NZ226774A - Fungicidal compositions comprising imidazole or triazole derivatives having halogenated substituents: treatment of crops - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £26774 % & * fa 0 NEW ZEALAND 22 6 7 7 A m Priority Date(s): ...

Complete Specification Filed: Class: .&D.I. <-*3>/Sbu fcS§> •27-U0V-1990' Publication Date: P.O. Journal, No: ... I.23&.-.

PATENTS ACT 1953 I PH ??87 PATENTS FORM MO. 5 & COMPLETE SPECIFICATION "COMPOUNDS CONTACTING TRIA20LE OR IMIDAZOLE GROUPS , USE THEREOF AS FUNGICIDES AND PREPARATIVE PROCESSES" *iWh v WE, RHONE-POULENC AGROCHIMIE, a French Body Corporate of lfc-20 Rue Pierre Baizet, Lyon 9e. France, 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: -l- (followed by page la) The present invention relates to compounds which are triazole or imidazole derivatives, a process for their preparation, use of them as fungicides, fungicidal compositions containing them and a method for combating 5 fungal diseases of crops using them.

Many compounds containing triazole groups, particularly for use as fungicides, are already known, in particular from .EP-A-O, 047, 594. The present invention seeks to provide compounds having improved properties in the 10 treatment of fungal diseases of crops, in particular in the treatment of piricularioses, of mildews and of rusts, especially of cereal crops.

The present invention provides a compound which is a triazole or imidazole derivative of formula I, shown at 15 the end of the description, in which A is (Y)nPh-(CHj) - wherein Ph is a phenyl nucleus, m is 0 or 1, preferably 0 and n is 0 or an integer less than 6, each Y, which may be identical or different to 20 each other Y, if n is greater than 1, is a halogen atom, a cyano or nitro group, or an unhalogenated or halogenated alkyl, alkoxy, phenyl, phenoxy, benzyl or benzyloxy group? Tr is a 1,2,4-triazol-l-yl group, Im is a 1,3-imidazol-l-yl group, & 22 6 7 74' n R1 to R5' w^ich "lay be identical or different, are each a hydrogen atom or an unsubstituted or substituted Cj-Cg alkyl, C^-Cg cycloalkyl, aryl {especially phenyl), aralkyl (especially benzyl), C^-Cg alkoxy, Cj-Cg alkanoyl or 5 aroyl (especially benzoyl) group, each such group, for ^ example, being substituted by at least one substituent \ chosen from halogen atoms and Cj-Cg alkoxy groups? is a hydrogen or halogen atom; an unsubstituted or substituted C^-Cg alkyl, Cj-Cg cycloalkyl, 10 aryl (especially phenyl) or aralkyl (especially benzyl) group, for example, being substituted by at least one substituent chosen from halogen atoms and C^-Cg alkoxy groups; a -Q-Rg group wherein 0 is 0 or S and Rg is a hydrogen atom or an unsubstituted or substituted C^-Cg 15 alkyl, C3~Cg cycloalkyl, aryl (especially phenyl) aralkyl (especially benzyl), acyl (especially acetyl or propionyl), thioacyl (especially thioacetyl or thioprooionyl), alkyloxythioyl, aryloxythioyl or aralkyloxythioyl groups (the term thioyl corresponding to a -C(=S)-S- group) each 20 such group for example being substituted by at least one substituent chosen from halogen atoms and C^-Cg alkoxy groups ? or a -NRgRg group wherein Rg and Rg, which may be identical or different, are each a 25 hydrogen atom or an unsubstituted or substituted C^-Cg alkyl, C^-Cg cycloalkyl, aryl (especially phenyl) or aralkyl (especially benzyl) group , each such group for example being substituted by at least one substituent chosen from O halogen atoms and C^-Cg alkoxy groups, or Rg and R^ may together form a single divalent hydrocarbon qroup containing from 3 to 6 carbon atoms, it being possible for one of the carbon atoms in the hydrocarbon group to be replaced by an 5 oxygen, sulphur or nitrogen atom, it also being possible for the hydrocarbon group to be substituted, for example by at least one substituent chosen from halogen atoms and unhalogenated or halogenated C^-Cg alkyl or C^-Cg alkoxy groups and a hydroxy group; and 10 Hal 1' and Hal 2, which may be identical or different, are each a halogen atom, preferably chlorine or bromine, Hal 1 and Hal 2 advantageously being identical; or an agriculturally acceptable salt thereof or complex thereof with a metal salt.

Examples of suitable salts and complexes are the hydrochloride, sulphate, oxalate, nitrate or arylsulphonate, and addition complexes with metal salts, especially with iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminium salts. By way of example, a complex 20 with zinc may be obtained by reacting a compound of formula I with zinc chloride.

The groups mentioned in the present text may, if possible, be linear or branched. The compounds of the present invention and intermediates used in the preparative 25 process can exist in one or more isomeric forms, according to the number of asymmetric centres in the molecule. The 22 6 7 7 invention therefore relates both to all the optical isomers and to their racemic mixtures and the corresponding diastereoisomers. The separation of the diastereoisomers and/or of the optical isomers may be carried out according 5 to methods which are known per se.

In view of the fungicidal applications in preferred compounds of the present invention Y is a halogen atom, preferably a chlorine atom, and n is 1, 2 or 3. Preferably n is 1 or 2 and Y is a halogen atom, preferably a 10 chlorine atom, in either an ortho and/or in the para position with respect to the -(CHj)- group. More oreferably n is 2 and each Y is a halogen atom, advantageously chlorine, in an ortho and in the para position with resoect to the "(CHj)- group.

The preferred compounds are those in which to Rg and X^ which may be identical or different, are each a hydrogen atom or a alkyl group and/or Hal 1 and Hal 2 are both chlorine atoms. More preferably, to R^ and X^ are each a hydrogen atom.

The triazole derivatives i.e. the compounds containing a triazole group, are preferred.

The compounds of the present invention may be prepared by the following process: Step a) A haloketone of formula Ila shown at the end of 25 the description, which may be obtained by a known process, in which A and R5 are as defined above and Z is a halogen 22 6 7 7 4 atom, is reacted with an organometallic compound of formula lib shown at the end of the description in which Rj to R4 and X^ are as defined above and M is an alkali metal, -Mg-Hal or -ZnHal, whetfein Hal is a halogen atom, for example in 5 a solvent preferably chosen from ethers such as diethyl ether or tetrahydrofuran, aliphatic, alicyclic or aromatic hydrocarbons such as hexane or toluene, at a temperature of from -50°C to the reflux temperature of the solvent and in a molar ratio IlasIIb of preferably from 1.1:1 to 0.2:1. The 10 reaction provides a compound of formula lie shown at the end of the description in which A, X^, Rj to and Z are as defined above after neutralization of the reaction mixture. This process is described in EP-A-0,033,501.

Step b) The compound of formula lie is subsequently reacted with an unsubstituted triazole or imidazole in the presence of organic or inorganic base, for example pyridine, triethylamine, sodium hydroxide, potassium hydroxide, or an alkali metal or alkaline-earth metal carbonate or 20 bicarbonate, and in a suitable solvent, for example an alcohol, ketone, amide, nitrile or aromatic hydrocarbon, any of which may be unhalogenated or halogenated, at a temperature of from 80°C to the reflux temperature of the solvent and in a molar ratio lie:imidazole or triazole of 25 preferably from 1.1:1 to 0.2:1. This results in a compound of the formula lid shown at the end of the description in 22 6 7 7 4 which A, X^, Rj to Rg, Tr and Im are as defined above. The reaction generally takes place via an epoxide intermediate of formula lie shown at the end of the description in which A, X^ and Rj to R5 are as defined above which may, if 5 desired, be isolated or prepared separately by known methods, for example, by reacting the compound of formula lie with one of the abovementioned bases, as described in EP-A-0,097,42 5.

In all cases, the introduction of the triazole or 10 imidazole ring i's advantageously performed in the presence of an acid-acceptor, in an anhydrous or nonanhydrous medium, in a solvent which is inert under the reaction conditions, and at a temperature of generally from 50 to 180°C, preferably at a temperature close to the boiling point of 15 the solvent. As acid-acceptors there may be mentioned inorganic bases, for example sodium hydroxide or potassium hydroxide, alkali metal or alkaline-earth metal carbonates, nitrogenous bases such as triethylamine, quaternary amines such as tetrabutylammonium hydroxide, and phosphonium 20 hydroxides. The solvents employed are advantageously polar aprotic solvents, for example dimethylformamide, dimethylacetamide, dimethyl sulphoxide,acetone, methyl ethyl ketone, acetonitrile and N-methylpyrrolidone, or polar protic solvents such as methanol or propanol. If desired, 25 this reaction may be carried out in the presence of a suitable catalyst, such as a phase-transfer catalyst, for example quaternary ammonium derivatives such as tetrabutyl-ammonium chloride. 22 6 7 7 The reaction is more preferably carried out with a molar ratio of triazole or imidazole derivative to compound lie of from 1.05:1 to 1.5:1.

When a solvent is employed, it is preferred to 5 use a medium comprising 1% to 70% by weight of the compound of formula lie or lie relative to the total weight of the solution.

The acid-acceptor should be present in at least a stoichiometric amount relative to the labile hydrogen atom 10 of the triazole or imidazole. In general, a molar ratio of from 1:1 to 2.5:1 is satisfactory.

It is to be understood that the salt derivative of the triazole or imidazole may be prepared separately and, in this case, the presence of an acid-acceptor is not 15 needed. This preparation may be carried out in an anhydrous or non-anhydrous medium in a solvent under the same operating conditions as those described for the in situ formation of the triazole or imidazole derivative converted into a salt.

Step c) Molecular halogen or mixed halogen is added to the compound of formula lid, preferably in an eguimolar amount, in an inert solvent such as an unhalogenated or halogenated aromatic or saturated hydrocarbon. This provides a compound of formula I. This addition may also be 25 carried out in a concentrated inorganic acid medium, which has the advantage of causing the compound of formula I to precipitate out in 22 6 7 7 4 the form of the corresponding salt.

Thus the present invention further provides a process for the preparation of a compound of the present invention which comprises reacting a compound of formula lid 5 with a molecular halogen or mixed halogen in a solvent and ^ if desired, converting the compound obtained to an agriculturally acceptable salt thereof or complex thereof with a metal salt.

The present invention also provides the use of a 10 compound of the -present invention as a fungicide.

The compounds of the present invention may be employed in both preventive and curative combat against fungi, especially of the basidiomycetes, ascomycetes, adelomycetes or fungi-imperfecti type, in particular rusts, 15 mildew, root-rot, fusarioses, helminthosporioses, septorioses and rhizoctones of vegetables and of plants in /~n, general and in particular of cereals such as wheat, barley, rye, oats, and their hybrids and also rice and corn.

The compounds according to the invention are 20 active in particular against fungi especially of the basidiomycetes, ascomycetes, adelomycetes or fungi-imperfecti type such as Botrytis cinerea, Erysiphe graminis, Puccinia recondita, Piricularia oryzae, Cercospora beticola, Puccinia striiformis, Erysiphe cichoracearum, 25 Fusarium oxysporum (melonis), Pyrenophora avenae, Septoria nodorum, Septoria tritici, Venturia inaequalis, Whetzelinia * 22 6 7 j 4 /~s, y"*v. u sclerotiorum, Monilia laxa, Mycosphaerella fijiensis, Marssonina panattoniana, Alternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporium herbarum, Helminthosporium oryzae, Penicillium expansum, Pestalozzia 5 sp., Phialophora cinerescens, Phoma betae, Phoma foveata, Phoma lingam, Ustilago maydis, Verticillium dahliae, Ascochyta pisi, Guigardia bidwellii, Corticium rolfsii, Phomopsis viticola, Sclerotinia sclerotiorum, Sclerotinia minor, Coryneam cardinale and Rhizoctonia solani. 10 They are also active aqainst the following fungi Acrostalagmus koningi, the Alternaria, the Colletotrichura, Corticium rolfsii, Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujikuroi, Horraodendron cladosporioides, Lentinus degener or tigrinus, Lenzites 15 quercina, Memnoniella echinata, Myrothecium verrucaria, Paecyclomyces varioti, Pellicularia sasakii, Phellinus megaloporus, Polystictus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, the Stereum, Stilbum sp. Trametes trabea, Trichoderma pseudokoningi and 20 Trichothecium roseum.

The compounds of the invention are especially advantageous because of their wide spectrum in respect of the diseases of the cereals (mildew, rust) and of rice (piriculariosis). They may also be of great interest 25 because of their activity on grey rot (Botrytis) and on cercosporioses, and, as a result, they may be applied to crops as varied as vines and market garden crops, in arboriculture and in tropical crops such as peanut, banana, coffee and pecan nut.

The comDounds may also be employed in the 5 treatment of seeds (e.g. cereals, cotton plant, beet, rape and fodder grains), for example in the form of coating or film-coating e.g. as described in US-A-3,989,501, col. 7, lines 17 to 23 and in FR-A- 2,588,442. It is also possible to employ aqueous streams.

In general, such formulations are already known; see, for example "Catalogue of pesticide formulation types and international coding system" published by the GIFAP, technical monograph No. 2, pages 12 to 14, revised in January, 1984.

Besides the applications described above, the compounds of the invention also exhibit excellent biocidal activity towards many other varieties of microorganisms, among which there may be mentioned fungi such as those of the genera; - Pullularia such as the species P. pullulans, - Chaetomium such as the species C. globosum, - Aspergillus such as the species Aspergillus niger and - Coniophora such as the species C. puteana.

Because of their biocidal activity, the compounds 25 of the invention make it possible to combat effectively microorganisms whose proliferation gives rise to many problems i-n the agricultural and industrial fields. To this 22 S 7 74 end, they are most especially suitable for the protection of plants or of industrial products such as wood, leather, paints, paper, ropework and plastics and industrial water circuits.

They are very particularly suited to the protection of lignocellulosic products and especially of wood, be it furniture, structural timber or timber exposed to inclement weather such as fencing timber, vine stakes or railway sleepers.

The compounds according to the invention, employed by themselves or in the form of compositions in wood treatment, are generally used with organic solvents and may be associated, if desired, with one or more known biocidal products such as pentachlorophenol, metal salts, especially those of copper, manganese, cobalt, chromium and zinc, derived from inorganic or carboxylic acids (heptanoic, octanoic, naphthenic acids), organic tin complexes, mercaptobenzothiazole, and insecticides such as the pyrethroids or organic chlorine derivatives.

Finally, they exhibit an excellent selectivity for crops.

They are applied advantageously in dosages of from 0.005 to 5 kg/ha, and more specifically of from 0.01 to 0.5 kg/ha.

The present invention provides a method for combating fungal disease of crops wherein an effective amount of a compound of the present invention is applied to is 2 2 § 7 7 o the crops or to the locus thereof.

For their use in practice, the compounds according to the invention are rarely employed by themselves. In most cases they form part of compositions. 5 These compositions, which may be employed to protect plants I against fungal diseases or to control plant growth, comprise a compound of the present invention in association with an , agriculturally acceptable carrier. This carrier may be a i % solid or liquid carrier. The composition may comprise a 1 » surface-active a'gent which should also be agriculturally \ | acceptable. In particular, the usual inert carriers and the t usual surface-active agents can be employed.

The term "carrier" denotes a natural or ^ synthetic, organic or inorganic substance which facilitates | 15 the application of the compound of the present invention to I the plant, seeds or soil. This carrier is therefore 1 generally inert and it must be agriculturally acceptable, especially on the treated plant. The carrier may be solid (for example clays, natural or synthetic silicates, silica, 20 resins, waxes and solid fertilizers) or liquid (water, alcohols, ketones, oil fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons and liquefied gases).

The surface-active agent may be an emulsifying, dispersing or wetting agent of ionic or nonionic type, for 25 example salts of polyacrylic acids, salts of 1ignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic 'w' 22 6 7 7 acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (especially alkylphenols or arylphenols), salts of esters of sulphosuccinic acids, taurine derivatives 5 (especially alkyltaurates), and phosphoric esters of alcohols or of phenols polycondensed with ethylene oxide. The presence of at least one surface-active agent is generally indispensable when the active substance and/or the inert carrier are not soluble in water and when the vector 10 agent in the application is water.

In this specification percentages, unless otherwise specified, are by weight.

As solid forms of compositions there may be mentioned powders for dusting or spraying (with a content of 15 compound of the present invention which may go up to 100%) and granulates, especially those obtained by extrusion, by compacting, by impregnation of a granular carrier, or by granulation from a powder (the content of compound of the present invention in these granulates being from 1 to 80% in 20 these latter cases).

As forms of compositions which are liquid or intended to constitute liquid compositions during application, there may be mentioned solutions, especially water-soluble concentrates, emulsifiable concentrates, 25 emulsions, flowables, aerosols, wettable powders (or spraying powder) and pastes.

The emulsifiable or soluble concentrates in most 22 67 7 4 n O cases comprise from 10 to 80% of the compound of the present invention, while ready for use emulsions or solutions generally comprise from 0.01 to 20% of the compound of the present invention.

These compositions may also comprise other ingredients, for example protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestrants and other known active substances with pesticidal properties (especially insecticides or 10 fungicides) or with properties which promote plant growth (especially fertilizers) or with properties controlling plant growth. More generally, the compounds according to the invention may be combined with any solid or liquid additives corresponding to the usual formulation techniques. 15 For example, in addition to the solvent, the emulsifiable concentrates may, when necessary, comprise from 2 to 20% of suitable additives such as stabilizers, surface-active agents, penetrating agents, corrosion inhibitors, colorants or adhesives, as referred to above. 20 In the case of a use of the compounds according to the invention as fungicides, the use dosages may vary within wide limits, especially depending on the virulence of the fungi and the climatic conditions.

As a general rule, compositions comprising from -25 0.5 to 5,000 ppm of the compound of the present invention are suitable; these values are indicated for the compositions which are ready for application: ppm means 22 67 7 4 'parts per million". The range of from 0.5 to 5,000 ppm :or respond: by weight) corresponds to a range of from 5 x 10~5 to 0.5% (percentages Insofar as the compositions which are adapted to 5 storage and to transport are concerned, these more advantageously comprise from 0.5 to 95% by weight of the compound of the present invention.

Thus, therefore, the compositions for agricultural use according to the invention may comprise the 10 compound of the present invention in a very wide range of amounts, for example from 5 x 10 ^% to 95% by weight.

The following Examples further illustrate the present invention.

The following is a concentrate: Example F (formulation) 1 - compound of the invention 400 g/1 - alkali metal dodecylbenzenesulphonate 24 g/1 - nonylphenol condensate with 10 molecules of ethylene oxide 16 g/1 - cyclohexanone 200 g/1 - aromatic solvent q.s 1 litre According to another formula of an emulsifiable concentrate, the following is employed: Example F 2 - compound of the invention 250 g - epoxidized vegetable oil 25 g 22 67 7 - mixture of alkylarylsulphonate and of polyglycol ether and of fatty alcohols - dimethylformamide 100 g 50 g - xylene 575 g Emulsions of any desired concentration, which are particularly suitable for application to foliage can be obtained from these concentrates by diluting with water.

Flowables, also apolicable in soraying, are prepared so as to obtain a stable fluid product which does 10 not settle and they usually contain from 10 to 75% of the compound of the present invention, from 0.5 to 15% of surface-active agents, from 0.1 to 10% of thixotropic agents, from 0 to 10% of suitable additives such as antifoams, corrosion inhibitors, stabilizers, penetrating 15 agents and adhesives and, as a carrier, water or an organic liquid in which the active substance is poorly soluble or insoluble; certain organic solid substances or inorganic salts may be dissolved in the carrier to help prevent sedimentation, or as antifreezes in the case of water. 20 Wettable powders (or spraying powder) are usually prepared so that they contain 5 to 95% of the compound of the present invention and, in addition to the solid carrier, usually from 0 to 5% of a wetting agent, from 3 to 10% of a dispersing agent and, when needed, from 0 to 10% of one or 25 more stabilizers and/or other additives such as penetrating agents, adhesives or anticaking agents and colorants.

By way of example, here are various compositions of wettable powders: 22 67 74 Example F 3; - compound of the invention 50% - calcium lignosulphonate (deflocculant) 5% - isopropylnaphthalenesulphonate (anionic wetting agent) 1% - anticaking silica 5% - kaolin (filler) 39% Another composition of a 70% strength spraying powder employs the following constituents: Example F 4 - compound of the invention - sodium dibutylnaphthylsulphonate - product of condensation, in proportions of 3/2/1, of naphthalenesulphonic acid, of phenolsulphonic acid and of formaldehyde - kaolin - Champagne chalk Another coraposition of 40% strength spraying powder employs the following constituents: Example F 5 - compound of the invention 400 g - sodium lignosulphonate 50 g - sodium dibutylnaphthalenesulphonate 10 g - silica 540 g Another coraposition of 25% strength spraying powder employs the following constituents: 700 g 50 g g 100 q 120 g 22 6 7 74 Example F 6 O - compound of the invention 250 g - calcium lignosulphonate 45 g - mixture of equal weights of Champagne chalk and of hydroxyethyl cellulose 19 g \ - sodium dibutylnaphthalenesulphonate 15 g - silica 195 g - Champagne chalk 195 g - kaolin 281 g 10 Another composition of 25% strength spraying powder employs the following constituents: Example F 7 - compound of the invention 250 g - isooctylphenoxy-polyoxyethylene-ethanol 25 g 15 - mixture of equal weights of Champagne chalk and of hydroxyethyl cellulose 17 g A - sodium aluminosilicate 543 g '■>—s - kieselguhr 165 g Another composition of 10% strength spraying 20 powder employs the following constituents: Example F 8 - compound of the invention 100 g - mixture of sodium salts of saturated fatty acid sulphates 30 g - product of condensation of naphthalenesulphonic acid with formaldehyde 50 g - kaolin 820 g 2267 7 4 To obtain these spraying powders or wettable powders, the active substances are mixed thoroughly with the additional substances in suitable mixers and are ground with the aid of mills or other suitable grinders. Spraying 5 powders whose wettability and dispersion are advantageous are thereby obtained; they can be suspended in water at any desired concentration and these suspensions can be very advantageously employed, in particular for application to plant foliage or seeds.

Pastes can be produced instead of wettable powders. The conditions and methods of producing and of using these pastes are similar to those for wettable powders or spraying powders.

As has already been stated, aqueous dispersions 15 and emulsions, for example the compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, are included within * the general scope of the present invention. The emulsions may be the water-in-oil or oil-in-water type and they may 20 have a thick consistency like that of a mayonnaise.

The granulates intended to be dropped onto the soil are usually prepared so that they are from 0.1 to 2 mm in size and they can be manufactured by agglomeration or impregnation. In general, the granulates comprise from 0.5 25 to 25% of the compound of the present invention and from 0 to 10% of additives such as stabilizers, slow-release modifying agents, binders and solvents. 22 67 According to an example of granulate composition, the following constituents are employed: Example F 9 - compound of the invention 50 g 5 - epichlorohydrin 2.5 g - cetyl polyglycol ether 2.5 g - polyethylene glycol 35 g - kaolin (particle size : 0.3 to 0.8 mm) 910 g In this particular case, the compound of the 10 present invention is mixed with epichlorohydrin and 60 g acetone is used to form a solution; polyethylene glycol and cetyl polyglycol ether are then added. Kaolin is watered with the solution obtained and acetone is then evaporated off under vacuum. A microgranulate of this kind is 15 advantageously employed for combatting soil fungi.

The compounds of the present invention may also be employed in the form of dusting powders; thus, a composition comprising 50 g of the compound of the present invention and 950 g of talc may be employed; it is also 20 possible to employ a composition comprising 20 g of the compound of the present invention, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting.

Examples I and II illustrate individual methods 25 of preparation compounds according to the invention and these compounds themselves. 22 6 7 7 Example I: Preparation of 1-[2- {2,4-dichlorophenyl)-2-hydroxy-4,5-dibromopentyl](1H)1,2,4-triazole. Compound No. 1.

Step a) Preparation of l-chloro-2- (2,4-dichlorophenyl)-4-penten-2-ol: An organomagnesium derivative is prepared by adding a solution of allyl bromide (180 ml) in 22 6 7 7 4 t e trahydrofuran (400 »l) to a suspension of magnesium (126 g) in tetrahydrofuran (400 ml) at 10°C.

A solution of atphaf2,4-trichloro acetophenone (232 g) in tetrahydrofuran (250 ml) is added at -10°C, 5 and the mixture is neutralized with acetic acid. It is washed with «ater, dried and evaporated down. A colourless oil C258 g) is obtained. Boiling point (3 x 10~2 mm Hg) » U0-UZ°C.

Step b) Preparation of 1 -C2-(2,4-dichI or opheny I )-2-10 hydroxy-4-pentenyl](1H)1,2,4-triazole A mixture of the product obtained in step a) (106 g), of triazole (55 g) and of potassium carbonate (160 g) is tieated for four hours at 120° in dimethyl-formamide (600 ml). The insoluble materials are filtered off, are washed with dimethylformamide and the reaction mixture is concentrated under vacuum. The residue, dissolved in methylene chloride, is washed with water and then concentrated. The product is obtained by crystallization from ethyl acetate after dilution with heptane. A pale pin* solid (97 g), melting at 101°, is isolated.

Step c) Preparation of compound No. 1 Th-e compound obtained in step b (35 g) in chloroform (200 ml) is treated with bromine at 0°. After the disappearance of colour, the solvent is evaporated off. A'sol id whicii has a melting point of 10L6°C i s obtained. o 22 6 7 7 4 f0*} Example II - Preparation of 1-[2-(2,4-dichlorophenyl)- 2-hydroxy-4, 5-d i ch lor open tyl) (1H)1,2,4 -triazole.

Compound No. 2.

The chlorohydrin (113 g) obtained in step a of 5 Example I, dissolved in DMF (100 ml) is run into a mixture of KjCO^ (207 g) and of 1,2,4-triazole (35.9 g) in DMF ■ o„ „ r. , i ->1-0. (900 ml) at 125 C. After heating at 125 C, filtration of the insolubles and evaporation, washing and recrystallization, the triazole derivative lid (103 g) is 10 obtained in the form of a light-brown solid.

This triazole derivative, dissolved in concentrated aqueous HC1, is treated with chlorine until the yellow colour persists. The mixture is then left at ambient temperature and is then diluted. The precipitate formed is 15 filtered off and treated with aqueous sodium bicarbonate. After extraction, drying, evaporation and crystallization, a white solid is obtained. Melting point 126°C.

The following compounds are obtained in the sar.e manner. 1-[2 - (4-Chlorophenyl)-2-hydroxy-4,5-dichloro- pentyl] (1H) 1 , 2, 4-tr iazole Compound No. 3 M.p. 82°C. w- 1-[2-(2,4-Dichlorophenyl)-2-hydroxy-3-methvl- 4, 5-dibromopentyl 3 (1H)1,2,4-triazole. Compound Nc , -i. Oil. 1-[2-(2,4-Dichlorophenyl)-2-hydroxy-3-methy1-25 4,5-dichloropentyl) (lH)l,2,4-triazole. Compound No. 5. Oil.

Examples III to V illustrate the fungicidal applications of the compounds according to the invention.

In these examples, the spraying operations with solutions or suspensions of active substances are carried 30 out under such conditions that the spraying of a solution or suspension at a concentration equal to 1 g/1 22 6 7 74 o o o corresponds on average to the application of approximately 2 micrograms of active substance per ca^ of plant foliage.

An aqueous emulsion of the active substance to 5 be tested, having the following composition, is prepared by fine grinding: - active substance to be tested: 60 mg - Tween 80 (surface-active agent consisting of an oleate of an ethylene oxide polycondensate derivative of sorbitan) diluted to 102 strength in water: 0.3 ml - made up to 60 ml with water.

This aqueous emulsion is then diluted with water to obtain the desired concentration.

In these examples it is considered that a product 15 provides a total protection against a fungal disease when the protection is at least 95%.

Example III - In vivo test on Piricularia oryzae, responsible for the piriculariosis of rice (rice blast) Rice, in pots, sown in a 50/50 mixture of en-20 riched peat and pozzolana, is treated at the stage when it is 10 cm in height by spraying with an aqueous emulsion ( spraying mixture) as defined above. The test plants are is repeated twice. After 24 hours the ^ inoculated by the application to the foliage of a suspension of spores 25 obtained as a pure culture (500 spores/ml).

The.contaminated plants are placed in an 22 67 74 o i - r\ o incubation cell at 25°C and 100X relative hum'dity for 24 h before being placed in an observation cell.

The reading is taken 8 days after the contamination. Under these conditions, a total protection is ob-5 served at 1 g/l in the case of the compounds 1, 2 and 3.

Example IV - In vivo test on Erysiphe graminis on barley (barley mildew) Barley, in pots, sown in a 50/50 mixture of enriched peat and pozzolana is treated at the stage when 10 it is 10 cm in height by spraying with an aqueous emulsion ( spraying mixture) at the concentration indicated above. The test is repeated twice. After 24 hours the barley plants are dusted with spores of Erys iphe gramin is, the dusting being carried out with the aid of diseased 15 plants.

The reading is taken 8 to 14 days after the contamination.

Under these conditions, the following results are obtained: at the dosage of 1 g/l, complete protec-20 tion with the compounds 1,2 and 3.

Example V - In vivo test on Puccinia recondita, responsible for wheat rust Wheat, in pots, sown in a 50/50 mixture of enriched peat and pozzolana, is treated at the stage 25 when it is U) cm in height by spraying with aqueous rs ZZ6 7 7 4 emulsions ( spraying mixture) as described above.

The test is repeated twice.

After 24 hours, an aqueous suspension of spores (SO,000 sp/cm^) is dusted onto the wheat; this suspension 5 having been obtained from contaminated plants. The wheat is then placed for 48 hours in an incubation cell at approximately 18°C and at 100X relative humidity.

After these 2 days, the wheat is taken to an observation cell where the relative humidity is returned to 10 60S. The check on the state of the plants is made between the 11th and the 15th day after the contamination, by comparison with the untreated control.

At the dosage of 1 g/l, complete protection with the compounds 1, 2 and 3 is observed.

O Example 6 - In vitro test on seed fungi and soil fungi The action of the compounds according to the invention on the following fungi, responsible for the diseases of cereals and other plants is investigated; 1) Botrytis cinerea sensitive to carbendazim and to 20 cyclic imides 2) Botrytis cinerea resistant to carbendazim and to cyclic imides 3) Fusarium oxysporum f.sp. melonis 4) R h i z oc ton i a solani 5) .PseudocercosporelLa herpotrichoides 6) Septoria nodorum 22 67 7 7) Fusarium culmorum 8) Fusarium nivale 9) Fusar ium roseum ) He I hi i n t ho spo r i um gram ine urn 11) Pyrenophora avenae 12) Helminthosporium teres 13) Rhizoctonia cerealis The numbers appearing before the names will be employed to identify the fungi in the table below.

In each test, the operating procedure is as fol lows: a nutrient medium consisting of potato, of glucose and of agar (PDA medium) is introduced by super-fusion into a series of Petri dishes (20 ml per dish) after sterilization in the autoclave at 120°C.

While the dishes are being filled, an acetone solution of the compound of the present invention is injected into the superfusion medium, to obtain the final desired concentration.

Petri dishes similar to the preceding ones, into 20 which similar quantities of a nutrient medium, not containing any compound of the present invention, are poured, are taken as a control.

After 24 or 48 h each dish is seeded by depositing a fragment of mycelium originating from a previous 25 culture of the same fungus.

The dishes are stored at 22°C for 2 to 10 days (depending on the fungus tested) and the growth of the 22 6 7 74 O W fungus in the dishes containing the compound of the present invention to be tested is then compared with that of the same fungus in the dish employed as control.

The degree of inhibition of the growth of the fungus is thus determined in the- case of each compound tested, considered at a dosage of 30 ppm.

Compound Fungi No. 1 2 3 u 6 7 1 95 ' 95 90 90 100 95 100 2 90 95 50 80 100 100 0 3 95 95 90 90 95 95 100 4 95 95 90 90 90 90 100 . 95 95 95 90 100 95 100 Compound Fungi No. 8 9 11 12 13 1 95 80 95 100 95 100 2 80 0 95 100 100 95 3 100 100 95 100 100 95 4 100 mm 100 95 95 100 — — 100 100 95 It has also been found that protection can' be attained by using a combination of one or more compounds of the present invention with at 20 least one further fungicide chosen from the following subclasses: 1.Chlorinated or nitrated benzene derivatives such as quintozene or chlorothalonil, 2. Oicarboximide derivatives such as captan» folpet, o « I 22 6 7 7 4 captafol, iprodione and procymidone, ' I 3. Derivatives containing one or more heterocyclic rings such as quinolines and morpholines , 4. Phosphorous acid derivatives such as metal phosphites, 5 S. Dithiocarbanic acid derivatives such as maneb or mancozeb, 6. Phenol derivatives such as dinocap, 7. Quinone derivatives such as dithianon, 8. Derivatives of carbamic acid and of benzimidazoIes 10 such as carbendazim, benomyl and thiophanate-methyl, 9. Sulphur derivatives, . Amines and amides such as dichloran, carboxin, tr i — forine, cymoxanil, metalaxyl and ofurace, 11. Diazines such as chinomethion at, fenarimol and 15 anilazine, N 12. Sulphamides such as dichlofluanide, 13. Guanidines such as doguadine, 14. Triazoles such as those described in British Patent No. 2,046,260.

The above are known active substances, most of them being described in detail in works such as "The Pesticide Manual" published by The British Crop Protection Council, the 7th edition of which dates from 1983 .

The combinations according to the invention are in most cases of binary type (a single further active - © 22 6774 substance K but ternary (2 further active substances) or quaternary (3 further active substances ) combinations can also be employed.

Among the active substances mentioned above, 5 particular preference will be given to the following:-chlorothaloniI, iprodione, fenpropimorph, tri-demorph, d inoc ap, dithianon, maneb, mancozeb, Al-fosetyl, captan , carbendazim, captafol, sulphur and diniconazol.

The chemical names of the products listed above 10 are indicated in the appended table.

The weight ratio of the compound according to the invention to the active substances described above is preferably from 0.0003:1 to 3,000:1 and advantageously from 0.001:1 to 1,000:1.

It is also possible to combine insecticides, repellents and germination regulators with the compounds or combinations described above.

Cl V' 22 677 4 Chlorothalonil Iprod ione Fenpropimorph Tr idemorph 0 i noc ap D i th i anon Maneb Mancozeb Al-fosetyl 15 Captan Carbendazim Captafol Diniconazol TABLE OF NOMENCLATURE Tetrachloroisophthalonitrile 3-(3,5-Dichlorophenyl)-N-isopropyl- 2,4-dioxoimidazolidine-l-carboxamide (0-Cis-4-[3-(.4-tert-butylphenyl)-2- methylpropyl]-2,6-diniethylinorpholine 2/6-0imethyl-4-tridecylmorpholine 2-(1-Methylheptyl)-4,6-dinitrophenyl crotonate ,10-0ihydro-5,10-dioxonaphthoC2,3-bD-1,4-d i thiaanthraquinone Manganese ethylenebisldi thiocarbamate) Complex of maneb with a zinc salt Aluminium tris-0-ethylphosphonate N-(Trichloromethylthio)cyclohex-4-ene-1,2-d i c a rbo x i m i de Methyl benzimidazol-2-ylcarbamate N-(1,1,2,2-Tetrachloroethylthio)cyclo- hex-4-ene-1,2-dicarboximide 1-(2,4-Dichlorophenyl)-4,4-dimethyl- 2-(1,2,4-triazol-1-yl)-1-penten-3-ol. This latter product is described in Patent GB 2,046,260, already mentioned.

Q 22 67 7 4 o, Tr or Im H<*1 1 r2 Rx Hal 2 Ha I r*s lib ! 4

Claims (5)

1. 22 6 7 7 4' -33- 226774 -34- WHAT <^WE CLA.W1 IG: A fungicidal composition which comorises a compound which is a triazole or imidazole derivative of formula I: in which A is (Y) Ph-(CH_)- wherein Ph is a ohenyl nucleus, m is 0 or n z m J 1 and n is 0 or an integer less than 6; each Y, which may be identical or different to each other Y if n is greater than 1, is a halogen atom, a cyano or nitro group or an unhalogenated or halogenated alkyl, alkoxy, phenyl, phenoxy, benzyl or benzyloxy group; Tr is a 1,2,4-triazol-l-yl group and Im is a 1,3-imidazol-l-yl group R1 to R5' may be identical or different, are each a hydrogen atom or an unsubstituted or substituted Cj-Cg alkyl, C3~Cg cycloalkyl, aryl, aralkyl, C^-Cg alkoxy, Cj~Cg alkanoyl or aroyl group; is a hydrogen or halogen atom; an unsubstituted or Tr or Im *5 R3 R4 Hal 2 I group; substituted C^-Cg alkyl, C^-C or aralkyl m 226774 -35- D o a -Q-Rg group wherein Q is 0 or S and Rg is a hydrogen atom or an unsubstituted or substituted Cj-Cg alkyl, C3""Cg cycloalkyl# aryl, aralkyl, acyl, thioacyl, alkyloxythioyl, aryloxythioyl or aralkyloxythioyl group or a -NRgRg group wherein Rg and Rg, which may be identical or different, are each a hydrogen atom or an unsubstituted or substituted C^-Cg alkyl, C^-Cg cycloalkyl, aryl or aralkyl group or Rg and Rg may together form a single divalent hydrocarbon group containing from 3 to 6 carbon atoms, it being possible for one of the carbon atoms in the hydrocarbon group to be replaced by an oxygen, sulphur or nitrogen atom, it also being possible for the hydrocarbon group to be substituted; and Hal 1 and Hal 2, which may be identical or different, are each a halogen atom; or an agriculturally acceDtable salt thereof or complex thereof with a metal salt^/ in association with an agriculturally acceptable carrier.

2. A composition according to claim 1 wherein m is 0. 3* A composition according to claim 1 or 2 which is a triazole derivative. 4. A composition according to any one of claims 1 to 3 wherein at least one of R^ to R^, which may be identical or j different, is a ^-Cg alkyl, C-j-Cg cycloalkyl, aryl, S aralkyl, Cj-Cg alkoxy, C^-Cg alkanoyl or aroyl group substituted by at least one substituent chosen from halogen atoms and C^-Cg alkoxy groups. 5. A composition according to any one of claims 1 to 4 ' o *5 fi i % 226774 -36- wherein at least one of Rj to R5 is an unsubstituted or substituted phenyl, benzyl or benzoyl group. 6. A composition according to any one of claims 1 to 4 wherein Rj to R5, which may be identical or different, are each a hydrogen atom or an unsubstituted or substituted Cj-Cg alkyl group. 7. A .composition according to claim 6 wherein R^ to Rg are each a hydrogen atom. 8. A composition according to any one of claims 1 to 7 wherein X, is a Cj-Cg alkyl, c3~cg cycloa^y1» aryl or aralkyl group substituted by at least one substituent chosen from halogen atoms and C^-Cg alkoxy groups; a -Q-Rg group wherein Q is 0 or S and Rg is a C^-Cg alkyl, C^-Cg cycloalkyl, aryl, aralkyl, acyl , thioacyl, alkyloxythioyl, aryloxythioyl or aralkyloxythioyl group substituted by at least one substituent chosen from halogen atoms and C1~Cg alkoxy groups; or a -NRgRg group wherein at least one of Rg and Rg, which may be identical or different, is a C^-Cg alkyl, C3~Cg cycloalkyl, aryl or aralkyl group substituted by at least one substituent chosen from*-halngen atoms and Cj-Cg alkoxy groups or Rg-Rg together form a single divalent hydrocarbon group containing from 3 to 6 carbon atoms, it being possible for one of the carbon atoms in the hydrocarbon group to be replaced with an oxygen, sulphur or nitrogen atom, substituted by at least one substituent selected from halogen atoms, and unhalogenated or halogenated C^-Cg alkyl or C^-Cg alkoxy groups and a hydroxy group. 2 2- 6 7 7 4 37- 9. A composition according to claim 8 wherein X is an unsubstituted or substituted phenyl or benzyl group or a -Q-Rg group wherein Q is 0 or S and Rg is an unsubstituted or substituted phenyl, benzyl, acetyl, thioacetyl, propionyl or thiopropionyl group. 10. A composition according to any one of claims 1 to 9 wherein Hal 1 and Hal 2, which may be identical or different, are each a chlorine or bromine atom. 11. A composition according to any one of claims 1 to 10 wherein Hal 1 and Hal 2 are identical. 12. -A composition according to any one of claims 1 to 11 wherein Y is a halogen atom and n is 1, 2 or

3. 13. A composition according to claim 12 wherein Y is a chlorine atom. 1

4. A composition according to claim 12 or 13 wherein n is 1 or 2, and Y is in either an ortho and/or in the para position with respect to the ""(CHj)- group. 1

5. A composition according to claim 1 wherein the compound of formula (I) is 1-(2-(2, 4-dichlorophenyl)-2-hydroxy-4,5-dibromopentyl] (1H) — 1,2,4-triazole, 1(2-(2,4-dichlorophenyl)-2-hydroxy-4,5-dichloropentyl] (1H)1,2,4-triazole, 1—[2-(4—chlorophenyl) - 2-hydroxy-4,5-dichloropenty1](1H)1,2,4-triazole, 1-J2-(2,4-dichlorophenyl)-2-hydroxy-3-methyl-4,5-dibromopentyl] (1H)1,2,4-triazole or 1-[2-(2,4-dichlorophenyl)- 2-hydroxy-3-methyl-4,5-dichloropentyl]-{lH)l,2,4-triazole. -38- A method for combating fungal disease of crops wherein an effective amount of a compound as defined in any one of claims 1 to 15 is applied to the crops or to the locus thereof. •J7# A method according to claim 16 wherein the compound as defined in any one of claims 1 to 15 is applied in an amount of from 0.005 to 5 kg/ha. ■jg A method according to claim 17 wherein the compound as defined in any one of claims 1 to 15 is applied in an amount from 0.01 to 0,5 kg/ha. 19* A method according to any one of claims 16 to 18 wherein the fungal disease is a piriculariosis, mildew or crop rust. 20. A method according to claim 16 substantially as hereinbefore described. fl.HOU£-eout£vc,.AC£SCMIti£ By ,.WrJf/Their authorisad Agent A. J. PARK & SON