2,4-triazolyl)4,4-dimethylpentan-3-ol, 100 ml of 1-chloropropane, 4 g of tetrabutylammonium bisulfate and 65 g of 50% strength aqueous sodium hydroxide solution is heated at 40°C for 24 hours, with vigorous stirring. 300 ml of water are then added to the mixture, and the mixture is extracted five times with 80 ml of methylene chloride each time. The combined extracts are extracted five times by shaking with 100 ml of water each time, dried over magnesium sulfate and concentrated under reduced pressure, finally at 80°C and under 0.1 mbar. The oily residue is left to stand with 30 ml of petroleum ether in a refrigerator at +5°C for 3 days. The colorless crystals which have precipitated are filtered off with suction, washed with pentane and dried. 9.8 g (69.2% of theory) of 1—(2',3'-dihydro-5'chlorobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)-3-(1-propoxy)-4,4-dimethylpentane of melting point 75-78’C (active ingredient No. 4) are obtained.

EXAMPLE 5 Cl Cl A solution of 22 g (0.06 mole) of 1—( 2', 3' —di— hydro-5',7'-dichlorobenzofuran-2'-yl)-2-(1,2,4-triazoll-yl )-4,4-dimethylpentan-3-ol (Example 17) in 60 ml of tetrahydrofuran is added dropwise to a suspension of 2.4 g (0.1 mole) of sodium hydride in 100 ml of dry tetrahydrofuran. After the mixture has been stirred at room temperature l'or 12 hours, 14.2 g (0.1 mole) of iodomethane are added. After the reaction mixture has been stirred for 20 hours, JO ml of water are carefully added and the mixture is concentrated. The residue is taken up in 350 ml of 10 ether, the mixture is washed twice with 100 ml of water each time and the ether phase is dried and concentrated. The residue is stirred with 50 ml of petroleum ether at 5°C for 1 hour. The colorless crystalline precipitate is filtered off with suction, washed with petroleum ether and dried. 11.4 g (49.5% of theory) of 1-(21,3'-dihydros' , 7' -dichlorobenzofuran-2'-yl)-2-(1,2,4-triazol-l-yl)3-methoxy-4,4-dimethylpentane of melting point 117-118°C are obtained (active ingredient No. 5).

EXAMPLE 5 Cl OH ^N\ 3 .- CH,C(CH3>3 A solution of 7 g (0.021 mole) of 1-(2',3'— dihydro-5'-chlorobenzofuran-2'-yl)-4,4-dime thylpentan3-one (Example 1) in 50 ml of tetrahydrofuran is added dropwise to a solution of 5.4 g (0.0406 mole) of methylmagnesium bromide in 30 ml of tetrahydrofuran and the mixture is stirred at room temperature for 20 hours.

It is then stirred into 800 ml of 10% strength aqueous ammonium chloride solution and extracted twice with 200 ml of methylene chloride each time. After the organic phase has been washed, and dried over magnesium sulfate, the methylene chloride is evaporated off under reduced pressure. The residue crystallizes at +5°C after 10 ml of petroleum ether and 10 ml of ether have been added. 3.2 g (43.6% of theory) of 1-(2',3'dihydro-51-chlorobenzofuran-21-yl)-2-(1,2,4-triazol-lyl)-3,4,4-trimethylpentan-3-ol are isolated as colorless crystals of melting point 144-146°C (active ingredient No. 6) Further examples of the compounds of the formula I according to the invention are given in the following Table 1. ε CJ ο, C. *4 O C X LJ ιη cm · cm cm r- m m · νο <Μ ητ Ο r·® t-ι η β- m Ο CM m rH c •rl ω 4) fi ® Ο CM CM · i-t CM ό m a- ό rl θ' CM® <ηθ Β- Ο η® mm σι η CM rH C •rt i ί Φ m ® Ch ® CM υ o =5 z ® Οι O o · O O m O Ό CM t·» ® · m mo CM · mo rH rH® rn O n® rl® rH · •® •® • in CM •CM Οβ n® O · ® p— -Γ CM fr- ® CM ® * O'® ® * Ό OX® ST rH a in a r-1 mo •rl rH · 1-1 r* rt O rH® «in Ch rl IC «33 «33 o •in ® O o · o m o * O f" o o n cm ι-· m O CM fr- · c*cm ® ® {— f C-. O' CM O r· rH r· O' rH O' o rH m Q •® O O o o ® O ® ® ® « e— m e— ri ® m in cm Ch m O σ\ cm σ' O O'CM O'rH Ό JT ® CM rH CM rH CM rH CM rt >> rH Ol o® O O O O m cm o® rH ® O O CM fr- O® in o m rH m rH m rH fCrt I φ O C-4 CM c •H CO Φ in c •rl CQ Φ Ch c Ή CQ Φ Ch Οι cn ΙΛ m in m rH rt c •H CQ Ch Φ Ch P Λ X H -rl b = ° Ο Ή σ» m m mi yOO « ll lb m in in o 4J ι m CM H O I em O rH I σι σι t- m σι rt rH I i lfl rH σι W ® rH rH K o CM CM CM CM CM CM rH rH rH rH H rH O O O O o o III I t I e·» ρ» r— ·— c*~ f— in ft in tn m in ΛΙ O in CM CM Ε r-l α cs o o c. £ >< Oj · τ-Ι OJ © © lf\ · J» Ol »-1 tfS At— SO * t—OJ ΙΛ-» ft® -O oi m © ίο -in O rΠ O τι© n m *ST a© tfS© © · « - © O JT® Ol so fi t— f* O' —co — © * O O O OJ Ifl-K fwvo jt O rt os τ-i fi O© o© in© in so so oj os cm OS O OS rl Π CSJ th (\ rl rlrl oi oj © O O CM οι οι π so ©so ft ft ft ft Osft m rl KS rl N rl G •K CO Q) G a O on tn · e— ό jt so οι · oi « ri f- η© n so -© *m *f— in - « p— Qso συ in * so •o in .=r oj s· tn n« th tn th tn n oi so * os * nm to o® t— η « co C—jt η n ri Cs th os oo ooi mo r-O so© so m Osoj os© os fl csi fi cm η οι π O© OO OO oi© tnm oj Os rl Ol m ft ft ft >Ari m n m ri G G G •Η ·Η CSI jt © « ·Η CQ CQ OS CM rl OS CO Φ 0) ,77 , k Ο «Μ © 0) k os (Μ n Os CM © I c— m m oj oi rH © I C— m JT OJ CM Ol OJ Ol rl rl rl rt © © © © I III — © © © m «««' m © t— © CJ CJ O| CSJ oi rl © i © JT C O · O οι r—«< ιοί® « « oi · w© rt e— ri m -p— - « »f« © - © o «so p—jt © m e— * «so in ή = © tH CO fl fl rJ «· * * A A AfOO © O OJ A η© O oj os so mo p—cm m© tH th rl rl ri © ©m m© mo © m © © mm Os ri Osoj osn οι η οι n csj n oo ο ο o m OO CM© osoj csj oj ft m oj oi icr m x *o w G G GGG •rl ·Η Ρ— ·Η ·Ή ·Η CO CQ * CO CO CO Q) Ο , Φ Φ 0) G G in in G G W ta> s o tr X3 eo OS O rl cj m m Φ G to X •H ε u x $ s O 1» b I I I m mm oi m m © m rs a 51828 in cm cm · i-ι Cm co vo VO · CM VC nzr •t— w \o cm t* · cm · cm O' rt in rtO •p— «cKO CM * c— · c—co 7CO -ovo rt^- rtCp »e~ · · CM · O O φ\00 O' O' ιηΌ «β* O r-ι CO rt rt ε rt As > CM © C\Oi mo COCO in cm O\rt CM rt d Ή oi v d ovo o o mov ov/n CO m*H W ri rt rt ino co m rt m in cm rt Π O'CM ΙΛ1 CM «1 c •H oi •H oi 0) d j Ό CM O' I m O' co Kl O' m O' o The compounds according to the invention, and the salts and metal complexes thereof, have an excellent action on a broad spectrum of fungi, especially plant-pathogenic fungi, particularly from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and may be used as foliar and soil fungicides.

The fungicides according to the invention are of particular interest for combatting numerous fungi in various crop plants or their seed, particularly wheat, rye, barley, oats, rice, Indian corn, cotton, soybeans, coffee, sugarcane, fruit and ornamentals in horticulture, and vegetables such as beans, and cucumbers and other Cucurbitaceae.

The new compounds are espeically suitable for combatting the following diseases: Erysiphe graminis in cereals, Erysiphe cichoriacearum in Cucurbitaceae, Podosphaera leucotricha in apples, Uncinula necator in grapes, Erysiphe polygoni in beans, Sphaerotheca pannosa in roses, Puccinia species in cereals, Rhizoctonia solani in cotton, Helminthosphorium species in cereals, Ustilago species in cereals and sugarcane, Rhynchosporium secale in cereals and, especially, Venturia inaequalis (apple scab).

The compounds are applied by spraying or dusting the plants with the active ingredients or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.

The compounds of the invention can be converted into the conventional formulations, e.g. solutions, 'emulsions, suspensions, dusts, powders, pastes and granules. The form in which the compound is applied depends entirely on the end use but should in every case ensure a fine and uniform distribution of the active ingredient.

The formulations are prepared in the conventional manner, for exampl. iiluti ;he active ingredient with solvents and/or carriers, with or without the addition of emulsifiers and dispersants, and where water is used as the diluent, with or without an organic auxiliary solvent. Suitable auxiliaries are, essentially, solvents, for example aromatics, e.g. xylene and benzene, chloroaromatics, e.g. chlorobenzenes, paraffins, e.g. petroleum fractions, alcohols, e.g. methanol, and butanol, amines, e.g. ethanolamine and dimethylformamide, and water; carriers, for example natural rock powders, e.g. kaolin, alumina, talc and chalk, and synthetic rock powders, e.g. highly disperse silica and silicates; emulsifiers, for example non-ionic and anionic emulsifiers, e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates, and dispersants, for example lignin, sulfite waste liquors and methylcellulose.

The fungicidal agents in general contain from 0.1 to 95? by weight of active ingredient, preferably from 0.5 to 90%.

The amounts used depend on the nature of the desired effect, and range from 0.02 to 3 kg and more of active ingredient per hectare. The new compounds may also be used for the protection of materials, e.g., for combating wood-destroying fungi such as Coniophora puteana and Polystictus versicolor. The new active ingredients may further be used as fungicidally active components of oily wood preservatives for the protection of wood against wood-discoloring fungi. The wood is treated with these agents for instance by impregnation or coating.

The agents, and the ready-to-use formulations obtained therefrom, e.g. solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in the conventional manner, e.g. by spraying, atomizing, dusting, scattering, treating seed or watering.

Examples of such formulations are given below.

I. 90 parts by weight of the compound of Example 1 is mixed with 10 parts by weight of N-methy1-^-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 10 parts by weight of the compound of Example 2 is dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and parts by weight of the adduct of Ao moles of ethylene with to 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

III. 20 parts by weight of the compound of Example 5 is dissolved in a mixture consisting of Ao parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of AO moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of the compound of Example 10 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 28O°C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of the compound of Example 17 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-°<-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.

VI. 3 parts by weight of the compound of Example 24 is intimately mixed with 97 parts by weight of particulate kaolin.

A dust is obtained containing 3? by weight of the active ingredient.

VII. 30 parts by weight of the compound of Example 18 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 3 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 40 parts by weight of the compound of Example 30 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable, aqueous dispersion.

Dilution in water gives an aqueous dispersion.

IX. 20 parts of the compound of Example 24 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

The agents according to the invention may, in these appli5 cation forms, contain other active ingredients together with those according to the invention, e.g. herbicides, insecticides, growth regulators and other fungicides or may be mixed with fertilizers and applied together with these. When the active ingredients are mixed with other fungicides, the fungicidal spectrum of action is lo in many cases broadened.

The list of fungicides given below, with which the compounds according to the invention can be combined, is intended to illustrate the possible combinations, but the invention is in no way limited to these.

Examples of fungicides which can be combined with the compounds of the invention are: sulfur, dithiocarbamates and their derivatives, e.g. iron(III) dimethyldithiocarbamate, zinc dimetnyldithiocarbamate, manganese N,N-ethylene-bis-dithiocarbamate, manganese zinc Ν,Ν-ethylenediamine-bis-dithiocarbamate, zinc Ν,Ν-ethylene-bis-dithiocarbamate, tetramethylthiuram disulfide, the ammonia complex of zinc Ν,Ν-ethylene-bis-dithiocarbamate and zinc N,N'-propylene-bis-dithiocarbamate, and the ammonia complex of zinc N,N'-propylene-bis-dithiocarbamate and Ν,Ν'-polypropylene-bis-(thiocarbamoyl)-disulfide; nitro derivatives, e.g. dinitro25 -(1-methylheptyl)-phenyl crotonate, 2-sec.-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate and 2-sec.-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic compounds, e.g. N-trichloromethylthiotetrahydrophthaliraide, N-(1,1,2,2-tetrachloroethylthio)-tetra51829 hydrophthalimide, N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimidophosphonothioate, 5-amino-l-(bis-(dimethylamino )-phosphinyl)-3-pheny1-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1, 2,4-thiadiazole, 2,3-dicyano-1, 4-dithiaanthraquinone, 2-thio-1,3-dithio-(4,5-b)-quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazole-carbamate, 2-methoxycarbonylamino-benzimidazole, 2-thiocyanatomethylthio-benzthiazole, 4-(2-chlorophenylhydrazone)~ -3-methyl-5-isoxazolone, pyridine-2-thio-l-oxide, 8-hydroxyquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-l,4-oxathiine, 2-fur-2-yl-benzimidazole, piperazine-1,4-diyl-bis-(1-(2,2,2-trichloroethyl)-formamide), 2-thiazol-4-yl-benzimidazole, 5-butyl-2-dimethylaraino-4-hydroxy-6-methyl-pyrimidine, bis-(D-chlorophenyl)-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene and various fungicides, e.g. dodecylguanidine acetate, 3-(2-(3» 5-dimethyl-2-hydroxycyclohexyl)-2-hydroxyethyl)-glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-ίί',N'-dimethyl-N-phenyl-sulfuric acid diaaide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, 2-cyano-N-(ethylaminocarbonyl)-2-(methoxyimino)-acetamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, l-(334-diehloroanilino)-i-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine and its salts, 2,6-dimethyl-N-cyclodecyl-morpholine and its salts, DL-me thy1-N-(2,6-dime thyl-phenyl)-N-fur-2-yl-alanate, methyl DL-N-(2,6-dimethyl-pheny1)-N-(21-methoxyacety1)-alanate, diiso51829 propyl 5-nitroisophthalate, 1-(1’,2',4'-triazol-l'-yl)-(4’-chlorophenoxy )-3,3-dimethylbutan-2-one, 1-(1',2',4'-fcriazol-1'-yl)-(4 -chlorophenoxy)-3,3"dimethylbutan-2-ol, N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone and N-(n-propyl)-N-(2,4,65 -trichlorophenoxyethyl)-N'-imidazolylurea.

The fungicidal action of the new compounds is demonstrated in the examples below. The prior art compounds (l-(2'-(2,4-dichlorophenyl)-2'-(2-propenyloxy)-ethyl)-lH-imidazole) (A) and 2,2-dimethyl-4-(1,2,4-triazol-l-yl)-5-phenyl-pentan-3-one (B) were used lo for comparison purposes.

EXAMPLE 1 Action on wheat mildew Leaves of pot-grown wheat seedlings of the Jubilar variety are sprayed with aqueous emulsions consisting of 80* (by weight) of active ingredient and 202 of emulsifier, and dusted, after the sprayed-on layer has dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The plants are then placed in a greenhouse at 20° to 22°C and 75 to 80% relative humidity. The extent of mildew spread is determined after 10 days.

In this experiment, compounds nos. 4, 5, 13, 16, 17, 18, and 30 had a better fungicidal action than active ingredient A. EXAMPLE 2 Action on leaf rust of wheat Leaves of pot-grown wheat seedlings of the Caribo variety are dusted with spores of leaf rust (Puccinia recondita). The pots are then placed in a high humidity (90-952) chamber at from 20 to 22°C for 24 hours. During this time, the spores germinate and the germ tubes penetrate into the leaf tissue. The infected plants are then sprayed to run-off with a 0.025 wt? aqueous liquor, the solids comprising 80? of active ingredient and 20? of ligninculfonate. After the spray coating has dried, the test plants are set up in a greenhouse at from 20 to 22°C and from 65 to 70? relative humidity. After 8 days, the degree of development of the rust fungi on the leaves is determined.

In this experiment, compounds nos. 5, 10, 17, 18 and 24 had a better fungicidal action than active ingredients A and B.

EXAMPLE 3 Action on cucumber mildew Leaves of pot-grown cucumber seedlings are sprayed with aqueous emulsions, the solids comprising 80? of active 'ingredient and 20? of emulsifier (lignin sulfonate), and dusted, after the sprayed-on layer has dried, with spores of cucumber mildew (Erysiphe cichoriacearum). The plants are then placed in a greenhouse at from 20° to 22°C and from 75 to 80? relative humidity. The extent of fungus development is determined after 10 days.

In this experiment, active ingredients nos. 1, 4, 5, 7, 8, 12, 13, 15, 16, 17, 18, 19, 20, 22, 24, 26, 28, 29, 30, 31, 32 and 33 had a good fungicidal action.

Claims (5)

CLAIMS 1. 2 1 than 1, Y is N or CH and Z is -CO- or -CR X (OR )-, where R 2 is hydrogen or alkyl of 1 to 4 carbon atoms and R is hydrogen, or is alkyl of 1 to 6 carbon atoms which is unsubstituted or substituted by chlorine, or is alkenyl of 3 to 5 carbon atoms which is unsubstituted or substituted by chlorine, or is alkynyl of 3 or 4 carbon atoms, or is benzyl, which may be substituted by fluorine, chlorine, bromine, nitro, trifluoro3 methyl or alkyl of 1 to 4 carbon atoms, or is -CO-R , where R is alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by halogen, alkoxy of 1 to 2 carbon atoms, oxo (=0) or carboxyalkyl of 2 to 5 carbon atoms, or an acid addition salt or metal salt complex thereof.

1. An azolylalkyl-2,3-dihydrobenzofuran of the formula R X, Ln where R Is hydrogen or alkyl of 1 to 4 carbon atoms, X is hydrogen, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 3 carbon atoms, alkenyl of 2 or 3 carbon atoms, phenyl or phenoxy and m is an integer from 1 to 4, and the Individual groups X are identical or different if m is greater 2.3- dihydrobenzofuran-2-yl-methyl halide of the formula R in which R, X and m have the meanings given in claim 1 and 15 Hal is chlorine, bromine or iodine, is reacted with a ketone of the formula ch 2 -co-c(ch 3 ) 3 in which Y has the meaning given in claim 1, or with an alkali metal enolate thereof, in the presence or absence of a solvent 20 or diluent, in the presence or absence of a strong inorganic or organic base, and with or without the addition of a reaction accelerator and/or phase transfer catalyst, at from 0° to 100°C, and the compound according to claim 1 thus obtained (Z being -CO-) is, if desired, reduced in the presence of 25 a solvent or diluent, at from -20 to 150°C, with hydrogen in the presence of a hydrogenation catalyst, or with a complex hydride, or with aluminum isopropoxide and isopropanol, or with sodium dithionite or electrochemically, to give a secondary alcohol according to claim 1 in which Z is the group -CH-, or the compound according to claim 1 in which Z is OH -CO- is reacted with a Grignard compound of the formula R^MgHal where R^ is alkyl of 1 to 4 carbon atoms and Hal is chlorine, bromine or iodine, in the presence or absence of a solvent or diluent and in the presence or absence of a magnesium or tetraalkyl-ammonium halide, at from 0 to 100°C, to give a tertiary alcohol according to claim 1, where Z is the group and the tertiary and secondary alcohol thus obtained are, if desired, reacted with an alkylating agent of the formula R 2 -Hal, where R has the meaning given in claim 1 and Hal is chlorine, bromine or iodine, or with an acid chloride of the formula

2. An azolylalkyl-2,3-dihydrobenzofuran as claimed in claim 1 wherein R is hydrogen or methyl, X is hydrogen, chlorine, bromine, methyl or methoxy, m is 1 or 2, Y is N 19 1 or CH and Z is CO or CR OR where R is hydrogen or methyl 2 and R is hydrogen, optionally chlorine-substituted alkyl of 1 to 6 carbon atoms, optionally chlorine-substituted benzyl or -COR 3 where R 3 is alkyl of 1 to 4 carbon atoms. 51828 3. 3 R -COCI or with an acid anhydride of the formula (R -CO^O, R having the meaning given in claim 1, in the presence or absence of a solvent or diluent and/or an inorganic or organic base and/or a reaction accelerator and/or a phase transfer catalyst, at from 0° to 100“C, and the compound according Q to claim 1 thus obtained (Z being -CO-R ) is, if desired, subsequently converted with acid into its acid addition salt or with a metal salt into its metal salt complex. 8. An azolylalkyl-2,3-dihydrobenzofuran when prepared by a process as claimed in the preceding claim. 9. The use of an azolylalkyl-2,3-dihydrobenzofuran as claimed in any of claims 1 to 6 or 8 as a fungicide. 10. A fungicide containing a solid or liquid carrier and an azolylalkyl-2,3-dihydrobenzofuran as claimed in any of claims 1 to 6 or 8. 11. A process for combating fungi, wherein the fungi or the objects to be protected against fungus attack are treated with an azolylalkyl-2,3-dihydrobenzofuran as claimed in any of claims 1 to 6 or 8.

3. 1 —'( 2,3-Dihydro-5,7-dichlorobenzofuran-2-yl )-2(1,2,4-triazol-1-yl)-3-methoxy-4,4-dimethylpentane.

4. 1-(2,3-Dihydro-5,7-dichlorobenzofuran-2-yl)-2(1,2,4-trlazol-l-yl)-3-hydroxy-4,4-dimethylpentane. 5. 1-(2,3-Dihydro-3-methy1-5,7-dichlorobenzofuran-2yl)-2-(1,2,4-triazol-l-yl)-4,4-dimethyl-pentan-3-one. 6. An azolylalkyl-2,3-dihydrobenzofuran as claimed in claim 1 and hereinbefore individually named or identified in any of the foregoing Examples 1 to 41. 7. A process for the manufacture of an azolylalkyl2.3- dihydrobenzofuran as claimed in claim 1, wherein a

5. 12. A process for combating fungus disease in a cereal crop wherein an azolylalkyl-2,3-dihydrobenzofuran as claimed in any of claims 1 to 6 or 8 is applied to the crop area or the cereal seed.