GB2355261A - Triazolopyrimidine fungicides - Google Patents

Abstract

The novel compounds of formula l: <EMI ID=1.1 HE=44 WI=83 LX=708 LY=572 TI=CF> <PC>wherein Ar, R<SP>1</SP>, Hal and L<SP>1</SP> through L<SP>5</SP> are defined in the specification, have selective fungicidal activity. The new compounds may be formulated with carriers and optionally adjuvants to produce fungicidal compositions useful for treating plants.

Description

2355261 FUNGICIDAL 7-ANILINO-TRIAZOLOPYRIMIDINES

BACKGROUND OF THE INVENTION- 1 -

This invention relates to certain triazolopyrimidine compounds, a process for their preparation, compositions containing such compounds, a method for combating a fungus at a locus comprising treating the locus 5 with such compounds, and their use as fungicides.

EP-A-0 071 792 claims compounds of the general formula NH 2 (R)n 3 N - N R -2 A N R in which R1 represents alkyl, halogen, alkoxy, cyano, cycloalkyl, aryl, aryloxy, arylthio, aralkyl, arylthio, arylalkyl, arylalkyloxy or arylalkylthio each optionally substituted by halogen or alkoxy; or (R')n represents a benzene, indane or tetrahydronaphthalene ring fused with the phenyl ring, aromatic moieties in the above groups being optionally substituted by alkyl, alkoxy, halogen or cyano; n is 1 or 2; R 2 and R 3 are each hydrogen, alkyl or aryl, A represents a nitrogen atom or a CR 4 group, and R 4 is as R 2 but can also be halogen, cyano or alkoxycarbonyl or together with R 3 can form an alkylene chain containing up to two double bonds. The compounds are said to be active against various phytopathogenic fungi, especially those of the phycomycete class. However evidence of fungicidal activity is only provided for these compounds against Plasmopara viticola, a member of the oomycete class of fungi. EP 0 550 113-A2 claims compounds of the general formula R 1 R 2 N N- R 3 <1, N 4 J" N, N R in which R' represents an optionally substituted alkyl, alkenyl, alkadienyl, cycloalkyl, bicycloalkyl or heterocyclyl group; R 2 represents a hydrogen atom or an alkyl group; R' represents an optionally substituted aryl group; 5 and R 4 represents a hydrogen or halogen atom or a group -NR5R' where R 5 represents a hydrogen atom or an amino, alkyl, cycloalkyl or bicycloalkyl group and R' represents a hydrogen atom or an alkyl group. However, there is no hint to triazolopyrimidine compounds in which any of R' and R 2 is an optionally substituted phenyl group. 10 SUMMARY OF THE INVENTION The present invention provides a compound of formula I

L 2 L 1 L 3 Ll'C Ar, N - N Y-R L 4 N L5 L 5 N N Hal in which Ar represents an optionally substituted phenyl group, and R1 represents a hydrogen atom or an optionally substituted alkyl, alkenyl, alkynyl, alkadienyl or phenyl group, or R1 may be connected to the ortho-position of the Ar group to form an optionally substituted azabicyclic ring system; Hal represents a halogen atom; and L' through L 5 each independently represent an hydrogen or halogen atom or an alkyl, alkoxy, haloalkyl, haloalkoxy or nitro group.

The new compounds have excellent selective fungicidal activity in various crops, in particular against diseases on rice such as rice blast and rice sheath blight.

It is an object of the present invention to provide novel, selective 5 fungicidal compounds.

It is also an object of the invention to provide methods for controlling undesired fungus by contacting said plants with a fungicidally effective amount of the new compounds.

It is another object of the invention to provide selective fungicidal 10 compositions containing the new compounds as active ingredients.

These and other objects and features of the invention will be more apparent from the detailed description set forth hereinbelow, and from the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

It has surprisingly been found that the compounds of formula I L 2 L L 3 Ll Ar, N-R L4 N- N L 5 N N Hal in which Ar, R1, Hal and L' through L5 have the meaning given above 20 have excellent fungicidal activity against a broad range of fungi, in particular against Pyricularia oryzae and Rhizoctonia solani. Unless otherwise stated, as used herein the term halogen atom may denote a bromine, iodine, chlorine or fluorine atom, and is especially a bromine, chlorine or fluorine atom, most preferably chlorine. 25 Optionally substituted moieties may be unsubstituted or have from one up to the maximal possible number of substituents. Typically, 0 to 3 substituents are present.

The terms alkyl, alkenyl, alkynyl, and alkadienyl, as used herein with respect to a radical or moiety, refer to a straight or branched chain radical or moiety having up to 10, in particular up to 6 carbon atoms.

Suitably an alkyl moiety has from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms. Highly preferred alkyl moieties include ethyl or, especially, a methyl group. Suitably, an alkenyl moiety has from 2 to 6 carbon atoms. A preferred alkenyl moiety is allyl or, especially, a 2 methylallyl group. Any alkenyl or alkynyl part of the substituents contains up to 10 carbon atoms, preferably up to 9 carbon atoms, more preferably up to 6 carbon atoms. Each optionally substituted group independently is substituted by one or more halogen atoms or nitro, cyano, cycloalkyl (preferably C3-6 cycloalkyl), cycloalkenyl (preferably C3-6 cycloalkenyl), haloalkyl (preferably C1.6 haloalkyl), halocycloalkyl (preferably C3-6 halocycloalkyl), alkoxy (preferably C1.6 alkoxy), haloalkoxy (preferably C1.6 haloalkoxy), trialkylsilyl (preferably tri-Cl-4 alkylsilyl), phenyl, halo- or dihalo-phenyl or pyridyl groups. Any alkyl, alkenyl or alkynyl group may be linear or branched.

The invention especially relates to compounds of formula 1, in which R1 represents a hydrogen atom or a Cl-10 alkyl or phenyl group, preferably a hydrogen atom or a methyl group.

The invention also relates to compounds of formula I in which R' is connected with the ortho-position of the Ar group to form an optionally substituted dihydroindol-1 -yl or tetrahydroisoquinolin-1 -yl group, in particular a 1,2,3,4-tetrahydroisoquinolin-1 -yl group.

Included in the scope of the present invention are (R) and (S) isomers and atropisomers of compounds of formula 1, which have a chiral center or in which the substituents Ll or L' and L 2 are different from L 5 or L 5 and L 4, and the racemates thereof, and salts, N-oxides and acid addition compounds.

Another preferred embodiment of the present invention comprises compounds of formula I wherein R' represents a hydrogen atom or a Ci-jo alkyl group or C3-1o alkenyl group.

Those compounds of formula I in which R' represents a hydrogen atom are particularly preferred.

L' through L 5 each independently preferably represent a hydrogen or a halogen atom, in particular fluorine or chlorine, or a methoxy group.

Preferred are those compounds of formula 1, in which at least one of L' and L 5 represents a fluorine or chlorine atom.

Particularly preferred are compounds of formula 1, in which the phenyl group 1! L L 3 IF is selected from 5, L 4 Cl F F F F F )9::9 4 Br F IF F F OMe and in which OMe represents a methoxy group.

Another preferred embodiment of the present invention comprises compounds of formula I wherein R1 represents a hydrogen atom or a C1.1o alkyl group orC3-1o alkenyl group.

Those compounds of formula I in which Ar represents a phenyl group substituted by one or more, preferably one, two or three, substituents selected from the group consisting of halogen atoms, alkyl, alkoxy, haloalky, haloalkoxy, nitro, cyano and alkoxycarbonyl groups are preferred. Ar most preferably represents a 2- or 4-methylphenyl or a 2-or 4-fluorophenyl group.

In another preferred embodiment of this invention, the phenyl group Ar is substituted by a group of formula A 2 ''W 3 (A) R X-CO -0-R wherein R 2 and R 3 each independently represent an alkyl group, W represents N or CH, and X represents 0 or NH. Preferably, R 2 and R 3 each represent a methyl group.

The compounds of this invention may be oils, gums, or, predominantly crystalline solid materials. They have valuable fungicidal properties, in particular their enhanced systemicity and enhanced fungicitoxity against rice diseases and powdery mildews compared to previously known fungicides. For example, they can be used in agriculture or related fields for the control of phytopathogenic fungi such as Alternaria solani, Botrytis cinerea, Cercospora beficola, Cladosporium herbarum, Corticium rolfsfi, Erysiphe graminis, Helminthosporium tritici repenfis, Leptosphaeria nodorum, Micronectriella nivalis, Monifinia fructi gena, Mycosphaerella figulicola, Mycosphaerella pinodes, Pyricularia grisea fsp. oryzae, Rhizodonia solani, Venturia inaequalis, Septoria trifici, Uncinula necator and Sclerofinia sclerotiorum, in particular for the control of Cercospora beficola, Pyricularia grisea f.sp. oryzae, Rhizoctonia solani and Venturia inaequalis. The compounds of the invention possess a high fungicidal activity within a wide concentration range, and may be used in agriculture by those skilled in the art without any significant difficulties.

Moreover, the compounds according to the invention exhibit enhanced residual control of fungi, in particular of rice sheath blight, compared with conventional fungicides.

Good control of phytopathogenic fungi is obtained using a compound as defined in formula I wherein at least one of L' and L5 represents a halogen atom; and/or R' represents a hydrogen atom or a methyl group.

Especially good results in terms of control of phytopathogenic fungi are obtained by using, for example, the following compounds of formula 1:

5-chloro-6-(2-chloro-6-fluorophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2,6-dif I uorophenyl)-7-(4-methylani I ino)-[ 1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-7-(4-methylanilino)-6-(2,4,6-trif I uorophenyl)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2-chlorophenyl)-7-(4-methylani I i no)-[ 1,2,4]tri-azolo [1,5-a]pyrimidine; 5-chloro-6-(2-f luorophenyl)-7-(2-methylani li no)-[ 1 2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2-chloro-6-fluorophenyl)-7-(2-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2,6-dif I uorophenyl)-7-(2-methylan i I i no)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2,4,6-trif I uorophenyl)-7-(2-methylan i I i no)-[ 1,2, 4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2-methylphenyl)-7-(2-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2,6-dif I uoro-4-methoxyphenyl)-7-(2-methylani I i no) [1,2,4]triazolo[1,5-a]pyrimidine; 5-chloro-6-(2-chlorophenyl)-7-(2-methylani I ino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2-bromo-5-chlorophenyl)-7-(2-methylaniI i no)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2-chlorophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(4-chlorophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(4-bromophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(4-methoxyphenyl)-7-(4-methylaniI i no)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(4-n itrophenyl)-7-(4-methylani I i no)-[ 1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2,6-dif I uorophenyl)-7-ani lino-[ 1,2,4]triazolo[1,5-a]pyri midi ne; 5-chloro-6-(2,6-dif I uorophenyl)-7-(3-methylaniii no)-[1,2,4]triazolo [1,5-alpyrimidine; 5-chloro-6-phenyl-7- (3-methylani I i no)j1,2,4]triazolo[1,5-a]pyri midi ne; 5-ch loro-6-phenyl-7- (3-ch I oroani I i no)-[ 1,2,4]tri azol o[1,5- a]pyri mid i ne; and 5-chloro-6-phenyl-7-(4-trifluoromethoxyanilino)-[1,2,4]triazolo [1,5-a]pyrimidine.

The present invention further provides a process for the preparation of a compound of formula I as defined above which comprises treating a compound of formula 11 L 2 LL L 3 Hal N N L L5 N Hal in which Ll through L 5 and Hal are as defined above, with an aniline or anilide of formula III M Ar R in which Ar and R1 are as defined above and M represents a hydrogen atom or a free or complexed metal atom, preferably selected from the group consisting of Li, Na, K, Zn and Cu, to produce a compound of formula 1.

Compounds of formula 11 are known; for example, such compounds have been described in EP 0 550 113. These compounds may be prepared by reacting 3-amino-1,2,4-triazole with a 2-phenyi-substituted malonic, acid ester of formula IV, L 2 L 51 L 3 RO_ CO Z:Z L 4 (IV) RO CO L 5 wherein R represents alkyl, under alkaline conditions, preferably using high boiling tertiary amines, for example tri-n-butylamine.

The resulting 5,7-dihydroxy-6-phenyltriazolopyrimidines are subsequently treated with a halogenating agent, preferably a brominating or chlorinating agent such as phosphorus oxybromide or phosphorus oxychloride, either neat or in the presence of a solvent. The reaction is suitably carried out at a temperature in the approximate range of from 0 OC to 150 OC, the preferred reaction temperature being from about 80 OC to about 125 OC. Suitable solvents include ethers, such as dioxane, diethyl ether and, especially, tetrahydrofuran; halogenated hydrocarbons such as dichloromethane; and aromatic hydrocarbons, for example toluene. The reaction is suitably carried out at a temperature in the approximate range of from 0 OC to 70 OC, the preferred reaction temperature being from about 10 OC to about 35 OC. It is preferred that the reaction is carried out in the presence of a base. Suitable bases include tertiary amines, such as triethylamine, and inorganic bases, such as potassium carbonate or sodium carbonate. Alternatively, an excess of the compound of formula III may serve as a base.

Anilines of formula III, wherein M represents a hydrogen atom, are well-known in the literature and commercially available; furthermore, such anilines may be prepared by methods known for analogous compounds.

The anilides of formula III, wherein M represents a metal atom, may be obtained from the corresponding amines by reaction with an alkyl lithium compound, optionally followed by a transmetallation reaction.

Due to excellent activity, the compounds of formula I may be used in cultivation of all plants where infection by phytopathogenic fungi is not desired, e.g. cereals, solanaceous crops, vegetables, legumes, apples, vine.

The invention further provides a fungicidal composition which comprises an active ingredient, which is at least one compound of formula 1 as defined above, and one or more carriers. A method of making such a composition is also provided which comprises bringing a compound of formula I into association with the carrier(s). Such a composition may contain a single active ingredient or a mixture of several active ingredients of the present invention. It is also envisaged that different isomers or mixtures of isomers may have different levels or spectra of activity and thus compositions of this invention may comprise individual isomers or mixtures of isomers of formula I compounds. A composition according to the invention preferably contains approximately from 0.5% to 95% by weight (w/w) of active ingredient(s).

A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated (which may for example be a plant, seed, soil, or water in which a plant grows), or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including material which is normally a gas but which has been compressed to form a liquid.

The compositions may be manufactured into, e.g., emulsion or emulsifiable concentrates, solutions, oil in water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, micro-capsules, gels, aerosols, tablets and other formulation types by wel I-establ i shed procedures. These procedures may include intensive mixing and/or milling of the active ingredients with other substances, such as fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally, solid and/or liquid auxiliaries and/or adjuvants. The type of composition and form of application (such as spraying, atomizing, dispersing or pouring) readily may be chosen according to the desired objectives and the given circumstances.

Solvents may be selected from aromatic hydrocarbons (e.g., Solvesso 0 200), substituted naphthalenes, phthalic acid esters, (e.g., dibutyl or dioctyl phthalate), aliphatic hydrocarbons (e.g., cyclohexane or paraffins), alcohols and glycols and their ethers and esters (e.g., ethanol, ethylene glycol mono- and dimethyl ether), ketones (e.g., cyclohexanone), strongly polar solvents (such as N-methyl-2-pyrrol i done, or ybutyrolactone), higher alkyl pyrrolidones (e.g., n-octylpyrrolidone or cyclohexylpyrrolidone), epoxidized plant oil esters (e.g., methylated coconut or soybean oil ester) and water. Mixtures of different solvents are often suitable.

Solid carriers, which may be used for dusts, wettable powders, water dispersible granules, or granules, may be mineral fillers, such as calcite, talc, kaolin, montmorillonite or attapulgite. The physical properties of a composition may be improved by addition of highly dispersed silica gel or polymers. Carriers for granules may be porous material, e.g. pumice, kaolin, sepiolite, bentonite; non-sorptive carriers may be calcite or sand. Additionally, a multitude of pre-granulated inorganic or organic materials may be used, such as dolomite or crushed plant residues.

Pesticidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surfactant facilitates this process of dilution. Thus, preferably at least one carrier in a composition according to the invention is a surfactant. For example, the composition may contain two or more carriers, at least one of which is a surfactant.

Surfactants may be nonionic, anionic, cationic or zwitterionic substances, and have good dispersing, emulsifying and wetting properties, depending on the nature of the formula I compound to be formulated. Surfactants may also comprise mixtures of individual surfactants.

Wettable powders of this invention may contain about 5 to 90% w/w of active ingredient, about 3 to 10% w/w of dispersing and wetting agents and, where necessary, about 0 to 10% w/w of stabi I izer(s) and/or other additives, such as penetrants or stickers. Dusts may be formulated as a dust concentrate having a similar composition to that of a wettable powder, but without a dispersant, and may be diluted in the field with additional solid carrier to make a composition containing approximately 0.5 to 10% w/w of active ingredient. Water dispersible granules and granules may have an approximate size between 0.15 mm and 2.0 mm, and may be manufactured by techniques known in the art. Generally, these granules will contain about 0.5 to 90% w/w active ingredient and about 0 to 20% w/w of additives, such as stabilizer, surfactants, slow release modifiers and binding agents. Emulsifiable concentrates of this invention may contain, in addition to a solvent or a mixture of solvents, about 1 to 80% w/v active ingredient, about 2 to 20% w/v emulsifiers, and about 0 to 20% w/v of other additives, such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates of the invention may be milled to obtain a stable, non-sedimenting, flowable product containing about 5 to 75% w/v active ingredient, about 0.5 to 15% w/v of dispersing agents, about 0. 1 to 10% w/v of suspending agents such as protective colloids and thixotropic agents, about 0 to 10% w/v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be dissolved in the formulation to assist in preventing sedimentation and crystalization or as antifreeze agents.

Aqueous dispersions and emulsions, for example compositions obtained by diluting the formulated product according to the invention with water, also lie within the scope of the invention.

The invention also encompasses compositions that enhance the duration of the protective activity of the compounds of this invention by including a carrier which will provide slow release of the pesticidal compounds into the environment of a plant which is to be protected.

The biological activity of the active ingredient also may be increased by including an adjuvant in the spray dilution. An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient, but is not itself significantly biologically active. The adjuvant can either be included in the formulation as a coformulant or carrier, or can be added to the spray tank together with the formulation containing the active ingredient. Adjuvants are known in the art.

As a commodity, the compositions preferably may be in a concentrated form, whereas the end user generally employs diluted compositions. The compositions of this invention may be diluted to a concentration down to about 0.001% of active ingredient. The doses preferably are in the approximate range of from 0.01 to 10 kg a.i./ha. Examples of formulations according to the invention include: Emulsion Concentrate (EC) Active Ingredient Compound of Example 5, below 30 % (w/v) Emulsifier(s) Atloxe 4856 B / Atloxe 4858 B ') 5 % (w/v) (mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics / mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics) Solvent Shellsolo A 2) to 1000 ml (mixture of C9 - Clo aromatic hydrocarbons) 15! uspension Concentrate (SC) Active Ingredient Compound of Example 5, below 50 % (w/v) Dispersing agent Soprophor@ IFIL 3) 3 % (w/v) (polyoxyethylene polyaryl phenyl ether phosphate amine salt) Antifoaming agent Rhodorsil@) 422 3) 0.2 % (w/v) (nonionic aqueous emulsion of polydimethylsiloxanes) Structure agent Kelzan@) S4) 0.2 % (w/v) (Xanthan gum) Antifreezing agent Propylene glycol 5 % (w/v) Biocidal agent Proxel@ 5) 0. 1 % (W/V) (aqueous dipropylene glycol solution containing 20% 1,2-benzisothiazolin-3 one) Water to 1000 ml Wettable Powder MP) Active Ingredient Compound of Example 5 60 % (w/w) Wetting agent Atlox@ 4995 1) 2 % (w/w) (polyoxyethylene alkyl ether) Dispersing agent Witcosperse@ D-606) 3 % (w/w) (mixture of sodium salts of condensed naphthalene sulfonic acid and alkylarylpolyoxy acetates Carrier/ Filler Kaolin 35 % (w/w) Water Dispersible Granules (WG) Active Ingredient Compound of Example 5 50 % (w/w) Dispersing / Witcosperse@ D-450 6) 8 % (w/w) Binding agent (mixture of sodium salts of condensed naphthalene sulfonic acid and alkyl sulfonates) Wetting agent Morwet@ EFW 6) 2 % (w/w) (formaldehyde condensation product) Antifoaming agent Rhodorsil@ EP 6703 3) 1 % (w/w) (encapsulated silicone) Disintegrant Agrimer@ ATF 7) 2 % (w/w) (cross-linked homopolymer of N-vinyl-2 pyrrolidone) Carrier / Filler Kaolin 35 % (w/w) 1) commercially available from ICI Surfactants 2) commercially available from Deutsche Shell AG 3) commercially available from Rh6ne-Poulenc 4) commercially available from Kelco Co.

5) commercially available from Zeneca 6) commercially available from Witco 7) commercially available from International Speciality Products The compositions of this invention can be applied to the plants or their environment either simultaneously with, or in succession with other active substances. These other active substances can be either fertilizers, agents which donate trace elements, or other preparations which influence plant growth. However, they can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, algicides, molluscicides, rodenticides, virucides, compounds inducing resistance into plants, biological control agents (such as viruses, bacteria, nematodes, fungi and other microorganisms), repellents of birds and animals, and plant growth regulators, or mixtures of several of these substances, if appropriate. These formulations also may comprise other substances conventionally used in the art of formulation, e.g., carriers, surfactants or other additives which promote application thereof.

The invention further encompasses combinations of formula I compounds with other pesticides which can have a synergistic effect on the pesticidal activity of the compound of formula 1.

Other fungicidal compounds which may be added to the formulations may be, for example, also capable of combating diseases of cereals (e.g. wheat), such as those caused by Erysipha, Puccinia, Septoria, Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on vines, early and late blight on solanaceous crops, and powdery mildew and scab on apples, etc.

Such mixtures of fungicides may have a broader spectrum of activity than the compound of formula I alone.

Examples of the fungicidal compounds suitable for use in formulations of this invnetion are anilazine, azoxystrobin, benalaxyl, benomyl, binapacryl, bitertanol, blasticidin S, Bordeaux mixture, bromuconazole, bupirimate, captafol, captan, carbendazim, carboxin, carpropamid, CGA 279202 (see AGROW No. 279, p. 17, 1998) chlorbenzthiazon, chlorothalonil, chlozolinate, copper-containing compounds such as copper oxychloride, and copper sulfate, cycloheximide, cymoxanil, cypofuram, cyproconazole, cyprodinil, dichlofluanid, dichlone, dichloran, diclobutrazol, diclocymet, diclomezine, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, diniconazole, dinocap, ditalimfos, dithianon, dodemorph, clodine, edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadone, fenapanil, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin acetate, fentin hydroxide, ferimzone, fluazinam, fludioxonil, flumetover, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, imazalil, iminoctadine, ipconazole, iprodione, isoprothiolane, iprovalicarb, kasugamycin, kitazin P, kresoxim-methyl, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methfuroxam, MON 65500 (see AGROW No. 305 of May 29,1998), myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothalisopropyl, nuarimol, ofurace, organo mercury compounds, oxadixyl, oxycarboxin, penconazole, pencycuron, phenazineoxide, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidione, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinomethionate, quinoxyfen, quintozene, spiroxamine, SSF-126, SSF-129, streptomycin, sulfur, tebuconazole, tecloftalame, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tolclofosmethyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin, XRD- 563, zarilamid, zineb, and ziram.

Examples of biological control agents suitable in the formulations of this invention include: Bacillus thuringiensis, Verticillium lecanfi, Autographica califomica NPV, Beauvaria bassiana, Ampelomyces quisqualis, Bacilis subtifis, Pseudomonas chlororaphis, Pseudomonas 5 fluorescens, Steptomyces griseoviridis and Trichoderma harzianum.

The formulations according to the invention may include a chemical agent that induces the systemic acquired resistance in plants, such as nicotinic acid or derivatives thereof, 2,2-dichloro-3,3dimethylcyclopropy1carboxylic acid, or BION.

The compounds of formula I can be mixed with soil, peat or other rooting media for the protection of the plants against seed-borne, soilborne or foliar fungal diseases.

The invention still further comprises the fungicidal use of a compound of formula I or a composition thereof; and a method for combating fungus at a locus, which comprises treating the locus (for example, plants subject to or subjected to fungal attack, seeds of such plants, or the medium in which such plants are growing or are to be grown) with such a compound or composition.

The present invention is of wide applicability in the protection of crop and ornamental plants against fungal attack. Typical crops which may be protected include vines, grain crops such as wheat and barley, rice, sugar beet, top fruit, peanuts, potatoes, vegetables and tomatoes. The durationof the protection is normally dependent on the individual compound selected, and also a variety of external factors, such as climate, whose impact may be mitigated by the use of a suitable formulation.

The following examples further illustrate the present invention. It should be understood, however, that the invention is not limited solely to the particular examples given below.

Example 1

5-Chloro-6-(2,6-d if I u orophenyl)-7-an i lino- 1,2,4-tri azolo[ 1. 5a]pyri mid i ne A mixture of aniline (4.2 mmoles) and dichloromethane (10 ml) is added to a mixture of 5,7dichloro-6-(2,6-difluorophenyl)-1,2,4-triazolo [1. 5a]pyrimidine (1.4 mmoles) and dichloromethane (30 ml) under stirring. The reaction mixture is stirred for 16 hours at room temperature and subsequently washed twice with 1 N hydrochloric acid and once with water. The organic layer is separated from the inorganic layer and dried with anhydrous sodium sulfate; the solvent is evaporated under reduced pressure. The resulting light brown oil is purified by chromatography to yield the desired product, which is a solid having a melting point of 145- 151 OC.

Examples 2-7

The compounds identified in Table I (by structure and melting point) are synthesized analogously to the procedure of Example 1.

Table I

L 8 L 7 L 6 L 2 L L 3 N-H N-N 5 L <1, N N Cl Example Ll L 2 L 3 L 4 L 5 L 6 L 7 L 8 melting point (' C) 2 IF H H H F CH3 H H 200 3 IF H H H F H CH3 H 183 4 F H H H F H H CH3 188 F H H H H H H CH3 6 H H H H H H CH3 H 185 7 H H H H H H Cl H 195-198 8 H H H H H H H OCF3 166-167 Biological Investigations A Evaluation of In Vivo Fungicidal Activity of Test Compounds Test compounds are dissolved in acetone and diluted with deionized water (95 parts water to 5 parts acetone) containing 0.05% TWEEN 200, a polyoxyethylene sorbitan monolaurate surfactant manufactured by Atlas Chemical Industries, to produce a solution having a concentration of 200 ppm of the test compound.

Plants are sprayed with the test solutions, dried, and inoculated with fungi later the same day. When disease symptom development is optimal, the plants are rated for disease control according to the rating scale shown below. Each test contains inoculated treated plants, inoculated untreated plants and inoculated plants treated with reference fungicides. The data obtained are shown in Table 11.

RATING SCALE Rating Range % Control 0 1 1-14 2 15-29 3 30-44 4 45-59 60-74 6 75-89 7 90-95 8 96-99 9 100 t no evaluation possible TARGETS Symbol Disease Pathocien AS Apple Scab Venturia inaequalis RB Rice Blast Pyricularia grisea f. sp. oryzae SBC Sugar Beet Cercospora Cercospora beticola Table 11

B Evaluation of In Vitro Fungicidal Activity against Rhizoctonia 5 solani Test compounds are dissolved in acetone to produce a formulation having a concentration of 25 ppm test compound, which is added to individual cell walls (24-cell-well plates, Corning), which were previously filled with a suspension of ground fungal mycelium in a chemically defined growth medium. After 3-7 days of incubation, inhibition of mycelial growth is recorded using the following scale. The data obtained are shown in Table 111.

RATING SCALE Batinq Deciree of Inhibition 0 None 3 slight moderate 7 severe 9 complete TARGET Symbol Disease Pathogen RHlZSO Rice sheath blight Rhizoctonia solani Example AS RB SBC 1 0 0 3 2 0 4 6 3 0 2 0 4 8 6 7 7 0 7 Table III

Example RHIZSO 1 1 7 2 7 3 0 4 0 7 Many embodiments not illustrated here will occur to those skilled in the art. This invention is not limited to the embodiments shown or described, but encompasses the entire scope of the subject matter of the appended claims.

Claims (10)

What is claimed is:

1 A compound of the formula I L 2 L 1 L 3 Ll Ar, N-R 1 1 N - N L 5 L N N Hal in which Ar represents an optionally substituted phenyl group, R1 represents a hydrogen atom or an optionally substituted alkyl, alkenyl, alkynyl, alkadienyl or phenyl group, or R1 may be connected to the orthoposition of the Ar group to form an optionally substituted azabicyclic ring system, Hal represents a halogen atom, Ll through L' each independently represent an hydrogen or halogen atom or an alkyl, alkoxy, haloalkyl, haloalkoxy or nitro group.

2. A compound according to claim 1 in which at least one of Ll and L5 represents a halogen atom.

3. A compound according to claim 1 wherein Ar represents a phenyl group, which is substituted by at least one substituent selected from the group consisting of halogen atoms, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, and alkoxycarbonyl groups.

4. A compound according to claim 1 wherein R1 represents a hydrogen or a C1.1o alkyl group.

5. A compound according to claim 4 wherein R1 represents a hydrogen atom.

6. A compound according to claim 1 selected from the group consisting of: 5-chloro-6-(2-chloro-6-fluorophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2,6-difluorophenyl)-7-(4-methylanilino)-[1, 2,4]triazolo [1,5-a]pyrimidine; 5-chloro-7-(4-methylanilino)-6-(2,4,6trifluorophenyl)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2chlorophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5chloro-6-(2-fluorophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5a]pyrimidine; 5-chloro-6-(2-chloro-6-fluorophenyl)-7-(2-methylanifino)-[l, 2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2,6-difluorophenyl)-7-(2methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2,4,6trifluorophenyl)-7-(2-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5chloro-6-(2-methylphenyl)-7-(2-methylanilino)-[1,2,4]triazolo [1,5a]pyrimidine; 5-chloro-6-(2-fluorophenyl)-7-(2-methylanilino)-[1,2, 4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2-chlorophenyl)-7-(2methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2-bromo-5chlorophenyl)-7-(2-methylanilino)-[1,2,4]triazolo [1,5-alpyrimidine; 5chloro-6-(2-chlorophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5a]pyrimidine; 5-chloro-6-(4-chlorophenyl)-7-(4-methylanilino)-[1,2, 4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(4-bromophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(4-methoxyphenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(4-nitrophenyl)-7-(4-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-(2,6-dif I uorophenyl)-7-ani I i no-[1,2,4]triazolo[ 1,5- a]pyrimidi ne; 5-chloro-6-(2,6-difluorophenyl)-7-(3-methylanilino)-[1,2,4]triazolo [1,5-a]pyrimidine; 5-chloro-6-phenyl-7-(3-methylanilino)-[1,2,4]triazolo[1,5-a]pyrimidine; 5-chloro-6-phenyl-7-(3-chloroanilino)-[1,2,4]triazolo[1,5-a]pyrimidine; and 5-chloro-6-phenyl-7-(4-trifluoromethoxyanilino)-[1,2,4]triazolo [1,5-a]pyrimidine.

7. A process for the preparation of a compound of formula I as defined in claim 1 which comprises treating a compound of formula 11 L 2 LL L 3 Hal N L5 J" N N Hal whereinin Ll through L 5 and Hal are as defined in claim 1, with an aniline of formula III M I Ar R wherein Ar and R1 are as defined in claim 1 and M represents a hydrogen atom or a free or complexed metal atom, to produce a compound of formula 1.

8. A fungicidal composition which comprises a carrier and at least one compound of formula I as defined in claim 1.

9. A method of combating fungus at a locus which comprises treating the locus with a fungicidal composition as defined in claim 8.

10. A method of combating fungus at a locus which comprises treating the locus with a fungicidally effective amount of a compound of formula I as defined in claim 1.