FR2784381A1 - Novel trichlorophenyltriazolopyrimidines, for use in fungicidal compositions - Google Patents

Abstract

The trichlorophenyltriazolopyrimidine derivatives (I) are new. The trichlorophenyltriazolopyrimidine derivatives of formula (I) are new: R<1> = 1-6C alkyl, 1-6C haloalkyl, 1-6C alkenyl, 3-8C cycloalkyl or norborn-2-yl R<2> = H, 1-6C alkyl, or R<1>+R<2>+interjacent N form 5-6C heterocyclic ring optionally substituted with 1-2 1-6C alkyl; and Hal = halogen. Independent claims are also provided for: (1) a process for the preparation of (I) comprising treating the trichlorophenyltriazolopyrimidine (II) with an amine HNR<1>R<2> (III) in which R<1>, R<2> and Hal are as defined above: (2) a compound of formula (II); (3) a fungicidal composition comprising a carrier and at least 1 compound (I); and (4) a method of combatting fungus at a locus by treating the locus with a compound (I).

Description

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The present invention relates to certain compounds having a triazolopyrimidine structure, a process for their preparation, compositions containing these compounds, a process for controlling a fungus at a site by treating the site with these compounds, and their use as fungicides.

dans laquelle R représente un atome d'halogène ou un groupe alkyle, alcoxy, cyano, cycloalkyle, aryle, aryloxy, arylthio, aralkyle, arylthio, arylalkyle, arylalkyloxy ou arylalkylthio, chacun étant éventuellement substitué par un atome d'halogène ou un groupe alcoxy ; oubien (R1)n représente un noyau de benzène, indane ou tétrahydronaphtalène condensé avec le noyau phénylique, les fragments aromatiques des groupes ci-dessus étant facultativement substitués par un atome d'halogène ou un groupe alkyle, alcoxy ou cyano ; est 1 ou 2 ; de R 2 et R 3 est un atome d'hydrogène ou un groupe alkyle ou aryle ; A représente un atome d'azote ou un groupe CR ; et R4 est défini comme R , mais peut aussi être un atome d'halogène, un groupe cyano ou un groupe alcoxycarbonyle, ou peut former avec R une chaîne alkylénique contenant jusqu'à deux doubles liaisons. Il est déclaré que ces composés sont actifs contre divers champignons phytopathogènes, notamment ceux de la classe des phycomycètes. EP-A-0 071 792 claims compounds of general formula

wherein R represents a halogen atom or an alkyl, alkoxy, cyano, cycloalkyl, aryl, aryloxy, arylthio, aralkyl, arylthio, arylalkyl, arylalkyloxy or arylalkylthio group, each being optionally substituted by a halogen atom or an alkoxy group ; or (R1) n represents a benzene, indane or tetrahydronaphthalene ring condensed with the phenyl ring, the aromatic moieties of the above groups being optionally substituted with a halogen atom or an alkyl, alkoxy or cyano group; is 1 or 2; of R 2 and R 3 is a hydrogen atom or an alkyl or aryl group; A represents a nitrogen atom or a CR group; and R4 is defined as R, but can also be a halogen atom, a cyano group or an alkoxycarbonyl group, or can form together with R an alkylene chain containing up to two double bonds. These compounds are said to be active against various phytopathogenic fungi, especially those of the class of phycomycetes.

However, the fungicidal activity of these compounds is only demonstrated against Plasmopara viticola, a member of the oomycete class.

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dans laquelle R représente un groupe alkyle, alcényle, alcadiényle, cycloalkyle, bicycloalkyle ou hétérocyclyle facultativement substitué ; R représente un atome d'hydrogène ou un groupe alkyle ; ou bien R et R2 forment, avec l'atome d'azote intercalaire, un hétérocycle facultativement substitué ; R représente un groupe aryle facultativement substitue ; et R représente un atome d'hydrogène ou d'halogène ou un groupe -NR R où R représente un atome d'hydrogène ou un groupe amino, alkyle, cycloalkyle ou bicycloalkyle et R représente un atome d'hydrogène ou un groupe alkyle. Ainsi, les composés dans lesquels Rest un groupe trichlorophényle sont inclus d'une façon générale par cette demande de brevet. Il est déclaré que ces composés sont actifs contre des champignons qui sont des membres de la classe des ascomycètes, tels que Venturia inaequalis, et de la classe des hyphomycètes, tels que Alternaria solani et Botrytis cinerea. Cependant, il n'est fait état d'aucun composé particulier dans lequel R est un groupe phényle trisubstitué aux positions 2,4, 6 par des atomes de fluor et/ou de chlore. US Patent No. 5,593,996 covers compounds of general formula 1

wherein R represents an optionally substituted alkyl, alkenyl, alkadienyl, cycloalkyl, bicycloalkyl or heterocyclyl group; R represents a hydrogen atom or an alkyl group; or R and R 2 together with the intercalating nitrogen atom form an optionally substituted heterocycle; R represents an optionally substituted aryl group; and R represents a hydrogen or halogen atom or a group -NR R where R represents a hydrogen atom or an amino, alkyl, cycloalkyl or bicycloalkyl group and R represents a hydrogen atom or an alkyl group. Thus, compounds in which Rest a trichlorophenyl group are generally included by this patent application. These compounds are said to be active against fungi which are members of the Ascomycete class, such as Venturia inaequalis, and the Hyphomycete class, such as Alternaria solani and Botrytis cinerea. However, no particular compound is reported in which R is a phenyl group trisubstituted at positions 2, 4, 6 by fluorine and / or chlorine atoms.

The present invention provides a compound of formula I

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in which
1 2
Ret R each independently represents a hydrogen atom or an optionally substituted alkyl, alkenyl, alkynyl, alkadienyl, haloalkyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl group, or
R1 and R2 together with the intercalating nitrogen atom form an optionally substituted heterocycle;
3 4 5
R, Ret R each independently represent a fluorine atom or a chlorine atom, provided that at least one of R3, Ret R is a chlorine atom; and
X represents a halogen atom.

The new compounds exert excellent fungicidal activity in various crops, especially against Piricularia oryzae (Magnaporthe grisea), the causative agent of rice blight disease.

An aim of the present invention is to provide novel selective fungicidal compounds.

Another object of the invention is to provide methods of controlling an undesirable fungus, in particular Piricularia oryzae which is the agent responsible for the browning of rice, by bringing plants into contact with a fungicidal amount of the new ones. compounds.

Another aim of the invention is to provide fungicidal compositions containing the new compounds as active ingredients.

These objects and characteristics of the invention, as well as others, will become more apparent from the detailed description which follows.

It has been found surprisingly that the compounds of formula I

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in which R to R5 and X are as defined above for formula I, exhibit excellent fungicidal activity against a wide range of fungi, in particular against Piricularia oryzae which is the agent responsible for rice blight.

As used herein, the expression "halogen atom" includes a bromine, iodine, chlorine or fluorine atom, and in particular a bromine, chlorine or fluorine atom, in particular a chlorine atom.

Optionally substituted moieties may be unsubstituted or have the maximum possible number of substituents from 1. Usually 0 to 2 substituents are present. The term "optionally substituted", as used herein with reference to a group, means that the group is substituted by one or more halogen atoms or nitro, cyano, hydroxyl, alkyl (preferably alkyl (- Ce), cycloalkyl (preferably C3-C6 cycloalkyl), cycloalkenyl (preferably C3-C6 cycloalkenyl), haloalkyl (preferably C1-C6 haloalkyl), halo-cycloalkyl (preferably C3-C6 halocycloalkyl), alkoxy (from preferably C 1 -C 6 alkoxy), haloalkoxy (preferably halo C 1 -C 6 alkoxy), trialkylsilyl (preferably tri (C 1 -C 4 alkyl) silyl), phenyl, halo or dihalo-phenyl or pyridyl.

The terms "alkyl", "alkenyl", "alkynyl", "alkadienyl", "haloalkyl", as used herein in connection with a group or moiety, denote straight or branched chain radicals or moieties. Preferably, these radicals or fragments have up to 10, in particular up to 6, carbon atoms. An alkyl moiety suitably has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. A preferred alkyl moiety is an ethyl group, or especially a methyl group. An alkenyl moiety advantageously has 2 to 6 carbon atoms. A preferred alkenyl moiety is an allyl group or in particular a group

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2-methylallyl. A haloalkyl moiety advantageously carries 1 to 6 fluorine atoms. Preferred haloalkyl moieties include 2,2,2-trifluoroethyl and 1,1,1-trifluoroprop-2-yl.

The term "aryl" as used herein in connection with a group or moiety means an aryl group having 6, 10 or 14 carbon atoms, preferably 6 or 10 carbon atoms, especially an optionally substituted phenyl group. with one or more halogen atoms and / or nitro, cyano, alkyl, preferably (-Ce) alkyl, and / or alkoxy, preferably C1-C6 alkoxy.

The term "heteroaryl", as used herein in connection with a group or moiety, denotes a heteroaryl group having 5 or 6 atoms forming a ring and selected from carbon, nitrogen, oxygen and sulfur atoms, one of which at least is a nitrogen, oxygen or sulfur atom, in particular a pyridyl, pyrimidyl, pyrazolyl or thienyl group.

The term "cycloalkyl" as used herein in connection with a group or moiety means a cycloalkyl group having 3 to 8 carbon atoms, preferably 5 to 7 carbon atoms, especially a cyclopentyl group optionally substituted with a or more halogen atoms and / or nitro, cyano, alkyl, preferably C1-C6 alkyl, and / or alkoxy, preferably C1-C6 alkoxy.

The term "bicycloalkyl" as used herein in connection with a group or moiety means a bicycloalkyl group having 5 to 10 carbon atoms, preferably 6 to 9 carbon atoms, especially a bicycloheptyl group optionally substituted with one or several halogen atoms and / or nitro, cyano, alkyl, preferably C1-C6 alkyl, and / or alkoxy, preferably C1-C6 alkoxy.

The term "heterocyclyl" as used herein in connection with a group or moiety refers to a saturated heterocycle residue having 5 or 6 ring atoms selected from carbon, nitrogen, oxygen and sulfur atoms, one of which

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at least is a nitrogen, oxygen or sulfur atom, optionally substituted by one or more halogen atoms and / or nitro, cyano, alkyl, preferably C1-C6 alkyl, and / or alkoxy, preferably C-C8 alkoxy. Particularly preferred are pyrrolidinyl, pyrrazolidinyl, piperidinyl, piperazinyl and morpholin-4-yl groups.

The invention relates in particular to the compounds of formula I in which any alkyl or haloalkyl portion of the groups R or R, which may be straight or branched chain, contains at most 10 carbon atoms, preferably 1 to 9 carbon atoms. carbon and better still 2 to 6 carbon atoms, any alkenyl or alkynyl portion of the Rou R2 substituents contains at most 10 carbon atoms, preferably 2 to 9 carbon atoms and better still 3 to 6 carbon atoms, any cycloalkyl portion of the R or R substituents contains 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms and more preferably 3 to 6 carbon atoms, any bicycloalkyl portion of the R or R substituents contains 5 to 9 carbon atoms, preferably 7 to 9 carbon atoms, and any aryl portion of the substituents
1 2 R or R contains 6, 10 or 14 carbon atoms, preferably 6 or 10 carbon atoms.

In a preferred embodiment, the invention includes the compounds of formula I in which R represents a C1-C6 alkyl group, straight or branched chain (especially a branched C3-C10 alkyl group), a C3-C10 cycloalkyl group. C8, a C5-C9 bicycloalkyl group, a (C3-C8 cycloalkyl) C1-C6 alkyl group, a (C1-C10 alkoxy) C1-C6 alkyl group, a C1-C6 haloalkyl group, or a phenyl group optionally substituted with 1 to 3 halogen atoms or C1-C12 alkyl, or C1-C10 alkoxy groups.

Also preferred compounds of formula 1 are those in which R represents a hydrogen atom, a C1-C12 alkyl group, or a C1-C10 haloalkyl group, in particular a hydrogen atom.

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When R represents a C1-C10 haloalkyl group, preferably a polyfluoroalkyl group, in particular a 2,2,2-trifluoroethyl group, a 2- (1,1,1-trifluoropropyl) group or a 2- ( 1,1,1-trifluorobutyl), R preferably represents a hydrogen atom.

When R1 is an optionally substituted C3-C8 cycloalkyl group, preferably a cyclo group
2 pentyl or cyclohexyl, R preferably represents a hydrogen atom or a C1-C6 alkyl group.

In another preferred embodiment of the invention, R and R form, with the intercalated nitrogen atom, an optionally substituted heterocycle, preferably an optionally substituted C3-C7 heterocycle, in particular a pyrrolidine, piperidine ring, tetrahydropyridine, particularly 1,2,3,6-tetrahydropyridine or azepane, which is optionally substituted with one or more C1-C10 alkyl groups, most preferably 4-methylpiperidine.

The invention relates in particular to the compounds
3 4 5 of formula I in which: R, R and R are chlorine atoms; R 3 is a chlorine atom, R 4 is a fluorine atom, and R is a fluorine or chlorine atom, preferably R5 is a chlorine atom; or R and R are fluorine atoms and Rest is chlorine atom.

représente de préférence un groupe choisi parmi

Therefore, in formula I, the phenyl group

preferably represents a group chosen from

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The (R) and (S) isomers of compounds of formula I having a chiral center and their racemates and salts, N-oxides and acid adducts are included within the scope of the present invention.

The compounds according to formula I can be oils, gums or waxy or crystalline solids. They exhibit interesting fungicidal properties such as increased systemic action and increased fungal toxicity against rice diseases and powdery mildew compared to known fungicides. For example, they can be used in agriculture or in related fields to combat phytopathogenic fungi such as Alternaria solani, Botrytis cinerea, Cercospora beticola, Cladosporium herbarum, Corticium rolfsii, Erysiphe graminis, Helminthosporium tritici repentis, Leptosphailriella nivectriella, Micronia nodorella fructigena, Mycosphaerella ligulicola, Mycosphaerella pinodes, Piricularia oryzae, Rhizoctonia solani and Sclerotinia sclerotiorum, Uncinula necator, in particular to combat Piricularia oryzae. The compounds of formula I according to the invention possess a great fungicidal activity in a wide range of concentrations and they can be used in agriculture without any difficulty.

In addition, the compounds according to the invention exert a better action 'against fungi, in particular rice blight, than conventional fungicides.

In terms of effect against phytopathogenic fungi, good results are obtained with a compound as defined by formula I in which:
X represents a chlorine atom,
R represents a hydrogen atom,
R and R represent chlorine atoms, and
R represents a chlorine or fluorine atom.

Considering the effect against phytopathogenic fungi, particularly good results are obtained using, for example, the following compounds of formula I:

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#bicyclo[2.2.1]hept-2-yl-[5-chloro-6-(2,6-dichloro-4-fluoro- phényl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-yl]amine ; # [5-chloro-6-(2-chloro-4,6-difluorophényl)-[1,2,4]triazolo- [1,5-a]pyrimidine-7-yl]cyclopentylamine ; # [5-chloro-6-(2-chloro-4,6-difluorophényl)-7-(4-méthyl- pipéridine1-yl)-[1,2,4]triazolo[1,5-a]pyrimidine ; # [5-chloro-6-(2-chloro-4,6-difluorophényl)-[1,2,4]triazolo- [1,5-a]pyrimidine-7-yl]-(2,2,2-trifluoréthyl)amine ; # [5-chloro-6-(2-chloro-4,6-difluorophényl)-[1,2,4]triazolo- [1,5-a]pyrimidine-7-yl]-(1,1,1-trifluoroprop-2-yl)amine ; # [5-chloro-6-(2-chloro-4,6-difluorophényl)-[1,2,4]triazolo- [1,5-[alpha]]pyrimidine-7-yl]diéthylamine ; # [5-chloro-6-(2-chloro-4,6-difluorophényl)-[1,2,4]triazolo- [1,5-a]pyrimidine-7-yl]isopropylamine ; # sec-butyl-[5-chloro-6-(2-chloro-4,6-difluorophényl)- [1,2,4]triazolo[1,5-a]pyrimidine-7-yl]amine ;

#bicyclo[2.2.1]hept-2-yl-[5-chloro-6-(2-chloro-4,6-difluorophényl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-yl]amine ; # but-2-yl-[5-chloro-6-(2,4,6-trichlorophényl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-yl]amine ; # isopropyl-[5-chloro-6-(2,4,6-trichlorophényl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-yl]amine ; # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] cyclopentylamine; # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) -7- (4-methyl-piperidin-1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine ; # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] - (2,2,2- trifluoroethyl) amine; # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] - (1,1,1- trifluoroprop-2-yl) amine; # [5-Chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] diethylamine; # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] isopropylamine; # sec-butyl- [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine;

#bicyclo [2.2.1] hept-2-yl- [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine -7-yl] amine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] cyclopentylamine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) -7- (4-methyl-piperidin1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] - (2,2,2- trifluoroethyl) amine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] - (1,1,1- trifluoroprop-2-yl) amine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo- [1,5- [alpha]] pyrimidin-7-yl] diethylamine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] isopropylamine; # sec-butyl- [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine;

#bicyclo [2.2.1] hept-2-yl- [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7 -yl] amine; # but-2-yl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # isopropyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine;

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phényl)-[1,2,4]triazolo[1,5-a]pyrimïdine-7-yl]amine ; et # 1,1,1-trifluoroprop-2-yl-[5-chloro-6-(2,4,6-trichloro-

phényl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-yl]amine. # [5-chloro-6- (2,4,6-trichlorophenyl) -7- (3-methylpiperidine-
1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine; # cyclopentyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] - triazolo [1,5-a] pyrimidin-7-yl] amine; # [5-Chloro-6- (2,4,6-trichlorophenyl) -7- (4-methylpiperidin-1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine; # diethyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # norborn-2-yl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # cyclopropyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # 2,2,2-trifluoroethyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # N-ethyl-N-2-methylallyl- [5-chloro-6- (2,4,6-trichloro-

phenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; and # 1,1,1-trifluoroprop-2-yl- [5-chloro-6- (2,4,6-trichloro-

phenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine.

dans laquelle 3 4 5 R , R , R et X sont tels que définis pour la formule I ; avec une amine de formule III

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 II

wherein R, R, R and X are as defined for formula I; with an amine of formula III

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in which
R1 and R 2 are as defined for formula I.

dans laquelle R3, R4 et R5 sont tels que définis pour la formule I, R représente un groupe alkyle, de préférence un groupe alkyle en C1-C6, notamment méthyle ou éthyle, dans des conditions alcalines, de préférence en utilisant des amines tertiaires à haut point d'ébullition, par exemple la tri-n-butylamine. Compounds of formula II are novel and can be prepared by reacting 3-amino-1,2,4-triazole with a 2- (2,4,6-trihalophenyl) substituted malonic acid ester of formula IV

in which R3, R4 and R5 are as defined for formula I, R represents an alkyl group, preferably a C1-C6 alkyl group, in particular methyl or ethyl, under alkaline conditions, preferably using tertiary amines at high boiling point, for example tri-n-butylamine.

The resulting 5,7-dihydroxy-6- (2,4,6-trihalogenophenyl) triazolopyrimidine is then treated with a halogenating agent, preferably with a brominating or chlorinating agent such as phosphorus oxybromide or Phosphorus oxychloride, without solvent or in the presence of a solvent. The reaction is advantageously carried out at a temperature between 0 C and 150 C, the preferred reaction temperature being 80 C to 125 C.

The compounds of formula IV are preferably prepared by the reaction of 2,4,6-trihalobromobenzene with sodium dialkyl malonates in the presence of a copper-I salt, for example as taught by J. Setsume et al. , Chemistry Letters, pages 367-370,1981.

Therefore, the invention relates to the novel intermediates of formula II, in particular 5,7-dichloro- 6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine , 5,7-dichloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine and 5,7-dichloro-6- (2 -chloro-

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4,6-difluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, the corresponding dialkyl (2,4,6-trihalophenyl) malonates of formula IV; and the corresponding 5,7-dihydroxy-6- (2,4,6-trihalo-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidines.

The reaction between the 5,7-dihalo-6- (2,4,6-trihalogenophenyl) triazolopyrimidines of formula II and the amine of formula III is preferably carried out in the presence of a solvent. Suitable solvents include ethers such as dioxane, diethyl ether and, in particular, tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene. The reaction is suitably carried out at a temperature in the approximate range of 0 C to 70 C, the preferred reaction temperature being 10 C to 35 C. It is also preferable 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 can serve as a base.

Due to their excellent activity, the compounds of formula I can be used in the cultivation of all plants for which infection by phytopathogenic fungi is undesirable, for example cereals, cultivated nightshades, vegetables, legumes, apple trees. , Vine.

The invention further provides a fungicidal composition which comprises an active ingredient which is at least one compound of formula I as defined above and one or more carriers. There is also provided a method of making such a composition which comprises bringing into association a compound of formula I 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 contemplated that different isomers or mixtures of isomers

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may have different degrees or spectra of activity and, thus, the compositions may include individual isomers or mixtures of isomers.

A composition according to the invention preferably contains 0.5% to 95% by weight (% w / w) of active ingredient.

A carrier in a composition according to the invention is any material with which the active ingredient can be formulated in order to facilitate application to the site to be treated (which can be, for example, a plant, seed, soil or soil. water where a plant grows), or to facilitate storage, transport or handling.

A support can be a solid or a liquid, including material which is normally a gas, but which has been compressed to form a liquid.

The compositions can be made by well-established techniques, for example in the form of emulsion or emulsifiable concentrates, solutions, oil-in-water emulsions, wettable powders, soluble powders, suspension concentrates, dusting powders, granules, etc. water dispersible granules, aerosol products, microcapsules, gels, tablets and other types of formulations. These techniques may include intensive mixing and / or grinding of the active ingredients with other substances such as fillers, solvents, solid carriers, surface active compounds (surfactants) and optionally solid auxiliaries and / or builders and / or builders. or liquids. The mode of application, for example spraying, atomizing, dispersing or pouring, can be chosen, as can the compositions, depending on the desired objectives and the particular circumstances.

Solvents which are suitable in the practice of the present invention include aromatic hydrocarbons, for example Solvesso 200, substituted naphthalenes, esters of phthalic acid such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, for example

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cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, for example ethanol, mono- and dimethyl ethers of ethylene glycol, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone or γ-butyrolactone, (higher alkyl) pyrrolidones, for example n-octylpyrrolidone or cyclohexylpyrrolidone, epoxidized vegetable oil esters, for example coconut or soybean oil ester methylated, and water. Mixtures of different solvents are often suitable.

The solid carriers, which can be used in dusting powders, wettable powders, water dispersible granules or granules, can be mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. The physical properties can be improved by the addition of highly dispersed silica gel or polymers. The supports for granules can be a porous material, for example pumice stone, kaolin, sepiolite, bentonite; non-adsorbent supports can be calcite or sand.

In addition, it is possible to use a multitude of organic or mineral materials previously granulated, such as dolomite or crushed plant residues.

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

The surfactants can be nonionic, anionic, cationic or zwitterionic substances, preferably having good dispersion properties,

<Desc / Clms Page number 15>

emulsification and wetting, depending on the nature of the compound of formula I which is to be formulated. Surfactants can also include mixtures of individual surfactants.

The wettable powders of the present invention suitably contain about 5 to 90% by weight of active ingredient and, in addition to a solid inert carrier, about 3 to 10% by weight of dispersing and wetting agents and about 0 to 10%. by weight of one or more stabilizers and / or other additives such as penetrating agents or adhesives. Dusting powders can be formulated as a fine powder concentrate having a composition similar to that of a wettable powder, but without a dispersant, and can be field diluted with another solid carrier to prepare a composition containing about 0.5 to 10% by weight of active ingredient.

The water dispersible granules and the granules are suitably about 0.15mm to 2.0mm in size and can be prepared by various techniques known in the art. In general, these granules contain about 0.5 to 90% by weight of active ingredient and about 0 to 20% by weight of additives such as stabilizer, surfactants, slow release agents and binders. .

The emulsifiable concentrates of the present invention suitably contain, in addition to a solvent or a mixture of solvents, about 1 to 80% w / v (w / v) active ingredient, about 2 to 20% by weight / volume of emulsifiers and about 0 to 20% w / v of other additives such as stabilizers, penetrators and corrosion inhibitors. Suspended concentrates can be ground to form a stable, non-settling fluid product, and they preferably contain about 5 to 75% w / v active ingredient, about 0.5 to 15% w / v dispersants. , about 0.1 to 10% w / v suspending agents such as protective colloids and thixotropic agents,

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about 0 to 10% w / v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrators and adhesives, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to help prevent sedimentation and crystallization or as anti-freeze agents.

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

The duration of the protective activity exerted by the compounds of the present invention can be improved by using a carrier which provides for slow release of the pesticidal compounds into the environment of a plant to be protected.

The biological activity of the active ingredient can also be increased by introducing an adjuvant into a spray dilution of the active ingredient. An adjuvant is defined herein as a substance which can enhance the biological activity of an active ingredient, but which is not substantially biologically active on its own. The adjuvant can be included in the formulation as an associated ingredient or carrier, or can be added to the spray tank along with the formulation containing the active ingredient.

For convenience, the compositions may preferably be in a concentrated form, while the end user generally uses dilute compositions.

The compositions can be diluted to a concentration of about 0.001% active ingredient, preferably for a dose in the range of approximately 0.01 to 10 kg a.i./ha.

Examples of formulations according to the invention are as follows:

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Emulsion concentrate (EC) Ingredient Compound of Example 5 30% (w / v) active Emulsifier (s) Atlox 4856 B / Atlox 4858 B1) 5% (mixture containing a calcium alkyl- (w / v) arylsulfonate, fatty alcohol ethoxylates and light aromatic compounds / mixture containing calcium alkylarylsulphonate, fatty alcohol ethoxylates and light aromatics) Shellsol A2 solvent) up to (mixture of 1000 ml C9-C10 aromatic hydrocarbons ) Suspended Concentrate (CS) Ingredient Compound of Example 5 50% (w / v) active Agent Soprophor FL3) 3% (w / v) dispersant (polyoxyethylene polyarylphenyl ether phosphate amine salt) Rhodorsil Agent 4223) 0.2% (w / v) antifoam (nonionic aqueous emulsion of polydimethylsiloxanes) Kelzan agent S4) 0.2% (w / v) structure (xanthan gum) Agent Propylene glycol 5% (w / v ) antifreeze

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Proxel Agent # 5) 0.1% (w / v) biocidal (aqueous solution of dipropylene glycol containing
20% 1,2-benzisothiazoline-
3-one) Water up to
1000 ml Wettable powder (MW) Ingredient Compound of Example 11 60% (w / w) active Atlox agent 49951) 2% (w / w) wetting (polyoxyethylene alkyl ether) Agent Witcosperse D-606) 3% (w / w) dispersant (mixture of sodium salts of condensed naphthalene sulfonic acid and alkylaryl polyoxyacetates) Carrier / Kaolin 35% (w / w) filler Water dispersible granules (GE) Ingredient Compound of Example 11 50% (w / w) active Dispersant / Witcosperse D-4506) 8% (w / w) binder (mixture of sodium salts of condensed naphthalenesulphonic acid and alkylsulphonates)

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Morwet EFW6) 2% (w / w) wetting agent (formaldehyde condensation product) Rhodorsil 'agent EP 67033) 1% (w / w) antifoam (encapsulated silicone) Disintegrant Agrimer ATF 2% (w / w) (crosslinked homopolymer of
N-vinyl-2-pyrrolidone) Carrier / Kaolin 35% (w / w) filler 1) commercially supplied by ICI Surfactants 2) commercially supplied by Deutsche Shell AG 3) commercially supplied by Rhône-Poulenc 4) commercially available from Kelco Co.

5) commercially supplied by Zeneca commercially supplied by Witco 7) commercially supplied by International Specialty
Products
The compositions of the present invention can be applied to plants or their environment, simultaneously or successively to other active substances. These other active substances can be fertilizers, agents providing trace elements, or other preparations which influence the growth of plants. They may also be selective herbicides, insecticides, fungicides, bactericides, nematicides, algicides, molluscicides, rodenticides, virucides, compounds conferring resistance to plants, biological control agents such as viruses, bacteria, nematodes, etc. fungi and other microorganisms, bird and animal repellents and plant growth regulators, or mixtures of more than one of these preparations,

<Desc / Clms Page number 20>

if necessary with other carrier materials conventionally used in the preparatory art, surfactants or other additives which facilitate application.

Further, the other pesticide may have a synergistic effect on the pesticidal activity of the compound of formula I.

The other fungicidal compound may be, for example, a compound which is also capable of combating diseases of cereals (eg wheat), for example those caused by species of Erysipha, Puccinia, Septoria, Gibberella and Helminthosporium, diseases seed and soil borne, and downy mildew and powdery mildew on grapevine, downy mildew and brown spot disease on cultivated nightshades, and powdery mildew and apple scab, etc. These mixtures of fungicides may have a broader spectrum of activity than the compound of formula I alone. In addition, the other fungicide can exert a synergistic effect on the fungicidal activities of the compound of formula I.

Examples of other fungicidal compounds are: AC 382042, alanycarb, aldimorph, ampropylfos, andoprim, anilazine, azaconazole, azafenidine, azoxystrobin, benalaxyl, benomyl, bethoxazine, binapacryl, bitertanol, blasticin S, Bordeaux mixture, captupazole, bomucimate, bomucimate , captan, carbendazim, carboxin, carpropamide, chlorbenzthiazon, chlorothalonil, chlozolinate, copper-containing compounds such as copper oxychloride and copper sulphate, cycloheximide, cymoxanil, cypofuram, cyproconazole, cyprodinil, dichlofluanic acidlobutichloride, dichlofluanole, dichlofluanole, dichlorazane, diclocymet, diclomezine, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, diniconazole, dinocap, ditalimfos, dithianon, dodemorph, dodine, edifenphos, epoxiconazole, feniramimol, etherimorph, diniconazole, dinocap, ditalimfos, dithianon, dodemorph, dodine, edifenphos, epoxiconazole, feniramimolametazanazan, feniramimol, etazenolametazanbone, feniramimole, etazenbolametazanimorphic fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin acetate e, fentin hydroxide, ferimzone, fluazinam,

<Desc / Clms Page number 21>

fludioxonil, flumetover, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetylaluminum, fuberidazole, furalaxyl, furametpyr, guazatin, hexaconazole, imazalil, iminoctadine, ipconazione, kasovaliolamypricothazine, ipricothazione, ipricothazin, 916azioneKpricothazine, ipricothazine, ipricothazine, ipricothazine, ipricothazin, 916azioneKpramyodine, ipricothazine -methyl, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methfuroxam, myclobutanil, neoazozin, nickel dimethyldithiocarbamate, nitrothalisopropyl, nuarimol, ofurace, organic compounds of mercury, pheonencoconidazin, oxadoconencyazine, phenenconencolazin, oxadoconidazine, pphenencolonidazin, oxadoconidazin, pheonencoconidazin, pphenencoconidazin, oxadoxyazin, pheonencoleconidazin, oxadixazine, phenencoleconidazin, phenencoleconidazin, oxadix-zine, nickel-dimethyldithiocarbamate, oxadix-zine phthalide, picoxystrobin, polyoxin D, polyram, probenazole, prochloraz, procymidione, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, chinomethionate, quinoxyfen, quintoxene, MONO-65amine (7281-silthiopamine) -500-ham SSF-126, SSF-129, streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifl uzamide, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanide, triadimefone, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforin, triticonazole, ziramide, zirbe-56amide, validamycin3, A.

In addition, the combination formulations according to the invention may contain at least one compound of formula I and any one of the biological control agents of classes such as the following: viruses, bacteria, nematodes, fungi and other microorganisms which are capable of controlling insects, weeds or plant diseases or of imparting host resistance to plants.

Examples of such biological control agents are: Bacillus thuringiensis, Verticillium lecanii, Autographica californica NPV, Beauvaria bassiana, Ampelomyces quisqualis, Bacillus subtilis, Pseudomonas chlororaphis, Pseudomonas fluorescens, Streptomyces griseoviridis and Trichoderma harzianum.

<Desc / Clms Page number 22>

In addition, the formulations according to the invention may contain at least one compound of formula I and a chemical agent which confers on plants an acquired systemic resistance, such as isonicotinic acid or its derivatives, 2,2-dichloro-acid. 3,3-Dimethylcyclopropylcarboxylic or BION.

The compounds of formula I can be mixed with soil, peat or other rooting medium for the protection of plants against fungal diseases transmitted by seeds, soil or leaves.

The invention further provides the use as a fungicide of a compound of formula I or of a composition as defined above, and a method for combating a fungus at a site (which consists of treating the site, which may be for example plants subject or subjected to fungal attack, seeds of these plants or the medium in which these plants grow or are to grow) with such a compound or such a composition.

The present invention finds wide applicability in the protection of cultivated plants and ornamental plants against fungal attack. Representative crop plants that can be protected include grapevine, cereals such as wheat and barley, rice, sugar beet, fruit trees, peanuts, potatoes, vegetables and tomatoes.

The duration of protection will normally depend on the individual compound chosen as well as various external factors such as climate, the effect of which can be mitigated by the use of an appropriate formulation.

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

<Desc / Clms Page number 23>

Example 1 Preparation of 1-bromo-2,6-dichloro-4-fluorobenzene
0.6 mol of bromine is added over 2 hours to a mixture of 1,3-dichloro-5-fluorobenzene (0.6 mol) and iron powder. The brown reaction mixture is stirred for 16 hours at room temperature then washed with dichloromethane and water. The organic phase is separated, washed with sodium hydrogencarbonate solution and dried over anhydrous sodium sulfate. The solvent is evaporated off under reduced pressure. The crude product is recrystallized from ethanol to give 61 g of the product in the form of a white powder having a melting point of 83 C.

Example 2 Preparation of diethyl (2,6-dichloro-4-fluorophenyl) malonate
0.49 mol of diethyl malonate is added over 2 hours to a mixture of sodium hydride (0.51 mol) and 1,4-dioxane (140 ml) between 55 and 60 C. The mixture is stirred for 10 minutes at 55 ° C. and 0.05 mol of copper-I bromide is added. After 15 minutes, a mixture of 1-bromo-2,6-dichloro-4-fluorobenzene (0.25 mol) and 1,4-dioxane (10 ml) is added. The reaction mixture is heated at 100 C for 15 hours and cooled to 15 C. 35 ml of 12N hydrochloric acid are slowly added between 15 and 20 C.

The precipitate is separated by filtration. The filtrate is extracted with diethyl ether. The organic phase is separated, dried over anhydrous sodium sulfate and filtered. The filtrate is evaporated under reduced pressure to give 44 g of the product in the form of yellow crystals having a melting point of 170 C. Diethyl (2-chloro-4,6-difluorophenyl) malonate is obtained in an analogous manner.

Example 3 Preparation of 5,7-dihydroxy-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine
A mixture of 3-amino-1,2,4-triazole (0.15 mol), of diethyl (2,6-dichloro-4-fluorophenyl) malonate (obtained

<Desc / Clms Page number 24>

in Example 2) and tributylamine (0.15 mol) is heated under reflux at 180 C for six hours. The reaction mixture is cooled to 70 ° C. An aqueous solution of sodium hydroxide (13.6 g / 200 ml of H2O) is added and the reaction mixture is stirred for 30 minutes. The organic phase is separated and the aqueous phase is extracted with diethyl ether. The aqueous phase is acidified with concentrated hydrochloric acid. A white precipitate is collected by filtration and dried to give 40.6 g of the product having a melting point of 267 C.

Example 4 Preparation of 5,7-dichloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine
A mixture of 5,7-dihydroxy-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo [1,5- [alpha]] pyrimidine (0.14 mol, obtained in 1 Example 3) and phosphorus oxychloride (110 ml) is refluxed at 120 ° C. for eight hours.

Phosphorus oxychloride is partially removed by distillation. The residue is poured into a mixture of dichloromethane and water. The organic phase is separated, dried over anhydrous sodium sulfate and filtered.

The filtrate is concentrated in vacuo, then applied to an instant chromatography column. The column is then eluted with a mixture of diethyl ether / petroleum ether (1: 2 by volume) to give 17 g of a yellow powder having a melting point of 149 C. 5,7-dichloro- (2- chloro-4,6-difluorophenyl) -1,2,4-triazolo [1,5-a] pyrimidine having a melting point of 124 C is obtained in an analogous manner.

Example 5 Preparation of 5-chloro-6- (2,6-dichloro-4-fluorophenyl) - 7- (4-methylpiperidin-1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine
A mixture of 4-methylpiperidine (3.0 mmol), triethylamine (3.0 mmol) and dichloromethane (10 ml) is added to a mixture of 5,7-dichloro-6- (2,6-dichloro-4 -fluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine (3.0 mmol) and dichloromethane (30 ml) with stirring. The mixture

<Desc / Clms Page number 25>

The reaction mixture is stirred for 16 hours at room temperature, then washed with 1N hydrochloric acid.

The organic phase is separated, dried over anhydrous sodium sulfate and filtered. The filtrate is evaporated under reduced pressure to give 1.05 g of a yellow powder having a melting point of 169 C.

Examples 6 to 20
The compounds of the following examples (Table I. Structure and melting point) are synthesized in a manner analogous to Example 5.

<tb>
<tb>

Point <SEP> of
<tb> Example <SEP> R <SEP> R2 <SEP> R5 <SEP> merge
<tb> (C)
<tb> 6 <SEP> cyclopentyle <SEP> H <SEP> Cl <SEP> 146
<tb> 7 <SEP> 2,2,2-trifluoroethyl <SEP> H <SEP> Cl <SEP> 202
<tb> 8 <SEP> ethyl <SEP> ethyl <SEP> Cl <SEP> 142
<tb> 9 <SEP> isopropyl <SEP> H <SEP> Cl <SEP> 182
<tb> 10 <SEP> 2-butyl <SEP> H <SEP> Cl <SEP> 157
<tb> 11 <SEP> norborn-2-yle <SEP> H <SEP> Cl <SEP> 208
<tb> 12 <SEP> cyclopentyle <SEP> H <SEP> F <SEP> 126
<tb> 13 <SEP> isopropyl <SEP> H <SEP> F <SEP> 105
<tb> 14 <SEP> ethyl <SEP> ethyl <SEP> F <SEP> 135
<tb> 15 <SEP> 2,2,2-trifluoroethyl <SEP> H <SEP> F <SEP> 203
<tb> 16 <SEP> 1,1,1-trifluoroprop-2-yl <SEP> H <SEP> F <SEP> 220
<tb>

<Desc / Clms Page number 26>

<tb>
<tb> TABLE <SEP> 1 <SEP> (continued)
<tb> Point <SEP> of
<tb> Example <SEP> R1 <SEP> R2 <SEP> R5 <SEP> merge
<tb> (C)
<tb> 17 <SEP> 1,1,1-trifluoroprop-2-yl <SEP> H <SEP> Cl
<tb> 18 <SEP> - (CH2) 2-CH (CH3) - (CH2) 2- <SEP> F
<tb> 19 <SEP> 2-butyl <SEP> H <SEP> F
<tb> 20 <SEP> norborn-2-yle <SEP> H <SEP> F
<tb>
Example 21 Preparation of diethyl 2,4,6-trichlorophenylmalonate
6.21 mol of diethyl malonate is added over 3 hours to a mixture of sodium hydride (5.13 mol) and 1,4-dioxane (1400 ml) between 55 and 60 C. The mixture is stirred for 10 minutes at 55 ° C. and 0.5 mol of copper-I bromide is added. A mixture of 2,4,6-trichlorobromobenzene (2.50 mol) and 1,4-dioxane (600 ml) is added.

The reaction mixture is heated at 100 C for 14 hours and cooled to 15 C. 350 ml of 12N hydrochloric acid are slowly added between 15 and 20 C. The organic phase is separated and the aqueous phase is extracted with acetate d. ethyl (250 ml) and toluene (200 ml). The combined organic phases are concentrated in vacuo. The residue is filtered through silica gel, washed with a mixture of petroleum ether / ethyl acetate (15: 1) and the solvent is removed by distillation. The residue is distilled off under vacuum to give 540 g of the product in the form of a white solid, 144-150 C at 40 Pa.

Example 22 Preparation of 5,7-dichloro- (2,4,6-trichlorophenyl) - 1,2,4-triazolo [1,5-a] pyrimidine
A mixture of 3-amino-1,2,4-triazole (0.15 mol), diethyl 2,4,6-trichlorophenylmalonate (0.15 mol, obtained in Example 21) and tributylamine (0, 15 mol) is

<Desc / Clms Page number 27>

heated to 170 ° C. and the ethanol formed during the reaction is removed by distillation. Then, the reaction mixture is cooled to 130 ° C. and 0.45 mol of phosphorus oxychloride is added over 30 minutes. The reaction mixture is heated at reflux for 6 hours. Slowly add 1.5 liters of a mixture of water and toluene (6: 5). The organic phase is separated, washed with dilute hydrochloric acid solution and water, dried and concentrated in vacuo to give a brown viscous oil (45 g) which contains 85% of the title product.

Example 23
A mixture of N, N-diethylamine (1.4 mmol), triethylamine (1.4 mmol) and dichloromethane (10 ml) is added to a mixture of 5,7-dichloro- (2,4,6-trichlorophenyl ) - 1,2,4-triazolo [1,5-a] pyrimidine (1.4 mmol) and dichloromethane (30 ml) with stirring. The reaction mixture is stirred for 16 hours at room temperature, then washed twice with 1N hydrochloric acid and once with water. The organic phase is separated, dried over anhydrous sodium sulfate and the solvent is evaporated off under reduced pressure. Treatment of the resulting light brown oil with 50 ml of tert-butyl methyl ether gives beige crystals having a melting point of 199-201 C.

Examples 24 to 33
The compounds of the following examples (Table II; structure and melting point) are synthesized in a manner analogous to Example 23.

<Desc / Clms Page number 28>

Exem 1 2 Point of Example RR Point of

<tb>
<tb> merge <SEP> (C)
<tb> 24 <SEP> 2-butyl <SEP> H <SEP> oil
<tb> 25 <SEP> isopropyl <SEP> H <SEP> oil
<tb> 26 <SEP> -CH2-CH (CH3) - (CH2) 3- <SEP> oil
<tb> 27 <SEP> cyclopentyle <SEP> H <SEP> 160
<tb> 28 <SEP> - (CH2) 2-CH (CH3) - (CH2) 2- <SEP> 220
<tb> 29 <SEP> norborn-2-yle <SEP> H <SEP> 155
<tb> 30 <SEP> cyclopropyle <SEP> H <SEP> oil
<tb> 31 <SEP> 2,2,2-trifluoroethyl <SEP> H <SEP> oil
<tb> 32 <SEP> 2-methylallyl <SEP> ethyl
<tb> 33 <SEP> 1,1,1-trifluoroprop-2-yl <SEP> H
<tb>
Biological Studies Determination of the Minimum Inhibitory Concentration of the Compounds Examined in the Serial Dilution Test
The MIC (Minimum Inhibitory Concentration) value which indicates the lowest concentration of the active ingredient in the growth medium which causes complete inhibition of mycelial growth, is determined by serial dilution assays using microtiter plates at 24 or 48 wells per plate. The dilution of the compounds under examination in the nutrient solution and the distribution into the wells are carried out by a TECAN RSP 5000 automatic sample processor.

The following concentrations of test compound are used: 0,04,0,10, 020,0,39, 0,78,1,56, 3,13,6,25, 12,50, 25,00,50 0.00 and 100.00 µg / ml (alternatively a starting concentration of 5.00 ppm with 12 serial dilutions is used). To prepare the nutrient solution, mix from the mixture of vegetable juice V8 (333 ml) with carbonate

<Desc / Clms Page number 29>

of calcium (4.95 g), the mixture is centrifuged, the supernatant (200 ml) is diluted with water (800 ml) and autoclaved at 121 C for 30 min.

The respective inocula (Alternaria solani, ALTESO; Botrytis cinerea, BOTRCI; Cochliobulus sativus, COCHSA; Magnamorthe grisea f. Sp. Oryzae, PYRIOR; Rhizoctonia solani RHIZSO; are added to the wells in the form of spore suspensions (50 ml; 5x 10 / ml) or agar slices (6 mm) of a culture of the fungus on agar.

After 6 to 12 days of incubation at the appropriate temperatures (18-25 C), MIC values are determined by visual examination of the plates (Tables III and IV).

<tb>
<tb>

TABLE <SEP> III
<tb> Ex. <SEP> N <SEP> ALTESO <SEP> BOTRCI <SEP> COCHSA <SEP> PYRIOR <SEP> RHIZSO
<tb> 5 <SEP> 0.39 <SEP> 0.39 <SEP> 0.78 <SEP> 0.04 <SEP> 12.5
<tb> 6 <SEP> 0.78 <SEP> 3.13 <SEP> 25 <SEP> 0.1 <SEP> 50
<tb> 7 <SEP> 3.13 <SEP> 6.25 <SEP>> 100 <SEP> 0.1 <SEP> 25
<tb> 8 <SEP> 0.78 <SEP> 0.78 <SEP>> 100 <SEP> 0.04 <SEP> 0.78
<tb> 9 <SEP> 12.5 <SEP> 12.5 <SEP>> 100 <SEP> 0.78 <SEP> 25
<tb> TABLE <SEP> IV
<tb> Example <SEP> N <SEP> PYRIOR
<tb> 23 <SEP> 0.10
<tb> 24 <SEP> 1.56
<tb> 25 <SEP> 0.39
<tb> 26 <SEP> 0.10
<tb> 27 <SEP> 0.20
<tb> 28 <SEP> 0, <SEP> 1 <SEP> 0 <SEP>
<tb> 29 <SEP> 0.39
<tb> 30 <SEP> 1.56
<tb> 31 <SEP> 0.04
<tb>

Claims (14)

1. Compound characterized in that it is represented by formula I

in which R and R2 each independently represent a hydrogen atom or an optionally substituted alkyl, alkenyl, alkynyl, alkadienyl, haloalkyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl group, or R1and R2 together with the intercalating nitrogen atom form an optionally substituted heterocycle; 3 4 5 R, R and R each independently represent a fluorine atom or a chlorine atom, provided that at least one of R3, Ret R5 is a chlorine atom; and X represents a halogen atom. 2. Compound according to claim 1, characterized in that R represents a C1-C6 alkyl, halo-C1-C6 alkyl or C2-C6 straight or branched chain alkenyl group, or a C1-C6 cycloalkyl or C5-C9 bicycloalkyl group, and R represents a hydrogen atom or a C1-C6 alkyl group, or else R1 and R2 together with the intercalating nitrogen atom form a heterocycle having 5 or 6 carbon atoms, optionally substituted by one or two C1-C6 alkyl groups. 3. Compound according to claim 1 or claim 2, characterized in that R represents a hydrogen atom. <Desc / Clms Page number 31> 4. A compound according to any one of claims 3 4 5 1, 2 and 3, characterized in that one of R, R and R represents a fluorine atom and the other two represent chlorine atoms. 5. Compound according to claim 4, characterized in that R and R represent chlorine atoms. 6. Compound according to any one of claims 1, 2 and 3, characterized in that R represents an atom of 4 5 chlorine and R and R represent fluorine atoms. 7. Compound according to claim 1, characterized in that it is chosen from the following compounds: # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] cyclopentylamine; # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) -7- (4-methyl-piperidin-1-yl) - [1,2,4] triazolo [1,5- [alpha] ] pyrimidine; # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] - (2,2,2- trifluoroethyl) amine; # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] - (1,1,1- trifluoroprop-2-yl) amine; # [5-Chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] diethylamine; # [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] isopropylamine; # sec-butyl- [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine;

#bicyclo [2.2.1] hept-2-yl- [5-chloro-6- (2,6-dichloro-4-fluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine -7-yl] amine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] cyclopentylamine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) -7- (4-methyl-piperidin1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] - (2,2,2- trifluoroethyl) amine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo-

[1,5-a] pyrimidin-7-yl] - (1,1,1-trifluoroprop-2-yl} amine; <Desc / Clms Page number 32> bicyclo [2.2.1] hept-2-yl- [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine- 7-yl] amine; # but-2-yl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # isopropyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # [5-Chloro-6- (2,4,6-trichlorophenyl) -7- (3-methylpiperidin-1-yl) - [1,2,4] triazolo [1,5- [alpha]] pyrimidine; # cyclopentyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # [5-Chloro-6- (2,4,6-trichlorophenyl) -7- (4-methylpiperidin-1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine; # diethyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] - triazolo [1,5-a] pyrimidin-7-yl] amine; # norborn-2-yl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] - triazolo [1,5-a] pyrimidin-7-yl] amine; # cyclopropyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # 2,2,2-trifluoroethyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; # N-ethyl-N-2-methylallyl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5- [alpha]] pyrimidin-7-yl ] amine; and # 1,1,1-trifluoroprop-2-yl- [5-chloro-6- (2,4,6-trichlorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine- 7-yl] amine.

# [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] diethylamine; # [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo- [1,5-a] pyrimidin-7-yl] isopropylamine; # sec-butyl- [5-chloro-6- (2-chloro-4,6-difluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidin-7-yl] amine; 8. Process for the preparation of a compound of formula I as defined in any one of claims 1 to 7, characterized in that it comprises the reaction of a compound of formula II <Desc / Clms Page number 33> wherein R 1 and R2 are as defined in any one of the preceding claims.

R3, R4, R5 and X are as defined in any one of the preceding claims, with an amine of formula III in which

9. Compound characterized in that it is represented by formula II

in which R3, R4, R5 and X are as defined in any one of claims 1 to 7. 10. A compound capable of leading by halogenation to a compound according to claim 9, characterized in that it is chosen from

5,7-dihydrocy-6- (2,4,6-trichlorophenyl) -I1,2,4] triazolo- [1,5-a] pyrimidine, 5,7 -dihydroxy-6- (2,6- dichloro-4-fluorophenyl) - [1,2,4] triazolo [1, 5-a] pyrimidine and 5,7-dihydroxy-6- (2-chloro-4,6-difluorophenyl) - [1,2, 4J-triazolo [1,5- a] pyrimidine. <Desc / Clms Page number 34> 11. Fungicidal composition, characterized in that it comprises a carrier and, as active ingredient, at least one compound of formula I as defined in any one of claims 1 to 7. 12. A method for combating a fungus at a site, characterized in that it comprises treating the site with a compound of formula I as defined in any one of claims 1 to 7. 13. The method of claim 12, characterized in that said fungus is Piricularia oryzae f.sp. grisea. 14. Use as a fungicide of a compound of formula I as defined in any one of claims 1 to 7.