AU616546B2

AU616546B2 - Compounds containing triazole or imidazole groups, use thereof as fungicides and preparative processes

Info

Publication number: AU616546B2
Application number: AU39233/89A
Authority: AU
Inventors: Alfred Greiner; Regis Pepin
Original assignee: Rhone Poulenc Agrochimie SA
Current assignee: Bayer CropScience SA
Priority date: 1986-04-23
Filing date: 1989-08-02
Publication date: 1991-10-31
Anticipated expiration: 2007-04-21
Also published as: FI91866C; BR8701922A; IL82271A0; NO871634L; JPH0812608A; ATE85335T1; DZ1069A1; DK174326B1; KR950011421B1; DK203987D0; AU601973B2; UA26370A; YU44624B; YU73487A; OA08586A; DE3783946D1; MA20949A1; NZ220050A; HUT44124A; IL82271A

Description

I. COMMONWEALTH OF AUSTRALIA PATENT ACT 1952 COMPLETE SPECIFICATION6 1 6 4 FOR OFFICE USE CLASS INT. CLASS Application Number: Lodged: Complete Specification Lodged Accepted Published: Priority: Related Art: NAME OF APPLICANT RHONE-POULENC AGROCHIMIE ADDRESS OF APPLICANT 14-20 Rue Pierre Baizet, 69009 Lyon, France S' NAME(S) OF INVENTOR(S) Alfred GREINER and Regis PEPIN ADDRESS FOR SERVICE: DAVIES COLLISON, Patent Attorneys 1 Little Collins Street, Melbourne. Vic. 3000.

COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED: "COMPOUNDS CONTAINING TRIAZOLE OR IMIDAZOLE GROUPS, USE THEREOF AS FUNGICIDES AND PREPARATIVE PROCESSES.' i The following statement is a full description of this invention, including the best method of performing it known to us: -1

.I

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 fungal diseases of crops using them.

Many compounds containing triazole groups, particularly for use as fungicides, are already known, in particular from,EP-A-0,047,594. 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.

S1. The present invention provides a compound which S is a triazole or imidazole derivative of formula I, shown at the end of the description, in which A is Ph-(CH 2 )m 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 k each other Y, if n is greater than 1, is a halogen atom, a cyano or nitro group, or an unhalogenated or halogenated.

alkyl.or alkoxy group;.

Tr is a 1,2,4-triazol-l-yl group, Im is a 1,3-imidazol-l-yl group, f -2-

R

1 to R 5 which may be identical or different, are each a hydrogen atom or an unsubstituted or substituted

C

1

-C

6 alkyl, C 3

-C

6 cycloalkyl, aryl (especially phenyl), aralkyl (especially benzyl), C-C 6 alkoxy, C 1 -Cg alkanoyl or aroyl (especially benzoyl) group, each such group, for example, being substituted by at least one substituent chosen from halogen atoms and C 1

-C

6 alkoxy groups;

X

1 is a hydrogen or halogen atom; an unsubstituted or substituted C 1

-C

6 alkyl, C 3

-C

6 cycloalkyl, aryl (especially phenyl) or aralkyl (especially benzyl) group, for example, being substituted by at least one I substituent chosen from halogen atoms and C -C 6 alkoxy .1 6 S* groups; a -Q-R 6 group wherein 0 is O or S and R 6 is a Shydrogen atom or an unsubstituted or substituted C1-C 6 K 15 alkyl, C 3

-C

6 cycloalkyl, aryl (especially phenyl) aralkyl ca b \'oxc- (especially benzyl) acyl (especially acetyl or propionyl), S 0 0 thioacyl (especially thioacetyl or thiopropionyl), alkyloxythioyl, aryloxythioyl or aralkyloxythioyl groups S(the term thioyl corresponding to a group) each 0. 20 such group for example being substituted by at least one substituent chosen from halogen atoms and C 1

-C

6 alkoxy 0 groups; or a -NR 8

R

9 group wherein R8 and Rg, which may be identical or different, are each a hydrogen atom or an unsubstituted or substituted C -C alkyl, C 3

-C

6 cycloalkyl, aryl (especially phenyl) or aralkyl (especially benzyl) group each such group for example being substituted by at least one substituent chosen from r I -3halogen atoms and C1-C 6 alkoxy groups, or R 8 and R 9 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, for example by at least one substituent chosen from halogen atoms and unhalogenated or halogenated C 1

-C

6 alkyl or C 1

-C

6 alkoxy groups and a hydroxy group; and 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 acceotable salt thereof or complex thereof with a metal salt.

15 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 o 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 process can exist in one or more isomeric forms, according to the number of asymmetric centres in the molecule. The T t I -4invention 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 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 chlorine atom, in either an ortho and/or in the para position with respect to the -(CH 2 )m group. More oreferably *e *S n is 2 and each Y is a halogen atom, advantageously S 1* chlorine, in an ortho and in the para position with resoect to the group.

The preferred compounds are those in which R to

SR

5 and X 1 which may be identical or different, are each a hydrogen atom or a C 1

-C

6 alkyl group and/or Hal 1 and Hal 2 are both chlorine atoms. More preferably, R 1 to R 5 and X 1 are each a hydrogen atom.

S" 20 The triazole derivatives i.e. the compounds S 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 IIa shown at the end of the description, which may be obtained by a known process, in which A and R 5 are as defined above and Z is a halogen atom, is reacted with an organometallic compound of formula IIb shown at the end of the description in which R1 to R 4 and X1 are as defined above and M is an alkali metal, -Mg- Hal or -ZnHal, whetein Hal is a halogen atom, for example in 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 -50oC to the reflux temperature of the solvent and in a molar ratio IIa:IIb of preferably from 1.1:1 to 0.2:1. The reaction provides a compound of formula IIc shown at the end of the description in which A, XI, R 1 to R 5 and Z are as defined above after neutralization of the reaction mixture.

This process is described in EP-A-0,033,501.

15 Step b) The compound of formula lIc 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 0e temperature of from 80 C to the reflux temperature of the solvent and in a molar ratio TIc:imidazole or triazole of S" 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 f$ Il -6which A, X 1

R

1 to R 5 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 1 and R1 to R 5 are as defined above which may, if desired, be isolated or prepared separately by known methods, for example, by reacting the compound of formula IIc with one of the abovementioned bases, as described in EP-A-0,097,425.

In all cases, the introduction of the triazole or imidazole ring is advantageously performed in the presence of an acid-acceptor, in an anhvdrous 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, 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 tetrabutylammonium chloride.

i I -7- The reaction is more preferably carried out with a molar ratio of triazole or imidazole derivative to compound IIc of from 1.05:1 to 1.5:1.

When a solvent is employed, it is preferred to use a medium comprising 1% to 70% by weight of the compound of formula IIc 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 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.

20 Step c) Molecular halogen or mixed halogen is added to the compound of formula IId, preferably in an equimc ir 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 carried out in a concentrated inorganic acid medium, which has the advantage of causing the compound of formula I to precipitate out in SO *e 6 S. OS

S,

S.

S. S

SO

0* S

S.

0 55

S

S S. S Se 5 *5 i II -8the 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 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 compound of the -present invention as a fungicide.

The compounds of the present invention may be employed in both preventive and curative combat against u fungi, especially of the basidiomycetes, ascomycetes, 6 f adelomycetes or fungi-imperfecti type, in particular rusts, so 4 mildew, root-rot, fusarioses, helminthosporioses, septorioses and rhizoctones of vegetables and of plants in 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 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, 6 Fusarium oxysporum (melonis), Pyrenophora avenae, Septoria nodoruu, Septoria tritici, Venturia inaequalis, Whetzelinia -9scierotiorum, Monilia laxa, Mycosphaerella fijiensis, Marssonina panattonlana, Alternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporlum herbarum, Helminthosporium oryzae, Penicillium expansum, Pestalozzla sp., Phialophora cinerescens, Phoma betae, Phoma foveata, Phoma lingai, Ustilago maydis, Verticillium dahliae, 4 Ascochyta pisi, Guigardia bidwelii, Corticlum rolfsii, Phornopsis viticola, Scierotinia sclerotiorumn, Scierotinia minor, Coryneum cardinale and Rhizoctonia solani.

J.0 They are also active aqainst the following fungi: 4 Acrostalagmus konirigi, the Alternaria, the Colletotrichum, .4 Corticium rolfsii, Diplodia natalensis, Gaeumannomyces 04 0)graminis, Gibberella fujikuroi, Hormodendron "N :cl adospor ioides, Lentinus degener or tigrinus, Lenzites quercina, Mernnoniella echinata, Myrothecium verrucaria, v o a Paecyclomyces varioti, Pellicularia sasakil, Phellinus rnegaloporus, Polystictus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, the Stereum, Stilbum @0 *sp. Trametes trabea, Trichoderma pseudokonifigi and Trichothecium roseum.

0S.. 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 0* ~(piriculariosis). They may also be of great interest because of their activity on grey rot (Botrytis) and on cercosporioses, and, as a result, they may be applied to r~ i i crops as varied as vines and market garden crops, in arboriculture and in tropical crops such as peanut, banana, coffee and pecan nut.

The compounds may also be employed in the treatment of seeds 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; *0 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 S.January, 1984.

I S* 15 Besides the applications described above, the compounds of the invention also exhibit excellent biocidal activity towards many other varieties of microorganisms, 1. among which there may be mentioned fungi such as those of the genera: 20 Pullularia such as the species P. pullulans, Chaetomium such as the species C. globosum, Aspergillus such as the species Aspergillus niger and S**0 Coniophora such as the species C. puteana.

Because of their biocidal activity, the compounds of the invention make it possible to combat effectively microorganisms whose proliferation gives rise to many problems ii the agricultural and industrial fields. To this

I-

-11end, 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, S* employed by themselves or in the form of compositions in j wood treatment, are generally used with organic solvents and may be associated, if desired, with one or more known 5 o biocidal products such as pentachlorophenol, metal salts, 15 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 J 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 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 -12the 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.

These compositions, which may be employed to protect plants 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 solid or liquid carrier. The composition may comprise a surface-active a'gent which should also be agriculturally acceptable. In particular, the usual inert carriers and the usual surface-active agents can be employed.

The term "carrier" denotes a natural or Ssynthetic, organic or inorganic substance which facilitates o 15 the application of the compound of the present invention to the plant, seeds or soil. This carrier is therefore 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, resins, waxes and solid fertilizers) or liquid (water, alcohols, ketones, oil fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons and liquefied gases).

S; The surface-active agent may be an emulsifying, dispersing or wetting agent of ionic or nonionic type, for example salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic -13acids, 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 (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 agent in the application is water.

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

S.o 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 2 0 these latter cases).

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

The emulsifiable or soluble concentrates in most I Im- I- I I 1- I

C.

II -14cases comprise from 10 to 801 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 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.

S

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.

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 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 -as- "parts per million". The range of from 0.5 to 5,000 ppm corresponds to a range of from 5 x 10 5 to 0.5% (percentages by weight).

Insofar as the compositions which are adapted to 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 compound of the present invention in a very wide range of -5 amounts, for example from 5 x 10 to 95% by weight.

The following Examples further illustrate the present invention.

,The following is a concentrate: S* 15 Example F (formulation) 1 compound of the invention 400 g/l alkali metal dodecylbenzenesulphonate 24 g/l nonylphenol condensate with 10 molecules of ethylene oxide 16 g/1 20 cyclohexanone 200 g/1 aromatic solvent q.s 1 litre According to another formula of an emulsifiable S* concentrate, the following is employed: Example F 2 compound of the invention 250 g epoxidized vegetable oil 25 g i i r-r' -16mixture of alkylarylsulphonate and of polyglycol ether and of fatty alcohols 100 g dimethylformamide 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 applicable in soraying, are prepared so as to obtain a stable fluid product which does 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 0antifoams, 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 sprayihg 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 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: -17- Example 3: compound of the invention 501 calcium lignosuiphonate (deflocculant) isopropylnaphthalenosulphoflate (anionic wetting agent) 1% anticaking silica kaolin (filler) 39% Another composition of a 70% strength spraying powder employs the following constituents: Example F 4 compound of the invention 700 g sodium dibutylnaphthylsulpohonate 50 g product of condensation, in proportions of 3/2/1, of naphthalenesulphonic acid, of phenolsuiphonic acid and of formaldehyde 30 q kaolin 100 Q Champagne chalk 12C g Another composition of 40% strength spraying powder employs the following constituents: Example F -compound of the invention 400 q -sodium lignosuiphonate 50 g sodium dibutylnaphthalenesulphonate 10 g siia540 g Another composition of 25% strength spraying powder employs the following constituents: -18- Example 6 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 Another composition of 25% strength spraying powder employs the following constituents: f 0 SExample 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 sodium aluminosilicate 543 g kieselguhr 165 g Another composition of 10% strength spraying powder employs the following constituents: Example F 8 compound of the invention 100 g S. mixture of sodium salts of saturated fatty Ga acid sulphates 30 g product of condensation of naphthalenesulphonic acid with formaldehyde 50 g kaolin 820 g

I

-19- 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 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 foliege or seeds.

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

•s As has already been stated, aqueous dispersions and emulsions, for example the compositions obtained by diluting a wettable powder or an emulsifiable concentrate *f e *o 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 have a thick consistency like that of a mayonnaise.

The granulates intended to be dropped onto the So 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 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.

:I

According to an example of granulate composition, the following constituents are employed: Example F 9 compound of the invention 50 g 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 S. cetyl polyglycol ether are then added. Kaolin is watered

O°

o with the solution obtained and acetone is then evaporated off under vacuum. A microgranulate of this kind is 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 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 of preparation compounds according to the invention and these compounds themselves.

A -21- Example-I: Preparation of l-(2-(2,4-dichlorophenyl)-2- (lH)1,2,4-triazole. Compound No.

1.

Step a) Preparation of l-chloro-2-(2,4-dichlorophenyl)- 54-penten-2-ol: An organomagnesiun derivative is prepared by adding a solution of allyl bromide (180 mil) in i i ~1 11_ i S22 tetrahydrofuran (400 8L) to a suspension of magnesium (126 g) in tetreaydrofuran (400 ML) at 10 0 Co.

A solution of alpha,2,4-trichloroacetophenone (232 g) in tetrahydrofuran (250 ml) is added at -10 0

C,

and the mixture is neutralized with acetic acid. It is washed with water, dried and evaporated down. A colourless oil (258 g) is obtained. Boiling point (3 x 102 mm Hg) a 140-1420C.

S* CC S Step b) Preparation of 1-E2-(2,4-dichlorophenyl)-2-

C

10 hydroxy-4-pentenyLl(1H)1,2,4-triazoLe A mixture of the product obtained in step a) S. S (106 of triazole (55 g) and of potassium carbonate (160 g) is heated for four hours at 1200 in dimethylformamide (600 al). The insoluble materials are filtered 15 off, are washed with dimrethylformamide and tfhe reaction mixture is concentrated under vacuum. The residue, dissolved in methyene chloride, is washed with water and *Se then concentrated. The product is obtained by crystal- Lization fram ethyl acetate after ditution with heptane.

20 A pale pint solid (97 melting at 1010., is isolated.

Ste c) Preparation of compound No. 1 The compound obtained in step b (35 g) in chltoroform (200 al) is treated with bromine at dO. After the disappearance of colour, the solvent is ev;aporated off.

A sot id which has a melting point of .1.6 0 C is obtained.

-23- Example II -Preparation of 1-[2--(2,4-dichlorophenxl) 2-hydroxy-4,5-dichloropentyll (lH)1,2,4-t'riazole.

Compound No. 2.

The chiorohydrin (113 g) obtained in step a of Example 1, dissolved in DMF (100 ml) is run into a mixture of R 2 C0 3 (207 g) and of 1,2,4-triazole (35.9 g) in DMF (900 ml) at 125 0 C. After heating at 125 0 C, filtration of the insolubles and evaporation, washing and recrystallization, the triazole derivative IId (103 g) is obtained in the form of a light-brown solid.

This triazole derivative, dissolved in ***concentrated aguequs HC1, is treated with chlorine until the yellow colour persists. The mixture is then left at ambient temperature and is then dilutei. The Precipitate formed is .15 filtered off and treated with aqueous sodium bicarbonate.

.e After extraction, drying, evaporation and crystallization, a 00 00 white solid is obtained. Melting point 126 C.

The following compounds are obtained in the sam~e manner: 1-[2-(4-Chlorophenyl)-2-hydroxy-4,5-dichloropentyl] (11)1,2,4-triazole Compound No. 3 M.p. 82 0

C.

1- 4-Dichlorophenyl) -2-hydroxy-3-methvl- (lH)l,2,4-triazole. Compound No. 4. Oil.

1 1-12- 4-Dichlorophenyl) -2-hydroxy-3-methylo25 4,5-dichloropentylj (lH)1,2,4-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 out under such conditions that the spraying of a solution or suspension at a concentration equal to 1 g/l I' r 24 corresponds on average to the application of approximately 2 micrograms of active substance per cm 2 of plant foliage.

An aqueous emulsion of the active substance to 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 S10 of sorbitan) diluted to 10% strength in water: 0.3 ml *0 made up to 60 ml with water.

SThis aqueous emulsion is then diluted with water

S

to obtain the desired concentration.

o* In these examples it is considered that a product provides a total protection against a fungal disease when the protection is at least e

S.

Example III In vivo test on Piricularia oryzae, responsible for the piricularios'is 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 A inoculated by the application to the foliage of a suspension of spores obtained as a pure culture (500 spores/ml).

The contaminated plants are placed in an j_ 25 incubation cell at 25 C and 100% relative humidity 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 observed 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 S, 10 it is 10 cm in height by spraying with an aqueous emulsion ,o spraying mixture) at the concentration indicated above. The test is repeated twice. After 24 hours the barley plants are dusted with spores of Erysiphe graminis, 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 pota, sown in a 50/50 mixture of enriched peat and pozzolana, is treated at the stage when it is 10 cm in height by spraying with aqueous 7 26 0S OS

S

j S* S S S 00 emulsions spraying mixture) as described above.

The test is repeaoed twice.

After 24 hours, an aqueous suspension of spores (50,000 sp/ca") is dusted onto the wheat; this suspension having been obtained from contaminated plants. The wheat is then placed for 48 hours in an incubation ctl' at approximately 18 0 C and at 100% relative humidity.

After these 2 days, the wheat is taken to an observation cell where the relative humidity is returned to 10 60%. 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.

15 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 investigatd: 1) Botrytis cinerea sensitive to carbendazim and to cyclic imides 2) Botrytis cinerea resistant to carbendazim and to cyclic imides 3) Fusarium oxysporum f.sp. melonis 4) Rhizoctonia solani 5) .Pseudocercosporella herpotrichoides 6) Septoria nodorum So S

S

55 o S k I 27 7) Fusarium cultorum 8) Fusarium nivaLt 9) Fusarium roseum Helminthosporium gramineum 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.

10 In each test, the operating procedure is as fol- S Lows: a nutrient medium consisting of potato, of glu- S 0 cose and of agar (PDA medium) is introduced by supere fusion into a series of Petri dishes (20 ml per dish) a after sterilization in the autoclave at 120 0

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 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 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 fungus in the dishes containing the compound of the present invention to be tested is then compared with that of the dame 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

ENNIS

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tested, considered at a dosage of 30 ppm.

OS SO S6 S 0 3* 50 S P 0s 06 *0 0 *6 6.

~0 0 .0 *3.0 0 SO 05 0 *0 OS P 06 *OS S *0 10 Compound No. 1 2 3 4 5 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 5 95 95 95 .90 100 95 100 Compound Fungi No. 8 9 10 11 12 13 Fungi 1 15 2 3 4 95 80 80 a 100 100 100 100 It has atso been 95 95 95 100 100 100 100 100 100 100 100 3. 0 00 Ii S.

found that pirotebtion can be attained by using a combination of one or more compounds of the present invention with at least one further fungicide chosen from the following subclasses: I.Chlorinated or nitrated benzene derivatives such as quintozene or chtorothatonit, 2. Dicarbo'ximide derivatives such as captan, folpet, -29captafoL, iprodione and procymidone, 3. Derivatives containing one or more heterocycLic rings such as quinoLines and morphoLines, 4. Phosphoroue acid derivatives such as metal phosphites, 5. Dithiocarbamic acid derivatives such as maneb or manc ozeb, 6. PhenoL derivatives such as dinocap, 7. Quinone derivatives such as dlithianon, 8. Derivatives of carbamic acid and of benzimidazoLes such as carbendlaz im, benomyL and thiophanate-methyl, 9. Sulphur derivatives, Amines and amidles such as dichLoran, carboxin, triforine, cymoxanil, metaLaxyL and ofurace, 4 11. Diazines such as chinomethionat, fenarirnoL and an i La z ine 12. SuLphamides such as'dichLofLuanide, 13. Guanidlines such as dloguadine, 14. TriazoLes such as those described in British Patent S 44No. 2,046,.260., The -above are known active substances, most of them being described in dletail in works such as "The Pesticide ManuiL" 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

I-

30 substance but ternary (2 further active substances) or quaternary (3 further active substances combinations can also be employed.

Among the active substances mentioned above, particular preference will be given to the following:chLorothalonil, iprodione, fenpropimorph, tri- I demorph, dinocap, dithianon, maneb, mancozeb, AL-fosetyl, captan carbendazim, captafol, sulphur and diniconazol.

t S* The chemical names of the products Listed above S 10 are indicated in the appended table.

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

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

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00 0 S 66 S. S 0@ 50 ChLorotIhaLon ii lprod jone Fenpropimorph Tr idemorph D inocap 10 Dithianon Maneb Manc ozeb AL-fosetyL 15 Captan Carbendlaz ir CaptafoL 20 DiniconazoL TABLE OF NOMENCLATURE, TetrachtoroisophthatonitriLe 3-(3,5-DichLorophenyL)-N-isopropyt- 2,4-dioxoimidazoLjdjn-e-l-carboxamide is-4-( 3-(4-tert-butyLphenyL me thyLp ropytl-2, 6-d imethyl mo rphot ine 2,6-DimethyL-4-tridecyLmorpho.ine 2-(1-MethyLheptyt)-4,6-dinitropheny.

c rotonate 5, 10-0 ihydro-5, 10-d joxonaph thotZ, 3-b)- 1,4- dith iaanthraquinone Manganese ethyLenebis~dith jocarbamate) CompLex of maneb with a zinc salt Aluminium tr is-O-ethyLphosphonate N-(TrichLorornethyLthio)cycLohex-4-ene- 1,2-dicarbox imide Methyl benz imidazoL-2-yLcarbamate N-(1,1,2,2-TetrachLoroethyLthio)cycLohex-4-ene-1,Z-dicarbox imide 1-(2,4-DichLorophenyL)-4,4-dimethyL- 2-(1,2,4-triazoL-1-yL)-l-penten-3-oL.

This Latter product is described in Patent GB 2,046,260, aLready mentioned.

-32- Tr or i

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Claims

1. A compound which is a triazole or imidazole derivative of formula I Tr or Th in which A is Ph-(CH 2 wherein Ph is a phenyl nucleus, m is 0 or 1 and n is 0 or an inieger 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 or alkoxy group; Tr is a l,2,4-triazol-l-yl group and im is a l,3-imidazol-1-yl group Rto which may be identical or different, are each a hydrogen atom or an unsubstituted or substitutedC -6 alkyl, C 3 -C 6 cycloalkyl, aryl, aralkyl, C I- C 6 alkoxy, C 1 -C 6 alkanoyl or aroyl group; xis a hydrogen or halogen atom; an unsubstituted or substituted C -C 6 alkyl, C 3 -C 6 cycloalkyl, aryl or aralkyl group; lir i S. 0.. 0 0 0 S 0O S 0* 00 S *SSS S 0 S. S S. SS S 05 *0 a -Q-R 6 group wherein Q is 0 or S and R 6 is a hydrogen atom or an unsubstituted or substituted C 1 -C 6 alkyl, C 3 -C 6 carboxyhc. 1 6 3 cycloalkyl, aryl, aralkyl,)acyl, thioacyl, alkyloxythioyl, aryloxythioyl or aralkyloxythioyl group or a -NR 8 R 9 group wherein R8 and Rg, which may be identical or different, are each a hydrogen atom or an unsubstituted or substituted C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, aryl or aralkyl group or R 8 and R 9 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 acceptable salt thereof or complex thereof with a metal salt.

2. A compound according to claim 1 wherein m is 0.

3. A compound according to claim 1 or 2 which is a triazole derivative.

4. A compound according to any one of claims 1 to 3 wherein at least one of R 1 to R 5 which may be identical or different, is a C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, aryl, aralkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkanoyl or aroyl group substituted by at least one substituent chosen from halogen atoms and C 1 -C 6 alkoxy groups.

A compound according to any one of claims 1 to 4 36 wherein at least one of R 1 to R 5 is an unsubstituted or substituted phenyl, benzyl or benzoyl group.

6. A compound according to any one of claims 1 to 4 wherein R 1 to R 5 which may be identical or different, are each a hydrogen atom or an unsubstituted or substituted C 1 -C alkyl group.

7. A compound according to claim 6 wherein R I to R are each a hydrogen atom.

8. A comoound according to any one of claims 1 to 7 wherein X, is a C -C alkyl, C 3 -C 6 cycloalkyl, aryl or aralkyl group substituted by at least one substituent chosen from halogen atoms and C -C 6 alkoxy groups; a -Q-R 6 group 0 oS wherein Q is O or S and R is a C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, aryl, aralkyl, acyl, thioacyl, alkyloxythioyl, aryloxythioyl or aralkyloxythioyl group substituted by at least one substituent chosen from halogen atoms and C1-C 6 alkoxy groups; or a -NRgRg group wherein at least one of Rg and R 9 which may be identical or different, is a C-C 6 1 o6 alkyl, C 3 -C 6 cycloalkyl, aryl or aralkyl group substituted by at least one substituent chosen from halogen atoms and C 1 -C 6 alkoxy groups or R 8 -R 9 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 -C 6 alkyl or C -C 6 alkoxy groups and a hydroxy group. M 111 B U S. C a 0 a. os 0 9 0 90 0 ~0 OS 00 .0 9 00 Od 0 9 p 00.. 0 @0 00 ft 00 0 d a a. 0 05 @0 S 0* S C 0~ 37

9. A compound according to claim 8 w~herein X is an unsubstituted or substituted phenyl or benzyl group or a group wherein Q is 0 or S and R6is an unsubstitutel or substituted phenyl, benzyl, acetyl, thioacetyl, propionyl or thiopropionyl group.

A compound 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 compound according to any one of claims 1 to wherein Hal 1 and Hal 2 are identical.

12. A compound according to any one of claims 1 to 11 wherein Y is a halogen atom and n is 1, 2 or 3.

13. A compound according to claim 12 wherein Y is a chlorine atom.

14. A compound 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 -(CH group.

15. A compound according to claim 1 which is 1-[2-(2,4-dichlorophenyl)-2-hydroxy-4,5-dibromopentyl) (lH)- 1,2,4-triazole, 1 (2,4-dichlorophenyl)-2-hydroxy-4,5- dichlorope-sityl] (lH)l,2,4-triazole, l-[2-(4-chlorophenyli- 2-hydroxy-4,5-dichloropentyl] (lH)l,2,4-triazole, 1- 4-dichlorophenyl) -2-hydroxy-3-methyl-4, pentyl] (lH)1,2,4-triazole or l-[2-(2,4-dichlorophenyl)- 2-hydroxy-3-methyl-4,5-dichloropentylj-(lH)1,2,4-triazole.

16. A process for the preparation of a compound as defined in-any one of claims 1 to 15 which comprises ALI I I 'i:iii---li l: I -i l' 'lii- S1 1 38 reacting a compound of formula lid: x 1 I A 3 R 4 in which Tr, Im, A, X and R to R 5 are as defined in claim 1 with a molecular halogen or mixed halogen in a solvent 1 and, if desired, converting the comoound obtained to an e agriculturally acceptable salt or complex thereof. f17. A process according to claim 16 substantially as described in Example I or II. Se18. A compound As defined in any one of claims 1 to S, 15 whenever prepared by a process as defined in claim 16 or

17. 19 So The stcp, -features, ompositions and .mpou... j referred to or indicated in the specificat' and/or claims K. of this application, indivia y or collectively, and any and all combin. s of any two or more of said steps' or Dated this 2nd day of August, 1989. RHONE-POULENC AGROCHIMIE, By its Patent Attorneys, DAVIES COLLISON