FR2765875A1 - New 5-alkyl-triazolo pyrimidine derivatives are fungicides - Google Patents

Abstract

5-Alkyl triazolo pyrimidine derivatives of formula (I) are new. R1 = alkyl, alkenyl, alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl (all optionally substituted); R2 = H, alkyl, alkenyl, alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl (all optionally substituted); or NR1R2 = optionally substituted heterocycle; R3 = alkyl; A = N or CR5; R4, R5 = H, alkyl or aryl; L = halo or alkyl or alkoxy (both optionally substituted); n = 0-5.

Description

This invention relates to certain triazolopyrimidine compounds, a process

  for their preparation, compositions containing these compounds, a method for controlling a fungus at a site comprising treating the site with such compounds and their use as fungicides. EP-A-0 071 792 claims compounds of the general formula NH2 (Rb. Ez -___ NN R3

A N2

A N R2

  wherein R1 represents an alkyl, halo, alkoxy, cyano, cycloalkyl, aryl, aryloxy, arylthio, aralkyl, arylalkyl, arylalkyloxy or arylalkylthio group, each optionally substituted by a halogeno group or

  alkoxy; or (R '), represents a benzene, indane or tetrahydro-

  naphthalene condensed with a phenyl ring, the aromatic groups in the above groups being optionally substituted with an alkyl, alkoxy, halo or cyano group; n is 1 or 2; R2 and R3 are each a hydrogen atom, an alkyl or aryl group, A represents a nitrogen atom or a CR4 group, and R4 is identical to R2 but may also be a halo, cyano or alkoxycarbonyl group or, together with R3, he

  can form an alkylene chain containing up to two double bonds.

  The compounds are said to be active against various fungi

  plant pathogens, particularly those of the phycomycete class.

  However, the only evidence of fungicidal activity of these compounds is Plasmopara viticola, an element of the oomycete fungi class. U.S. Patent 5,593,996 claims compounds of the general formula R R2 N / R3 NN

<

N N R4

  wherein R 'represents an optionally substituted alkyl, alkenyl, alkadienyl, cycloalkyl, bicycloalkyl or heterocyclyl group; R2 represents a hydrogen atom or an alkyl group; or R1 and R2, together with the nitrogen atom adjacent to these two radicals, represent an optionally substituted heterocyclic ring; R3 represents an optionally substituted phenyl or naphthyl group; and R4 represents a halogen atom or a group -NR5R6 where R5 represents a hydrogen atom or an amino, alkyl, cycloalkyl or

  bicycloalkyl and R6 represents a hydrogen atom or an alkyl group.

SUMMARY OF THE INVENTION

  The present invention provides a compound of formula I

R N-R2 r ;.

N -R <t (L) n

N - N

R 4-

A N R3

  in which R 'is optionally substituted alkyl, alkenyl, alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl, R2 is hydrogen, alkyl, alkenyl, alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl, optionally substituted, or R 'and R2, together with the nitrogen atom adjacent to these two radicals, represent an optionally substituted heterocyclic ring, R3 represents an alkyl group, R4 represents a hydrogen atom or an alkyl or aryl group, L represents a halogen atom or an optionally substituted alkyl or alkoxy group, A represents N or CR5, where Rs has the meaning given for R4, and

  n is zero or is an integer from 1 to 5.

  The new compounds have excellent fungicidal activity

selective in various crops.

  An object of the present invention is to provide novel compounds

selective fungicides.

  An object of the invention is also to provide methods for killing against an undesirable fungus, comprising contacting said plants with an effective fungicidal amount of the novel compounds. Another object of the invention is to provide selective fungicidal compositions containing the novel compounds as active agents. These and other objects and features of the invention will become apparent

  reading the detailed description presented below, and

appended claims.

  It has been surprisingly found that the compounds of formula I

1 2

R 1. N.R2

N-N (L) n

R4 N ... N (4

A N R3

  wherein R1 to R4, A, L and n have the meanings given above for formula I possess excellent fungicidal activity against

wide mushroom range.

  Unless otherwise indicated, as used herein, the term halogen atom may designate a bromine, iodine, chlorine or fluorine atom,

  and in particular a bromine, chlorine or fluorine atom.

  - The optionally substituted groups may be unsubstituted or have a number of substituents ranging from 1 to maximum

  possible. Typically, 0 to 2 substituents are present.

  Unless otherwise indicated herein, the terms alkyl, alkenyl, alkynyl, alkadienyl, used herein for a radical or group, denote a straight or branched chain radical or group. As a rule, these radicals contain up to 10, in particular up to 6, carbon atoms. An alkyl group advantageously comprises 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. A preferred alkyl group is an ethyl group or in particular a methyl group. A

  The alkenyl group advantageously has 2 to 6 carbon atoms.

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  A preferred alkenyl group is an allyl group or in particular a

2-methylallyl group.

  Unless otherwise indicated herein, the term aryl, used herein for a radical or a group, refers to an aryl group having 6, 10 or 14 carbon atoms, preferably 6 or 10 carbon atoms, in particular a phenyl group optionally substituted by one or more halogen atoms, nitro groups, cyano, alkyl, preferably alkyl

  C 1 -C 6, alkoxy, preferably C 1 -C 6 alkoxy.

  Unless otherwise indicated herein, the term heteroaryl, used herein for a radical or a group, refers to a heteroaryl group having 5 or 6 ring atoms selected from carbon, nitrogen, oxygen and sulfur, of which at least one is an atom

nitrogen, oxygen or sulfur.

  Unless otherwise indicated herein, the term cycloalkyl, as used herein for a radical or a group, means a cycloalkyl group having 3 to 8 carbon atoms, preferably 5 to 7 carbon atoms, in particular the cyclohexyl group optionally substituted with one or more several halogen atoms, nitro groups, cyano, alkyl, preferably

  C 1 -C 6 alkyl, alkoxy, preferably C 1 -C 6 alkoxy.

  Unless otherwise indicated herein, the term heterocyclyl or heterocyclic ring, used herein for a moiety or group, refers to a saturated heterocyclyl group having 5 or 6 atoms in the ring selected from carbon, nitrogen, oxygen and sulfur, of which at least one is a nitrogen atom, oxygen or sulfur optionally substituted by one or more halogen atoms, nitro groups, cyano, alkyl, preferably C 1 -C 6 alkyl, alkoxy, preferably C1-C6 alkoxy, especially pyrrolidinyl, pyrazolidinyl,

  piperidinyl, piperazinyl or morpholin-4-yl.

  The invention relates in particular to compounds of general formula I in which any alkyl portion of the groups R 'to R 4, which may be straight or branched chain, contains up to 10 carbon atoms, preferably up to 9 carbon atoms. carbon, more preferably up to 6 carbon atoms, any alkenyl or alkynyl portion of the substituents R 'to R4 contains up to 10 carbon atoms, preferably up to 9 carbon atoms, more preferably up to 6 carbon atoms. carbon, any cycloalkyl portion of the substituents R to R4 contains from 3 to 10 carbon atoms, preferably from 3 to 8 carbon atoms, more preferably from 3 to 6 carbon atoms, and any aryl portion of the substituents R'l to R4 contains 6, 10 or 14 carbon atoms, preferably 6 or 10 carbon atoms, and wherein each optionally substituted group is independently substituted by one or more halogen atoms, or nitro, cyano, alkyl, preferably alkyl groups in C-C6, cycloalkyl, preferably C3-C6 cycloalkyl, cycloalkenyl,

  preferably C 3 -C 6 cycloalkenyl, haloalkyl, preferably

  C 1 -C 6 alkyl, halogenocycloalkyl, preferably C 3 -C 6 halocycloalkyl, alkoxy, preferably C 1 -C 6 alkoxy, haloalkoxy,

  C1-C6 haloalkoxy, phenyl, halogeno- or dihalogeno-

  phenyl or pyridyl. Any alkyl, alkenyl or alkynyl group can be linear or branched. A heterocyclic group of 4 to 6 members may be any heterocyclic group containing 4 to 6 atoms in the ring, interrupted by one or more heteroatoms selected from sulfur, nitrogen and oxygen, preferably oxygen. A halogen atom advantageously denotes a fluorine, chlorine or bromine atom. The invention relates in particular to the compounds of general formula I in which R 'represents a C 1 -C 10 alkyl group,

  C1-C10 haloalkyl, C3-C6 cycloalkyl, (C3-C3 cycloalkyl)

  C8) (C1-C6) alkyl, (C1-C10) alkoxy (C1-C6) alkyl or phenyl, especially (C1-C10) fluorinated alkyl, and R2 represents a group

  C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 8 cycloalkyl) C 1 -C 6 alkyl

  C6, (C1-C6) alkoxy, (C1-C6) alkyl or phenyl, especially hydrogen. The compounds of formula I in which the phenyl group is particularly preferred are

F

  A _ (! L) n is selected from FI Ci F F F

F FF F F

  The compounds according to the general formula I are oils, gums or solids which are predominantly crystalline. They are of greater value for all of their fungicidal properties, in particular their increased systemic character and increased fungitoxicity against tomato aternaria. For example, they can be used in agriculture or in related fields for the control of phytopathogenic fungi, such as Alternaria solani, Botrytis cinerea, Cercospora beticola, Cladosporium herbarum, Corticon rolfsii, Erysiphe graminis, Helminthosporium tritici repentis, Leptosphaeria nodorum , Micronectriella nivalis, Monilinia fructigena, Mycosphaerella ligulicola, Mycosphaerella pinodes, Pyricularia grisea sp. oryzae, Rhizoctonia solani and Scerotinia scerotiorum, especially for the control of Alternaria solani and Botrytis cinerea. The compounds of general formula I according to the invention have a high fungicidal activity in a wide range of concentrations and can be used in agriculture without

difficulties.

  In addition, the compounds according to the invention have an improved residual action against fungi compared to conventional fungicides. Good results in terms of controlling phytopathogenic fungi are obtained with a compound as defined by formula I in which: R3 represents a methyl group; R1 represents a straight or branched chain C1-C6 alkyl group, in particular ethyl or isopropyl, C3-C7 cycloalkyl, in particular cyclopentyl, straight or branched chain C1-C6 haloalkyl, in

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  2,2,2-trifluoroethyl or 1,1,1-trifluoroprop-2-yl, or C2-C6 straight or branched chain alkenyl, in particular allyl or 2-methylallyl, and R2 represents a hydrogen atom or C1-C6 alkyl, in particular methyl or ethyl; or R1 and R2, together with the nitrogen atom adjacent to both radicals, represent a 5- or 6-membered heterocyclic ring optionally substituted with one or two C1-C6 alkyl groups, particularly when R1 and R2 , together with the nitrogen atom adjacent to both radicals, represents an optionally substituted piperidin-1-yl group, such as piperidin-1-yl or 4-methylpiperidin-1-yl;

  A is N and R4 is a hydrogen atom.

  Compounds of formula IA are particularly preferred

N-N 2

L N L 3 (IA)

NN CH3

  in which R 'and R2 have the given meanings, and L, L2 and L3 each independently represent a hydrogen atom,

  fluorine or chlorine of which at least one is a fluorine or chlorine atom.

  Particularly good results in terms of controlling phytopathogenic fungi are obtained using, for example, the following compounds of formula I:

  6- (2-chloro-6-fluorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl) -

  [1,2,4] triazolo [1,5-a] pyrimidine; 6- (2-fluorophenyl) -5-methyl-7- (4-

  methylpiperidin-1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine; the 6- (2-chloro

  phenyl) -5-methyl-7- (4-methylpiperidin-1-yl) - [1,2,4] triazolo [1,5-a] -

  pyrimidine; 6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N, N-diethylamino) -

  [1,2,4] triazolo [1,5-a] pyrimidine; 6- (2-chloro-6-fluorophenyl) -5 methyl

  7- (N-ethylamino) - [1,2,4] triazolo [1,5-a] pyrimidine; 6- (2-chloro-6-fluorophenyl)

  phenyl) -5-methyl-7- (N- (2,2,2-trifluoroethyl) amino) - [1,2,4] triazolo [1,5a] -

  pyrimidine; 6- (2,6-difluorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl)

  [1,2,4] triazolo [1,5-a] pyrimidine; 6- (2,6-dichlorophenyl) -5-methyl-7 (4-

  methylpiperidin-1l-yl) - [1,2,4] triazolo [1,5-a] pyrimidine; 6- (2-chloro-6-

  fluorophenyl) -5-methyl-7- (N-isopropylamino) - [1,2,4] triazolo [1,5-a] -

  pyrimidine; 6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N-cyclopentyl)

  amino) - [1,2,4] triazolo [1,5-a] pyrimidine; 6- (2,6-difluorophenyl) -5-

  methyl-7- (N, N-diethylamino) - [1,2,4] triazolo [1,5-a] pyrimidine, the 6- (2-

  chloro-6-fluorophenyl) -5-methyl-7- (N-ethyl-N-2-methylallylamino) - [1,2,4] -

  triazolo [1,5-a] pyrimidine; (2,4,6-trifluorophenyl) -5-methyl-7- (4-methyl)

  piperidin-1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine; the 6- (2,4,6trifiuoro-

  phenyl) -5-methyl-7- (piperidin-1-yl) - [1,2,4] triazolo [1,5-a] pyrimidine; the (2-

  chloro-6-fluorophenyl) -5-methyl-7- (piperidin-1-yl) - [1,2,4] triazolo [1,5-a] -

  pyrimidine; (2-Fluorophenyl) -5-methyl-7- (piperidin-1-yl) - [1,2,4] triazolo-

  [1,5-a] pyrimidine; 6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N- (1,1,1-

  trifluoroprop-2-yl) aminino- [1,2,4] triazolo [1,5-a] pyrimidine; the 6- (2,6-

  difluorophenyl) -5-methyl-7- (N- (1,1,1-trifluoroprop-2-yl) amino) - [1,2,4] -

  triazolo [1,5-a] pyrimidine; 6- (2,4,6-trifluorophenyl) -5-methyl-7- (N-)

  (1,1,1-trifluoroprop-2-yl) amino) [1,2,4] triazolo [1,5-a] pyrimidine; the 6-

  (2,4,6-Trifluorophenyl) -5-methyl-7- (N, N-diethylamino) - [1,2,4] triazolo

  [1,5-a] pyrimidine; 6- (2,4,6-trifluorophenyl) -5-methyl-7- (N-methylamino) -

[1,2,4] triazolo [1,5-a] pyrimidine.

  The present invention further provides a process for preparing a compound of formula I wherein R 3 is a methyl group which comprises (a) treating a 5-haloazolopyrimidine of formula II,

NOT

  (L). R4 NN (II) AN Hal wherein A, R1, R2, R4, L and n have the meanings given for formula I, with a dialkyl manolate in the presence of a base, (b) heating the malonate of resulting aminoazolopyrimidin-5-yl of formula III,

R .., 2

N (L) n

R4 NN -N (111)

  s -1R A COOR COOR in which R1, R2, R4, A, L and n have the meanings given for

  Formula I, and R represents an alkyl group in the presence of an acid.

  In addition, the compounds of formula I can also be prepared from 7-aminotriazolopyrimidines of formula IV, NH 2

NR4- N N

A N R3 (IV)

  wherein R3, R4, A, L and n have the meanings given for formula I, which are treated with a halogenating agent in the presence of a diazotising agent, and by treatment of the compound of general formula V resulting Hal. L) 2sH> (L) N.N '

R4 <(V)

A N R

  wherein R3, R4, A, L and n are as defined above; and Hal represents a chlorine or bromine atom, with an amine of the general formula VI Rk N - H (VI) R2 in which R

  R1 and R2 are as defined above.

  Compounds of formula IV are known, for example, according to US Pat.

European Patent 0 071 792.

  The reaction between 5-halo-7-amino-6-phenyltriazolo

  pyrimidines of formula II, which are known from U.S. Patent No. 5,593,996, and the alkyl malonate is advantageously carried out in the presence of a solvent. Suitable solvents include ethers, such as dioxane, diethyl ether and, in particular, tetrahydrofuran, optionally halogenated hydrocarbons such as mineral oil, dichloromethane and aromatic hydrocarbons, for example toluene, nitriles and the like. such as acetonitrile, or mixtures of these solvents. The reaction is advantageously carried out at a temperature in the range of

  0 C to 100 C, the preferred reaction temperature being from 20 C to 70 C.

  It is also preferred to carry out the reaction in the presence of a strong base. Suitable strong bases include hydrides such as sodium hydride and organometallic compounds such as butyllithium and amides such as

  than sodium amide or lithium diisopropylamide.

  The compounds of general formula I are found to possess fungicidal activity. Therefore, the invention further relates to a fungicidal composition which comprises an active substance, which is at least one compound of formula I as defined above, and one or more vehicles. It also relates to a method of manufacturing such a composition which comprises bringing into association a compound of formula I as defined above with the vehicle or vehicles. Such a composition may contain a single active substance or a mixture of several active substances of the present invention. It is also contemplated that different isomers or isomeric mixtures may have different levels or different activity spectra and therefore the compositions may include isomers

  or mixtures of isomers.

  A composition according to the invention preferably contains from 0.5% to

  95% by weight (weight / weight) of active substance.

  A vehicle in a composition according to the invention may be any material with which the active substance is formulated to facilitate the application to the place to be treated, which may be, for example, a plant, a seed or a soil, or to facilitate storage, transportation or handling. A vehicle may be a solid or a liquid, including a material that is normally a gas but has been compressed to give

liquid.

  The compositions may be made, for example, of emulsion concentrates, solutions, oil-in-water emulsions, wettable powders, soluble powders, suspension concentrates,

  dust, in granules, in water-dispersible granules, in microparticles

  capsules, gels and other types of formulation by well-established procedures. These procedures involve intensive mixing and / or grinding of the active substances with other substances, such as fillers, solvents, solid carriers, surfactant compounds (surfactants) and, optionally, auxiliaries and / or solid and / or liquid builders. The form of application, such as spraying, atomization, dispersion or pouring, may be chosen

  as the compositions according to the desired purposes and the given circumstances.

  The solvents may be aromatic hydrocarbons, for example Solvesso 200, substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, for example cyclohexane or paraffins, alcohols and alcohols. glycols, as well as their ethers and esters, for example ethanol, monomethyl ether and ethylene glycol dimethyl ether, ketones

  such as cyclohexanone, strongly polar solvents such as N-

  methyl-2-pyrrolidone or butyrolactone, (higher alkyl) pyrrolidone

  lidones, for example n-octylpyrrolidone or cyclohexylpyrrolidone, esters of epoxidized vegetable oils, for example coconut oil ester or methylated soybean, and water. Mixtures of different liquids

often agree.

  Solid vehicles, 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 can be improved by the addition of a highly dispersed silica gel or polymers. The vehicles for the granules may be a porous material, for example pumice, kaolin, sepiolite, bentonite; non-sorbent vehicles may be calcite or sand. In addition, a multitude of mineral or organic materials granulated beforehand

  can be used, such as dolomite or milled vegetable residues.

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

less is a surfactant.

  The surfactants may be nonionic, anionic, cationic or zwitterionic substances, with good dispersion, emulsification and wetting properties depending on the nature of the compound of general formula I to be formulated. Surfactants can also be

  mixtures of individual surfactants.

  The compositions of the invention may be formulated, for example, as wettable powders, water-dispersible granules, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and the like. aerosols. Wettable powders usually contain 5 to 90% w / w of active substance and usually contain, in addition to the inert solid carrier, 3 to 10% w / w dispersants and wetting agents and, if necessary, 0 to 10% in weight / weight of one or more stabilizers and / or other additives such as penetrating or tackifying agents. The dusts are usually formulated as a dust concentrate having a composition similar to that of a wettable powder, but without a dispersing agent, and can be diluted in the field with another solid carrier to give a composition usually containing 0.5 to 10% in weight / weight of active substance. Water dispersible granules and granules are usually prepared to have a size of between 0.15 mm and 2.0 mm and can be manufactured by a multitude of techniques. Generally, these types of granules will contain 0.5 to 90% w / w of active substance and 0 to 20% w / w of additives, such as a stabilizer, surfactants, additives to delay the release and binding agents. The so-called "dry flowable" compounds consist of relatively small granules having a relatively high active substance concentration. Emulsifiable concentrates usually contain, in addition to a solvent or a mixture of solvents, from 1 to 80% w / v of active substance, from 2 to 20% w / v of emulsifiers and from 0 to 20% by weight. % w / v other additives, such as stabilizers, penetrants and corrosion inhibitors. Suspended concentrates are usually ground to a stable flowable product, which does not sediment, and usually contain 5 to 75% w / v of active substance, 0.5 to 15% w / v dispersants, from 0.1 to 10% w / v of suspending agents, such as protective colloids and thixotropic agents, from 0 to 10% w / v of other additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and tackifiers, and water or an organic liquid in which the active substance is substantially insoluble; some S5 organic solids or mineral salts may be present dissolved in the formulation to help prevent sedimentation and crystallization or in

as antifreeze agents for water.

  Dispersions and aqueous emulsions, for example the compositions obtained by diluting the product formulated according to the invention

  with water, also fall within the scope of the invention.

  The use of a vehicle that provides a slow release of pesticide compounds into the environment of a plant to be protected is of particular interest for prolonging the duration of the activity.

  protecting the compounds of this invention.

  The biological activity of the active substance can also be increased by incorporating an adjuvant into the spray dilution. An adjuvant is defined herein as a substance that can increase the biological activity of an active substance, but is not itself significantly biologically active. The adjuvant may be incorporated into the formulation as a co-formulation agent or carrier, or may be added to the spray tank with the formulation

containing the active substance.

  For convenience, the compositions may preferably be in concentrated form, while the end user generally employs diluted compositions. The compositions can be diluted to a concentration of 0.001% of active substance. Doses are usually

  in the range of 0.01 to 10 kg of active substance / ha.

  Examples of formulations according to the invention are: Emulsion concentrate (CE) Active substance Compound of Example 1 30% (wt / vol) Emulsifier (s) Atlox 4856 B / Atlox 4858 Bl) 5% (weight / vol ) Shellsol solvent A2) at 1000 mL Emulsion concentrate (EC) Active substance Compound of Example 1 50% (wt / vol) Dispersing agent Soprophor FL3) 3% (wt / vol) Antifoaming agent Rhodorsil 4223) 0, 2% (wt / vol) Kelzan S4 Structural Agent 0.2% (wt / vol) Antifreeze Agent Propylene Glycol 5% (wt / vol) Biocidal Agent Proxel 5) 0.1% (wt / vol) Water 1000 mL Wettable Powder (PM) Active Substance Compound of Example 1 60% (wt / wt) Atlox wetting agent 4995 ') 2% Witcosperse dispersant D-606) (wt / wt) Vehicle / filler Kaolin 3% (wt / wt) )% (wt / wt) Water dispersible granules (GE) Active substance Compound of Example 1 50% (wt / wt) Agent Dispersant Witcosperse D-4506) 8% / binder (wt / wt) Morwet wetting agent EFW6) Rhodorsil EP Agent antifoam 67033) 2% Crumbling Agrimer ATF7) (weight / weight) Vehicle / filler Kaolin 1% (wt / wt) 2% (wt / wt)% (wt / wt) Identity of the ingredients used in the examples Name Identity Agrimer ATF7) cross-linked homopolymer of N-vinyl-2-pyrrolidone Atlox 4856 B / mixture containing an alkylarylsulfonate of Atlox 4858 B ') calcium, ethoxylates of fatty alcohols and light aromatic compounds / mixture containing a calcium alkylarylsulfonate, Atlox ethoxylates 4995) Kelzan of fatty alcohols and light aromatic compounds S4) polyethoxylated alkyl ether Morwet EFW6) xanthan gum Propylene glycol condensation product of formaldehyde Proxel 5) aqueous dipropylene glycol solution containing Rhodorsil 4223) 20% 1,2-benzisothiazolin-3-one emulsion Rhodorsil aqueous nonionic EP 67033) Shellsol A2 polydimethylsiloxanes) encapsulated silicone Soprophor FL3) aromatic hydrocarbon mixture C9-CI0

  polyoxyethylenepolyarylphenylamine amine salt

ether phosphate

  Witcosperse D-4506) mixture of sodium salts of naphthalene

  sulphonic and condensed alkyl sulphonates

  Witcosperse D-606) mixture of sodium salts of naphthalene

  sulphonic and fused alkylaryl polyoxyacetates 1) available from ICI Surfactants 2) available from Deutsche Shell AG 3) available from Rhône-Poulenc 4) available from Kelco Co.) available from Zeneca 6) available from Witco 7) available from International Specialty Products The compositions of this invention may also include other compounds having biological activity, for example compounds having similar or complementary fungicidal activity or compounds having plant growth regulating activity, herbicide or insecticide. These fungicide mixtures may have a broader spectrum of activity than the compound of general formula I alone. In addition, the other fungicide may have a synergistic effect on the fungicidal activity of the compound of general formula I. Examples of other fungicidal compounds are as follows! anilazine, azoxystrobin, benalaxyl, benomyl, binapacryl, bitertanol, S blasticidine, Bordeaux mixture, bromucanozole, bupirimate, captafol, 1O captan, carbendazim, carboxine, carpropamid, chlorbenzthiazon, chlorothalonil, chlozolinate, copper-containing compounds such as oxychloride copper and copper sulfate, cycloheximide, cymoxanil, cypofuram, cyproconazole, cyprodinil, dichlofluanid, dichlone, dichloran, diclobutrazol, dichlocymet, diclomide, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, diniconazole, dinocap, ditalimfos, dithianon, dodemorph, dodine , edifenphos, epoxiconazole, etaconazole, ethirimol, etidiazole, famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin acetate, fentin hydroxide, ferimzone, fluazinam, fludioxonil, flumetover, fluquinconazole, flusilazole , flusulfamide, flutolanil, fluriafol, folept, fosetyl-aluminum, fuberisa zole, furalaxyl, furametpyr, guazatin, hexaconazole, imazalil, iminoctadine,

  ipconazole, iprodione, isoprothiolane, kasugamycin, kitazine P. kresoxim-

  methyl, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,

  metconazole, methfuroxam, myclobutanil, neoasozine, dimethyldithio-

  nickel carbamate, nitrothalisopropyl, nuarimol, ofurace, organo-mercuric compounds, oxadixyl, oxycarboxin, penconazole, pencycuron, phenazine oxide, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidione, propamnocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinomethionate, quinoxyfen, quintozene, spiroxamine, SSF-126, SSF-129, streptomycinr, sulfur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamnid, thiophanate-methyl, thiram, tolclofosmethyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A,

  vinclozoline, XRD-563, zarilamid, zineb, ziram.

  In addition, the joint formulations according to the invention may contain at least one compound of formula I and any compound of the following classes of biological control agents, such as viruses, bacteria, nematodes, fungi and other microorganisms. -organisms suitable for the control of insects, weeds or plant diseases or for the induction of plant resistance to a host. Examples of these biological control agents are: Bacillus thuringiensis, Verticillium lecanii, Autographica califomnica NPV, Beauvaria bassiana, Ampelomyces quisqualis, Bacilis subtilis, Pseudomonas fluorescens,

  Streptomyces griseoviridis and Trichoderma harzianum.

  In addition, the formulations according to the invention may contain at least one compound of formula I and a chemical agent which induces an acquired systemic resistance to plants such as, for example, the acid

  nicotinic acid or its derivatives, 2,2-dichloro-3,3-dimethylcyclopropyl-

carboxylic acid or BION.

  The compounds of general formula I can be mixed with soil, peat or other culture media for the protection of plants against fungal diseases developing on the seeds,

earth or leaves.

  The invention further relates to the use as a fungicide of a compound of general formula I as defined above or a composition as defined above, and a method for controlling a fungus in a place, which includes the treatment of the place, which may be for example plants subject to fungal attack, the seeds of these plants or the medium in which these plants grow

  or must grow with such a compound or composition.

  The present invention has a wide field of application in the protection of crops and decorative plants against a fungal attack. Typical crops that can be protected include vineyards, cereal crops such as wheat and barley, rice, sugar beet.

  sugar, flowering fruits, peanuts, potatoes and tomatoes.

  The duration of protection normally depends on the individual compound chosen, and also on a variety of external factors such as climate, the impact of which is usually weakened by the use of a suitable formulation. The following examples illustrate in detail the present invention. It will be understood, however, that the invention is not limited solely to the particular examples given below.

Example 1

  6- (2-Chloro-6-fluorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl) - [1,2,4] -

triazolo [1,5-a] pyrimidine

  1A [6- (2-Chloro-6-fluorophenyl) -7- (4-methylpiperidin-1-yl) -f [1,2,4] -

  Diethyl triazolo [1,5-al] pyrimidin-5-yl] malonate Sodium hydride (0.27 g of a 50% dispersion in mineral oil, 5.65 mmol) was added to the reaction mixture. diethyl malonate (20 mL). We

  dilute the mixture with acetonitrile and add (2-chloro-6-

  fluorophenyl) -5-chloro-7- (4-methylpiperidin-1-yl) - [1,2,4] -triazolo [1,5-a] -

  pyrimidine (obtained according to U.S. Patent No. 5,593,996, 2.0 g, 4.71 mmol).

  The reaction mixture is heated to 60 ° C. and stirred for 20 hours.

  Aqueous ammonium chloride (50 mL) is added and the mixture is acidified with dilute hydrochloric acid. The reaction mixture was extracted with ethyl acetate (3 x 50 mL). The combined organic phases are dried and concentrated. The residue is purified by column chromatography (silica, toluene mixture: ethyl acetate 9: 1). The pure product is obtained in the form of buff-colored crystals

  (0.95 g) having a melting point of 162 - 163 C.

  1B 6- (2-Chloro-6-fluorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl) -

  [1,2,4] -triazolo [1,5-a] pyrimidine A mixture of 1A (0.5 g, 1 mmol) and concentrated hydrochloric acid is heated at 80 ° C. for 24 hours. The reaction mixture is cooled and adjusted to pH 5 by the addition of aqueous sodium hydroxide. The reaction mixture is extracted with ethyl acetate. The combined organic phases are dried and concentrated. The residue is purified by

  column chromatography (silica, toluene mixture: ethyl acetate 2: 1).

  The pure product is obtained in the form of buff-colored crystals (0, 27

  g) having a melting point of 177 - 178 C.

Examples 2-22

  The following examples are synthesized (Table I: Structure and point of

  melting) in a similar manner to Example 1.

NRL L3

N-R 2x

N- N

N N CH3

  Example R1 R2 L1 L2 L3 Melting Point (C)

  2 - (CH 2) 2-CH (CH 3) - (CH 2) 2 - F H H 197-199

  3 - (CH 2) 2 -CH (CH 3) - (CH 2) 2 - Cl H H 201-202 4 C2Hs-C 2 H 5 F Cl H 147-148

C2H5- H F CF H 140-141

6 F3C-CH2- H F Cl H

7 - (CH 2) 2 -CH (CH 3) - (CH 2) 2 F H H

8 - (CH2) 2-CH (CH3) - (CH2) 2- C1 CF H

  9 2-propyl H F Ci H cyclopentyl H F C1 H

11 C2H5- C2H5- F F H

12 CH2.C (CH3) -CH2 C2H5-F Ci H

13 - (CH 2) 2 -CH (CH 3) - (CH 2) 2 - F F F

14 - (CH2) 5- F F F

- (CH2) 5- F Cl H

16 - (CH2) 5- F H H

17 - (CH2) 5- F F H

  1,1,1-Trifluoroprop-2-ylH FCl H 19 1,1,1-trifluoroprop-2-ylH F H 1,1,1-trifluoroprop-2-ylH F F F

21 C2H5- C2H5- E F F

  22 C2Hs-H F F F Biological studies Determination of the effective dose for an inhibition of more than 90% by the compounds studied in the test of successive dilutions with various phytopathogenic fungi

2765875

  DE> 90 (Effective Dose> 90%) is determined by successive dilution tests using Microtiter plates with 24 or 48 wells per plate. Dilution of the test compounds in the nutrient solution and distribution in the wells is performed using a TECAN RSP 5000 Robotic Sample Processor. The following test compound concentrations are used: 0.05, 0.10, 0.20, 0.39, 0.78, 1.56, 3.13, 6, 25, 12.50, 25.00, 50 , 00 and 100.00 gg / mL. For the preparation of the nutrient solution, a vegetable juice V8 (333 ml) was mixed with calcium carbonate (4.95 g), centrifuged, and the supernatant (200 ml) was diluted with 0% of water. (800 mL), and placed in an autoclave at 121 ° C for 30 minutes. The respective inoculumins (Alternaria solani, ALTESO, Botrytis cinerea, BOTRITI, Leptosphaeria nodorum, LEPTNO, Phytophthora infestans, PHYTIN, Pyrenophora teres, PYRNTE, Rhizoctonia solani, RHIZSO) are placed in the wells as spore suspensions (50 mL, 5x105). / mL) or agar plates (6 mm) from a culture of

mushroom on agar.

  After 6-12 days of incubation at suitable temperatures (1825 ° C.), ED values> 90 are determined by visual inspection of the plates. The lowest concentration in the dilution series with mycelial growth less than 10% is defined as the

  DE value> 90 (Table II, n.t. = not tested).

Table II

  Ex. N ALTESO BOTRCI LEPTNO PHYTIN PYRNTE RHISZO 1- 0, 2 0.78 1.56 n.t. 0.78 50

2 3.13 12.5 n.t. 100 100 n.t.

3 0.78 1.56 n.t. n.t. 100 n.t.

  4 25 n.t. n.t. n.t. n.t. 3.13 50 25 n.t. 100 n.t. 50

Claims (12)

  1. Compound of general formula I Rk N 'R2 N N- (L) n N R3   wherein R1 is optionally substituted alkyl, alkenyl, alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl, R2 is hydrogen, alkyl, alkenyl, alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl, optionally substituted, or RIet R2, together with the nitrogen atom adjacent to these two radicals, represents an optionally substituted heterocyclic ring, _ represents an alkyl group, R4 represents a hydrogen atom or a group alkyl or aryl, L represents a halogen atom or an optionally substituted alkyl or alkoxy group, A represents N or CR5, where R5 has the meaning given for R4, and   n is zero or is an integer from 1 to 5.   2. Compound according to claim 1, characterized in that R3 represents a methyl group.   3. Compound according to claim 1 or 2, characterized in that R; is a straight or branched chain C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, straight or branched chain C 1 -C 6 haloalkyl, or straight or branched chain C 2 -C 6 alkenyl, and R 2 is a carbon atom, hydrogen or a C 1 -C 6 alkyl group, or R 1 and R 2, together with the adjacent nitrogen atom, represent a heterocylic ring with 5 or 6 carbon atoms optionally   substituted with one or two C 1 -C 6 alkyl groups.   4. Compound according to any one of the preceding claims, characterized in that A is N, and R4 is a hydrogen atom.   5. A compound according to any one of the preceding claims,   characterized in that R1 and R2, together with the adjacent nitrogen atom, represent a   heterocyclic group selected from piperidin-1-yl and 4- methylpiperidin-1-yl.   6. A compound according to any one of the preceding claims of formula IA R L N-2 L3 <-N J (IA) N N CH3   wherein R1 and R2 have the given meanings, and Lt, L2 and L3 each independently represent a hydrogen atom,   fluorine or chlorine, at least one being a fluorine or chlorine atom. 7. Compounds of formula I below:   6- (2-chloro-6-fluorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl) - [1,2,4] - triazolo [1,5-a] pyrimidine   6- (2-fluorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl) - [1,2,4] triazolone [1,5-a] pyrimidine   6- (2-Chlorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl) - [1,2,4] triazolone [1,5-a] pyrimidine   6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N, N-diethylamino) - [1,2,4] - triazolo [1,5-a] pyrimidine   6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N-ethylamino) - [1,2,4] triazolo [1,5-a] pyrimidine   6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N- (2,2,2-trifluoroethyl) amino) - [1,2,4] triazolo [1,5-a] pyrimidine   6- (2,6-difluorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl) - [1,2,4] - triazolo [1,5-a] pyrimidine   6- (2,6-dichlorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl) - [1,2,4] - triazolo [1,5-a] pyrimidine   6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N-isopropylamino) - [1,2,4] -   triazolo [1,5-a] pyrimidine 6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N-cyclopentylamino) - [1,2,4] triazolo [1,5-a] pyrimidine   6- (2,6-difluorophenyl) -5-methyl-7- (N, N-diethylamino) - [1,2,4] triazolo- [1,5-a] pyrimidine   6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N-ethyl-N-2-methylallylamino) -   [1,2,4] triazolo [1,5-a] pyrimidine   6- (2,4,6-trifluorophenyl) -5-methyl-7- (4-methylpiperidin-1-yl) - [1,2,4] - triazolo [1,5-a] pyrimidine   (2,4,6-Trifluorophenyl) -5-methyl-7- (piperidin-1-yl) - [1,2,4] triazolo [1,5-a] - pyrimidine   (2-Chloro-6-fluorophenyl) -5-methyl-7- (piperidin-1-yl) - [1,2,4] triazolo- [1,5-a] pyrimidine   (2-fluorophenyl) -5-methyl-7- (piperidin-1-yl) - [1,2,4] triazolo [1,5-a] - pyrimidine   6- (2-chloro-6-fluorophenyl) -5-methyl-7- (N- (1,1,1-trifluoroprop-2-yl) - [1,2,4] triazolo [1,5-a] pyrimidine   6- (2,6-difluorophenyl) -5-methyl-7- (N- (1,1,1-trifluoroprop-2-yl) amino) - [1,2,4] triazolo [1,5-a] pyrimidine   6- (2,4,6-trifluorophenyl) -5-methyl-7- (N- (1,1,1-trifluoroprop-2-yl) -   amino) - [1,2,4] triazolo [1,5-a] pyrimidine   6- (2,4,6-trifluorophenyl) -5-methyl-7- (N, N-diethylamino) - [1,2,4] triazolo [1,5-a] pyrimidine   6- (2,4,6-trifluorophenyl) -5-methyl-7- (N-ethylamino) - [1,2,4] triazolo [1,5-   a] pyrimidine. 8. Process for the preparation of a compound of formula I, in which R3 represents a methyl group, characterized in that it comprises (a) the treatment of a 5-haloazolopyrimidine of formula II 1 2   ## STR5 ## wherein A, R 1, R 2, R 4, L and n have the meanings given for formula I and Hal represents a halogen atom, with a malonate in the presence of a base, (b) heating the resulting aminoazolopyrimidin-5-yl malonate of formula III 1 2 RxNR2 A (L) n 4N -'KN / OR TO N R - N.'N. (111)   Wherein R1, R4, A, L and n have the meanings given in   preceding claims, and R represents an alkyl group, in the presence of an acid.   A compound of formula III wherein R, R, R 2, R 4, A, L and n have the meanings given in preceding claims.   10. Fungicidal composition, characterized in that it comprises a vehicle and, as active agent, at least one compound of formula I such   as defined in any one of claims 1 to 7.   11. Method for controlling a fungus at a place, characterized in that it comprises the treatment of the place with a compound of formula I such   as defined in any one of claims 1 to 7 or with a   composition as defined in claim 10.   12. Use as a fungicide of a compound of formula I as   defined in any one of claims 1 to 7 or a composition   as defined in claim 10.