JP2000103790A - Bactericidal and fungicidal trihalophenyl- triazopyrimidines - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound exhibiting excellent bactericidal and fungicidal activities, particularly against Pyricularia oryzae which is the causative agent of rice blast disease. SOLUTION: This compound is represented by formula I [R1 and R2 are each H, a (substituted)alkyl or the like or form a (substituted)heterocyclic ring together with the interjacent nitrogen atom; R3 to R5 are each F or Cl and at least one thereof is Cl; X is a halogen], e.g. 5-chloro-6-(2,6-dichloro-4- fluorophenyl)-7-(4-methyl-piperiding-1-yl)-[1,2,4]triazo[1,5-α]pyrimidine. The compound of formula I is obtained by reacting a compound of formula II e.g. 5,7-dichloro-6-(2,6-dichloro-4-fluoro-phenyl)-[1,2,4]triazolo[1,5-α]pyrimidine} with a compound of formula III (e.g. 4-methylpiperidine), preferably in the presence of a base such as triethylamine and a solvent such as dischloromethane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to certain triazolopyrimidine compounds, methods for their preparation, compositions containing the compounds, and treatment of fungi and molds at a location comprising treating the location with the compound. It relates to methods of controlling and their use as fungicides.

[0002] EP-A-0071792 has the general formula

[0003]

Embedded image Wherein R ¹ is alkyl, halogen, each of which is optionally substituted with halogen or alkoxy,
Alkoxy, cyano, cycloalkyl, aryl, aryloxy, arylthio, aralkyl, arylthio, arylalkyl, arylalkyloxy or arylalkylthio, or (R ¹ ) _n is benzene, indane or tetrahydrogen fused to a phenyl ring Represents a naphthalene ring, wherein the aromatic moiety in the above groups is optionally substituted by alkyl, alkoxy, halogen or cyano, n is 1 or 2, and R ² and R ³ are each hydrogen, alkyl or aryl, a represents a nitrogen atom or a CR ⁴ group, and R ⁴
Is as defined for R ² but may be halogen, cyano or alkoxycarbonyl or may be combined with R ³ to form an alkylene chain containing up to two double bonds. I'm charging. These compounds are useful for various phytopathogenic fungi and molds, especially algal fungi.
It is said to be active against those of the class (phycomycete). However, the proof of bactericidal / fungicidal activity is
It is shown only for these compounds against Plasmopara viticola, a member of the class Oomycete. US Patent 5,593,99
No. 6 is general formula 1

[0004]

Embedded image Wherein R ¹ represents an optionally substituted alkyl, alkenyl, alkadienyl, cycloalkyl, bicycloalkyl or heterocyclyl group, R ² represents a hydrogen atom or an alkyl group, or R ¹ and R ² Represents together with an intermediate nitrogen atom an optionally substituted heterocyclic ring, R ³ represents an optionally substituted aryl group, and R ⁴
Represents hydrogen or a halogen atom or a group —NR ⁵ R ⁶ , wherein R ⁵ represents a hydrogen atom or an amino, alkyl, cycloalkyl or bicycloalkyl group and R ⁶ represents a hydrogen atom or an alkyl group. Include. Therefore, compounds wherein R ³ is a trichlorophenyl group are generally included by this patent application. These compounds are of the class Ascomycetes, for example,
Venturia inaequalis and Hyphomycetes classes, such as Alternaria solani and Botrytis cinerea (Bo
trytis cinerea), which is said to be active against fungi and molds. However, if R ³ is 2,
No single compound is disclosed which is a phenyl group trisubstituted at the 4,6-position by a fluorine and / or chlorine atom.

[0005]

SUMMARY OF THE INVENTION The present invention provides a compound of formula I

[0006]

Embedded image [Wherein R ¹ and R ² are each independently a hydrogen atom or optionally substituted alkyl, alkenyl,
An alkynyl, alkadienyl, haloalkyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl group, or R ¹ and R ² together with an intermediate nitrogen atom, optionally substituted heterocycle R ³ , R ⁴ and R ⁵ each independently represent a fluorine or chlorine atom, provided that at least one of R ³ , R ⁴ and R ⁵ is a chlorine atom, and X is A halogen atom].

The novel compounds are found in a variety of crops, in particular Pyricularia oryzae (Pyr), a causative agent of rice blast.
icularia oryzae) [Magnaport
he grisea)].

It is an object of the present invention to provide new selective fungicidal compounds.

It is also an object of the present invention to provide a method for controlling undesirable fungi and fungi, in particular, Pyricularia oryzae, a causative agent of rice blast, by contacting a rice plant with a fungicidally and fungicidally effective amount of a novel compound. It is an object of the invention.

It is another object of the present invention to provide a fungicidal and fungicidal composition containing a novel compound as an active ingredient.

[0011] These and other objects and features of the present invention will become more apparent from the detailed description set forth below and the appended claims.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Formula I

[0013]

Embedded image Wherein R ^{1 to} R ⁵ and X have the meanings indicated above with respect to formula I, against a wide range of fungi and fungi, in particular the pyrricularia, a causative agent of rice blast. It was surprisingly found that Oryzae exhibited excellent bactericidal and fungicidal activity.

The term halogen, as used herein, refers to bromine, iodine, chlorine or fluorine, and especially bromine,
It includes chlorine or fluorine atoms, especially chlorine atoms.

The optionally substituted moieties may be unsubstituted or have one to the maximum possible number of substituents. Typically, there are 0-2 substituents. The term "optionally substituted" as used herein with respect to a group means that the group is subject to one or more halogen atoms, or nitro, cyano,
Hydroxy, alkyl (preferably C _1-6 alkyl),
Cycloalkyl (preferably C _3-6 cycloalkyl),
Cycloalkenyl (preferably C _3-6 cycloalkenyl), haloalkyl (preferably C _1-6 haloalkyl), halocycloalkyl (preferably C _3-6 halocycloalkyl), alkoxy (preferably C _1-6 alkoxy), It may be substituted by haloalkoxy (preferably C _1-6 haloalkoxy), trialkylsilyl (preferably tri-C _1-4 alkylsilyl), phenyl, halo- or dihalo-phenyl or pyridyl group. I do.

The terms alkyl, alkenyl, alkynyl, alkadienyl, haloalkyl as used herein with respect to groups or moieties refer to straight or branched groups or moieties. Preferably, such groups or moieties have up to 10, especially up to 6, carbon atoms. Suitably, the alkyl moiety has 1 to 6, preferably 1 to 4, carbon atoms. Preferred alkyl moieties are ethyl or, in particular, methyl groups. Suitably, the alkenyl moiety has 2 to 2 carbon atoms.
6. Preferred alkenyl moieties are allyl or, especially, 2-methylallyl. Suitably, the haloalkyl moiety has 1 to 6 fluorine atoms. Preferred haloalkyl moieties are 2,2,2-trifluoroethyl and 1,1
Includes 1,1-trifluoroprop-2-yl groups.

The term wherein aryl as used with respect to a radical or moiety, optionally substituted with one or more halogen atoms, nitro, cyano, alkyl, preferably C _1-6 alkyl, and / or alkoxy, preferably C _1-6 alkoxy, having 6, 10 or 14 carbon atoms, preferably 6 or 10 carbon atoms which may be substituted
Refers to aryl groups, especially phenyl.

The term heteroaryl as used herein with respect to groups or moieties is selected from carbon, nitrogen, oxygen and sulfur, with 5 or 6 rings such that at least one of them is nitrogen, oxygen or sulfur. A heteroaryl group having atoms, especially pyridyl, pyrimidyl, pyrazolyl or thienyl.

The term cycloalkyl, as used herein with reference to a group or moiety, optionally refers to one or more halogen atoms, nitro, cyano, alkyl, preferably C _1-6 alkyl, and / or alkoxy, preferably alkoxy. C _1-6 alkoxy refers to a cycloalkyl group having 3 to 8, preferably 5 to 7 carbon atoms which may be substituted by C _1-6 alkoxy, especially cyclopentyl.

The term bicycloalkyl as used herein with respect to groups or moieties optionally refers to one or more halogen atoms, nitro, cyano, alkyl, preferably C _1-6 alkyl, and / or alkoxy,
Preferably, it refers to a C 5-6, preferably 6-9, bicycloalkyl group, particularly bicycloheptyl, which may be substituted by C _1-6 alkoxy.

The term heterocyclyl as used herein with respect to groups or moieties is selected from carbon, nitrogen, oxygen and sulfur, with 5 or 6 ring atoms such that at least one of them is nitrogen, oxygen or sulfur. A saturated heterocyclyl group optionally substituted by one or more halogen atoms, nitro, cyano, alkyl, preferably C _1-6 alkyl, and / or alkoxy, preferably C _1-6 alkoxy Point out. Pyrrolodinyl, pyrazolidinyl, piperidinyl, piperazinyl and morpholin-4-yl are particularly preferred.

The invention is especially directed to the alkyl or haloalkyl moiety of the radical R ¹ or R ² , which may be linear or branched, having up to 10 carbon atoms, preferably 1 to 9, and more preferably 2 carbon atoms. -6, wherein the alkenyl or alkynyl moiety of the substituent R ¹ or R ² has up to 10 carbon atoms, preferably 2-9, and more preferably 3-6, and the substituent R ¹ or R ² The cycloalkyl moiety has 3 to 10, preferably 3 to 8, more preferably 3 to 6, and the bicycloalkyl moiety of the substituent R ¹ or R ² has 5 to 9, preferably 7 to 9 carbon atoms. And the aryl moiety of the substituent R ¹ or R ² has 6 carbon atoms;
A compound of formula I which is 10 or 14, preferably 6 or 10.

In a preferred embodiment, the present invention relates to a linear or branched R ¹ optionally substituted by one to three halogen atoms or C _1-10 alkyl or C _1-10 alkoxy groups. C _1-10 alkyl (particularly a branched C _3-10 alkyl group), C _3-8 cycloalkyl, C _5-9 bicycloalkyl, C _3-8 cycloalkyl-C _1-6 alkyl, C _{1 Includes} compounds of Formula I that represent a _-10 alkoxy-C _1-6 alkyl, C _1-10 haloalkyl or phenyl group.

R ² is a hydrogen atom, C _1-10 alkyl or C
Preference is also given to compounds of the formula I which represent a _1-10 haloalkyl radical, in particular a hydrogen atom.

R ¹ is a C _1-10 haloalkyl group, preferably a polyfluorinated alkyl group, especially 2,2,2-trifluoroethyl, 2- (1,1,1-trifluoropropyl) or 2- When representing a (1,1,1-trifluorobutyl) group, R ² preferably represents a hydrogen atom.

R ¹ is optionally substituted C
_{When representing a 3-8} cycloalkyl group, preferably a cyclopentyl or cyclohexyl group, R ² preferably represents a hydrogen atom or a C _1-6 alkyl group.

In another preferred embodiment of the invention, R ¹ and R ² together with an intermediate nitrogen atom are optionally substituted heterocyclic rings, preferably optionally substituted heterocyclic rings. Pyrrolidine, piperidine, tetrahydropyridine, especially 1,2,3,6-tetrahydropyridine, optionally substituted by one or more C _1-7 heterocyclic rings, in particular optionally substituted by one or more C _1-10 alkyl groups. Or forming an azepane ring, most preferably 4-methylpiperidine.

The present invention particularly relates to a compound wherein R ³ , R ⁴ and R ⁵ are chlorine atoms; R ³ is a chlorine atom, R ⁴ is a fluorine atom and R ⁵ is a fluorine or chlorine atom; R ⁵ is a chlorine atom; or R ³ and R ⁴ are a fluorine atom and R ⁵ is a chlorine atom.

Thus, in formula I, the phenyl group

[0030]

Embedded image Is preferably

[0031]

Embedded image Represents a group selected from

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

The compounds according to formula I may be oils, gums, or waxy or crystalline solid substances. They exhibit enhanced fungicidal properties against rice illness and mildew, such as systemic action and increased fungal toxicity, compared to known fungicides. For example, they are phytopathogenic fungi and fungi, such as Alternaria solani, Botrytis cinerea, Cercospora beticola, Cladosporium herbarum, Corticium. Corticiumrolfsii, Erichife Graminis
(Erysiphe graminis), Helminthosporium tritici repenti
s), Leptosphaeria nodrum
orum), Micronectriell
a nivalis), Monilinia fructigena (Monilinia fru)
ctigena), Mycosphaere Ligricola (Mycosphaere)
lla ligulicola), Mycosperaella Pinodes (Mycosp
haerella pinodes), Pyricula oryzae (Pyricula)
ria oryzae), Rhizoctonia sola
ni) and Sclerotinia sclerotiorum (Scleroti
nia sclerotiorum), Uncinula n
ecator), in particular for the control of Pyricularia oryzae, and can be used in agriculture or related fields. The compounds of the formula I according to the invention have a high fungicidal activity over a wide concentration range and can be used without difficulty in agriculture.

Furthermore, the compounds according to the invention show an increased suppression of fungi and molds, especially rice blast, as compared to conventional fungicides.

Using a compound as defined in formula I wherein X represents a chlorine atom, R ² represents a hydrogen atom, R ³ and R ⁵ represent a chlorine atom and R ⁴ represents a chlorine or fluorine atom, Good results are obtained with regard to the control of phytopathogenic fungi and molds.

Good results are obtained with respect to the control of phytopathogenic fungi, for example by using the compounds of the formula I: [5-chloro-6- (2,6-dichloro-4-) Fluoro-phenyl)-[1,2,4] triazolo
[1,5-α] pyrimidin-7-yl] -cyclopentyl-
Amine, [5-chloro-6- (2,6-dichloro-4-fluoro-phenyl) -7- (4-methyl-piperidine-1
-Yl)-[1,2,4] triazolo [1,5-α] pyrimidine, [5-chloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] triazolo [1,5-α] pyrimidin-7-yl]-(2,2,2-trifluoro-ethyl) -amine, [5-chloro-6- (2,6-dichloro-4)
-Fluoro-phenyl)-[1,2,4] triazolo [1,5
-Α] pyrimidin-7-yl]-(1,1,1-trifluoro-prop-2-yl) -amine, [5-chloro-6-
(2,6-dichloro-4-fluoro-phenyl)-[1,2,
4] triazolo [1,5-α] pyrimidin-7-yl] -diethyl-amine, [5-chloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] triazolo
[1,5-α] pyrimidin-7-yl] -isopropyl-amine, sec-butyl- [5-chloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] Triazolo [1,5-α] pyrimidin-7-yl] -amine, bicyclo [2.2.1] hept-2-yl- [5-chloro-6-
(2,6-dichloro-4-fluoro-phenyl)-[1,2,
4] triazolo [1,5-α] pyrimidin-7-yl] -amine, [5-chloro-6- (2-chloro-4,6-difluoro-phenyl)-[1,2,4] triazolo [1 , 5-α] pyrimidin-7-yl] -cyclopentyl-amine, [5-
Chloro-6- (2-chloro-4,6-difluoro-phenyl) -7- (4-methyl-piperidin-1-yl)-[1,
2,4] triazolo [1,5-α] pyrimidine, [5-chloro-6- (2-chloro-4,6-difluoro-phenyl)-
[1,2,4] triazolo [1,5-α] pyrimidin-7-yl]-(2,2,2-trifluoro-ethyl) -amine, [5
-Chloro-6- (2-chloro-4,6-difluoro-phenyl)-[1,2,4] triazolo [1,5-α] pyrimidine-
7-yl]-(1,1,1-trifluoro-prop-2-yl) -amine, [5-chloro-6- (2-chloro-4,6-
Difluoro-phenyl)-[1,2,4] triazolo [1,5
-Α] pyrimidin-7-yl] -diethyl-amine, [5
-Chloro-6- (2-chloro-4,6-difluoro-phenyl)-[1,2,4] triazolo [1,5-α] pyrimidine-
7-yl] -isopropyl-amine, sec-butyl-
[5-chloro-6- (2-chloro-4,6-difluoro-
Phenyl)-[1,2,4] triazolo [1,5-α] pyrimidin-7-yl] -amine, bicyclo [2.2.1] hept-
2-yl- [5-chloro-6- (2-chloro-4,6-difluoro-phenyl)-[1,2,4] triazolo [1,5-
α] 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, [5-chloro-6- (2,4,6-trichlorophenyl) -7- (3
-Methyl-piperidin-1-yl]-[1,2,4] triazolo [1,5-α] pyrimidine, cyclopentyl- [5-chloro-6- (2,4,6-trichlorophenyl)-[1, Two,
4] triazolo [1,5-a] pyrimidin-7-yl] -amine, [5-chloro-6- (2,4,6-trichloro-phenyl) -7- (4-methyl-piperidin-1-yl) ]-
[1,2,4] triazolo [1,5-α] pyrimidine, diethyl- [5-chloro-6- (2,4,6-trichlorophenyl)-[1,2,4] triazolo [1,5-] a] Pyrimidine-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] pyrimidine-
7-yl] -amine, N-ethyl-N-2-methylallyl- [5-chloro-6- (2,4,6-trichlorophenyl)-[1,2,4] triazolo [1,5-a] Pyrimidine-7
-Yl] -amine and 1,1,1-trifluoroprop-2-yl- [5-chloro-6- (2,4,6-trichlorophenyl)-[1,2,4] triazolo [1, 5-a] Pyrimidin-7-yl] -amine.

The present invention further provides a compound of formula II

[0038]

Embedded image Wherein R ³ , R ⁴ , R ⁵ and X are as defined for formula I, with a compound of formula III

[0039]

Embedded image There is also provided a process for the preparation of a compound of formula I as defined above comprising treatment with an amine of the formula wherein R ¹ and R ² are as defined for formula I.

The compound of formula II is new and 3-amino-1,2,4-triazole is converted to a compound of formula IV

[0041]

Embedded image Wherein R ³ , R ⁴ and R ⁵ are as defined for formula I and R represents alkyl, preferably C _1-6 alkyl, especially methyl or ethyl. ,
It can be prepared by reacting a (6-trihalophenyl) -substituted malonic ester under alkaline conditions, preferably using high-boiling tertiary amines such as tri-n-butylamine.

The resulting 5,7-dihydroxy-6- (2,4,
The 6-trihalophenyl) -triazolopyrimidine is subsequently treated with a halogenating agent, preferably a brominating or chlorinating agent, such as phosphorus oxybromide or phosphorus oxychloride, neat or in the presence of a solvent. The reaction is between 0 ° C and 15
The reaction is suitably carried out at a temperature in the range of 0 ° C, the preferred reaction temperature being between 80 ° C and 125 ° C.

The compound of the formula IV is preferably, for example, J. Se.
tsume et al. Chemistry Letters, pp. 367-370, 1981
Prepared by the reaction of 2,4,6-trihalobromobenzene with a sodium dialkylmalonate in the presence of a copper (I) salt.

Thus, the present invention provides novel intermediates of the formula II, in particular 5,7-dichloro-6- (2,4,6-trichloro-phenyl)-[1,2,4] triazolo [1,5- α] pyrimidine,
5,7-dichloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] triazolo [1,5-α] pyrimidine and 5,7-dichloro-6- (2- Chloro-4,
6-difluoro-phenyl)-[1,2,4] triazolo
[1,5-α] pyrimidine, the corresponding (2,4,6-trihalophenyl) -malonate dialkyls of formula IV, and the corresponding 5,7-dihydroxy-6- (2,4,6-trihalophenyl )-[1,2,4] triazolo [1,5-α] pyrimidines.

The reaction between the 5,7-dihalo-6- (2,4,6-trihalophenyl) -triazolopyrimidines of the formula II and the amine of the formula III is preferably carried out in the presence of a solvent. Suitable solvents include ethers such as dioxane, diethyl ether and especially tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic hydrocarbons such as toluene. The reaction is 0
It is suitably carried out at a temperature in the approximate range of from 0C to 70C, the preferred reaction temperature is from 10C to 13C. It is also preferable to carry out the reaction in the presence of a base. Suitable bases include tertiary amines, such as triethylamine, and inorganic bases, such as potassium carbonate or sodium carbonate.
Alternatively, an excess of the compound of formula III may be used as a base.

Due to their excellent activity, the compounds of the formula I are suitable for all plants which are not desired to be infected by phytopathogenic fungi, such as cereals, solanaceous crops, vegetables, legumes,
It can be used in growing apples and grapes.

The invention further provides a fungicidal composition which comprises at least one active compound of the formula I as defined above and one or more carriers. Also provided is a method of preparing such a composition comprising combining a compound of Formula I with one or more carriers. Such compositions may contain a single active ingredient of the present invention or a mixture of several active ingredients. It is also conceivable that different isomers or mixtures of isomers may have different activity levels or ranges and that the compositions therefore comprise individual isomers or mixtures of isomers.

The composition according to the invention is preferably between 0.5 and
Contains 95% (w / w) active ingredient.

The carrier in the composition according to the invention may be used for facilitating its application to the place to be treated, for example a plant, seed, soil or water in which the plant grows, or for storage, It is a substance that can be combined with the active ingredient to facilitate transport or handling. The carrier can be a solid or liquid, and includes substances that are usually gaseous but are pressurized to form a liquid.

The composition may be prepared by known processes, for example, as an emulsion or emulsifiable concentrate, a solution, an oil-in-water emulsion, a wettable powder, a soluble powder, a concentrated suspension, a powder, a granule, a water-dispersible granule. It can be manufactured into agents, aerosols, microcapsules, gels, tablets and other formulation types. These steps involve strong mixing of the active ingredient with other substances, such as fillers, solvents, solid carriers, surface-active compounds (surfactants), and optionally solid and / or liquid auxiliaries and / or adjuvants. And / or grinding. Depending on the desired purpose and the given environment, the application forms can be selected as well as the composition, for example spraying, spraying, dispersing or pouring.

[0051] Suitable solvents are aromatic hydrocarbons in the practice of the present invention, for example, Solvesso (Solvesso) ^R 200, substituted naphthalenes, phthalates, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons,
For example, cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol mono- and dimethyl ether, ketones such as cyclohexanone, strong polar solvents such as N-methyl-2-pyrrolidone, or Includes gamma-butyrolactone, higher alkylpyrrolidones such as n-octylpyrrolidone or cyclohexylpyrrolidone, epoxidized vegetable oil esters such as methylated palm or soybean oil esters and water. Mixtures of different solvents are often suitable.

Solid carriers which can be used for dusts, wettable powders, water-dispersible granules or granules are mineral fillers, such as calcite,
It may be talc, kaolin, montmorillonite or attapulgite. Physical properties can be improved by the addition of highly dispersible silica gel or polymers. The carrier for the granules may be a porous material, such as pumice, kaolin, sepiolite, bentonite, and the non-sorbent carrier may be calcite or sand. In addition, a number of pre-granulated inorganic or organic substances, such as dolomite or milled plant residues, may be used.

The pesticidal compositions are often stored and transported in concentrated form, which is subsequently diluted by the user prior to application. The presence of a small amount of a surfactant, a carrier, facilitates this dilution step. Therefore, preferably at least one carrier in the composition according to the invention is a surfactant. For example, the composition can contain two or more carriers, at least one of which is a surfactant.

The surfactant preferably has good dispersibility,
Nonionic, anionic, having emulsifying and wetting properties,
It may be a cationic or amphoteric surfactant, which depends on the nature of the compound according to Formula I to be formulated. Surfactants also include mixtures of individual surfactants.

[0055] The wettable powder of the present invention is suitably about 5-90.
In addition to the w / w% active ingredient, and the solid inert carrier, about 3-10 w / w% dispersing and wetting agents, and about 0-10 w / w% of one or more stabilizers and And / or contains other additives, such as penetrants or adhesives. Dusts can be formulated as concentrated powders having a composition similar to that of a wettable powder but free of dispersants, and diluted in situ with another solid carrier to about 0.5.
Compositions containing from 10 to 10% w / w of active ingredient can be prepared. The water-dispersible granules and granules are suitably about 0.15.
It has dimensions between 0.5 mm and 2.0 mm and can be manufactured by various techniques known in the art. Generally, these granules contain from about 0.5 to 90% w / w active ingredient and from about 0 to 20% w / w additives such as stabilizers, surfactants, delayed release modifiers and binders. Agent,
Will be contained. The emulsifiable concentrate of the present invention is suitably, in addition to the solvent or solvent mixture, about 1-80 wt /
It contains, by volume, active ingredient, about 2-20% w / v emulsifier and about 0-20% w / v other additives such as stabilizers, penetrants and corrosion inhibitors. Stable non-
The concentrated suspension may be milled to give a depositable flowable product, and preferably from about 5 to 75% w / v active ingredient, from about 0.5 to 15% w / v dispersion. Agent,
About 0.1 to 10% w / v suspension, such as protective colloid and thixotropic agent, about 0 to 10% w / v
Contains other additives such as foam inhibitors, corrosion inhibitors, stabilizers, penetrants and tackifiers, and organic liquids in which water or active ingredients are substantially insoluble to prevent deposition and crystallization Certain organic solids or inorganic salts may be present dissolved in the formulation to assist in the preparation of or as a cryoprotectant.

Aqueous dispersions and emulsions, such as compositions obtained by diluting the formulated product according to the invention with water, are also within the scope of the invention.

The duration of the protective activity of the compounds according to the invention can be increased by using carriers which will release the pesticidal compound slowly in the environment of the plant to be protected.

The biological activity of the active ingredients can be increased by including an adjuvant in the spray dilution. Adjuvants are defined herein as substances that can increase the biological activity of the active ingredient, but are not biologically active to some extent by themselves. The adjuvant may be included in the formulation as a co-formulation or carrier, or may be added to the spray tank together with the formulation containing the active ingredient.

For convenience, the compositions are preferably in concentrated form, but the end user will generally use the diluted compositions. The composition can be diluted to a concentration of about 0.001% active ingredient, preferably in the range of about 0.01 to 10 kg active ingredient / ha.

Examples of formulations according to the invention are given below: Concentrated emulsion (EC) active ingredient Compound of Example 5 30% (w / v) Emulsifier Atlox ^R 4856B / Atlox ^R 4858B ¹⁾ 5% (w / w ⁾ Volume) [mixture containing calcium alkylaryl sulfonate, fatty alcohol ethoxylates and light aromatics / mixture containing calcium alkylaryl sulfonate, fatty alcohol ethoxylates lightweight aromatic] Solvent Shellsol ^R A ^{2 )} and 1000 ml (C ₉ -C ₁₀ aromatic mixtures hydrocarbons) compound 50 percent of suspension concentrate (SC) active ingredient example 5 (weight / volume) dispersing agent Soprophor ^R FL ^{3) 3%} (wt (Volume) (polyoxyethylene polyarylphenyl ether phosphate amine salt) Antifoaming agent Rhodorsil ^R 422 ³⁾ 0.2% (weight / volume) (nonionic aqueous emulsion of polydimethylsiloxanes) Structural agent Kelzan ^R S ⁴⁾ 0. 2% (weight / volume) (xanthan gum) Antifreeze Propylene glycol 5% (weight / volume) Biocide Proxel ^R5) 0.1% (weight / volume) (20% 1,2-benisothiazolin-3-one A water-dispersible powder (WP) active ingredient containing 1,000 ml of water 60% (weight / weight) of the compound of Example 11 Wetting agent Atlox ^R 4995B ¹⁾ 2% (weight / weight) (polyoxyethylene Alkyl ether) Dispersant Witcosperse ^R D-60 ⁶⁾ 3% (w / w) (mixture of sodium salt of condensed naphthalenesulfonic acid and alkylaryl polyoxyacetate) Carrier / filler kaolin 35% (w / w) water Dispersible granule (WG) active ingredient Compound of Example 11 50% (w / w) Dispersant / Witcosperse ^R D-60 ⁶⁾ 8% (w / w) Binder (sodium salt of condensed naphthalenesulfonic acid and alkyl) Sulfonate mixture) Wetting agent Morwet ^R EFW ⁶⁾ 2% (w / w) Condensation product of aldehyde) Foaming inhibitor Rhodorsil ^R EP6703 ³⁾ 1% (w / w) (encapsulated silicone) Disintegrant Agrimer ^R ATF ⁷⁾ 2% (w / w) (N-vinyl-2-pyrrolidone Carrier / filler kaolin 35% (weight / weight) ¹⁾ Commercially available from ICI Surfactants ²⁾ Commercially available from Deutsche Shell AG ³⁾ Commercially available from Rhoene-Poulenc ⁴⁾ Commercially available from Kelco Co. ⁵⁾ Commercially available from Zeneca ⁶⁾ From Witco Commercially available ⁷⁾ Commercially available from International Specialty Products The composition of the present invention may be applied to plants or their environment simultaneously or sequentially with other active substances. Can be.
These other active substances are fertilizers, reagents that supply rare elements,
Or it can be other formulations that affect plant growth. They induce resistance in selective herbicides, insecticides, fungicides, fungicides, bactericides, nematicides, algicides, molluscides, rodenticides, viricides, plants Compounds, biological inhibitors such as viruses, bacteria, nematodes, fungi and other microorganisms, bird and animal repellents, and plant growth regulators, or even mixtures of several of these formulations. It can be and optionally be used in conjunction with other carrier materials, surfactants or other additives which facilitate application, which are commonly used in compounding techniques.

In addition, other pesticides may have a synergistic effect on the pesticidal activity of the compounds of the formula I.

Other fungicidal compounds include, for example, cereal (wheat) diseases such as Erysipha, Puccinia, Septoria, Gibberella
(Gibberella) and Helminthosporium
(orium) species, capable of controlling grape seed and soil-borne diseases and downy mildew and mildew, early and late blight of solanaceous crops, and mildew and rot of apples It is. These mixtures of fungicides may have a broader activity range than the compounds of the formula I alone. In addition, other sterilization
Fungicides may have a synergistic effect on the fungicidal activity of the compounds of formula I.

Examples of other fungicidal compounds are: AC382042, alanycarb
b), aldimorph, ampropylphos (am
propylfos), andoprim (andoprim), anilazine (ani
lazine), azaconazole, azafenidin, azoxystrobin,
Benalaxyl, benomyl, bethoxazin, binapacryl, bitertanol, blasticidin S (blasticid S)
in S), Bordeaux mixture, bromuconazole, bupirimat
e), captafol, captan, carbendazim, carboxin,
Carpropamid, chlorbenzthiazone
(chlorbenzthiazon), chlorothaloni
l), chlozolinate, copper-containing compound,
For example, copper oxychloride, copper sulfate, cycloheximide
(cycloheximide), cymoxanil, cypofuram, cyproconazole, cyprodinil, cyprodinil, dichlofluanid
anid), dichlone, dichloran,
Diclobutrazol, diclosimet
(diclocymet), diclomezine, dietofencarb, difenoconazole (dife
noconazole), diflumetorim, dimethirimol, dimethomorph,
Diniconazole, dinocacap
p), ditalimfos, dithianon (dithian
on), dodemorph, dodine, edifenphos, epoxyconazole (epoxico
nazole), etaconazole, etaboxam
(ethaboxam), ethirimol (ethirimol), etridiazole (etridiazole), famoxadone (famoxadone), fenanidone (fenanidone), fenapanil (fenapanil), fenarimol (fenarimol), fenbuconazole (fenbucon
azole), fenfuram, fenhexamide (f
enhexamid), fenpiclonil, fenpropidin, fenpropimorph
pimorph), fentin, fentin acetate
(fentin acetate), fentin hydroxide
droxide), ferimzone (ferimzone), fluazinam (fl
uazinam), fludioxonil, flumetover, fluquinconazo
le), flusilazole, flusulfamide
(flusulfamide), flutlanil (flutolanil), flutriafol (flutriafol), folpet (folpet), fosetyl-aluminium (fosetyl-aluminium), fveridazole (fuberidazole), furaxyl (furalaxyl), furametpyr (furametpyr), guazatine (guazatine) , Hexaconazole, imazalil,
Iminoctadine, ipconazole (ipcon
azole), iprodione, iprovalicarb
(iprovalicarb), ISK-916, isoprothiolane (i
soprothiolane), kasugamycin, kitazin P, kresoxim-methyl (resoxim-me
thyl), mancozeb (mancozeb), maneb (maneb), mepanipyrim (mepanipyrim), mepronil (mepronil), metalaxyl (metalaxyl), metconazole (metconazole), mesfloxam (methfuroxam), microbutanil (myclobut)
anil), neoasozin, nickel dimethyldithiocarbamate, nitrothalisopropyl (nitrothal
isopropyl), nuarimol, off-race (ofura
ce), organic mercury compounds, oxadixyl, oxpoconazole, oxycarboxine
(oxycarboxin), penconazole, pencuron, phenazineox
ide), phthalide, picoxystrobin (pico
xystrobin), polyoxin D, polyram (p
olyram), probenazole, prochloraz
(prochloraz), procymidione, propamocarb, propiconazol
ole), propineb, pyrazophos
s), pyrifenox, pyrimethanil (pyri
methanil), pyroquilon, pyroxifur (py
roxyfur), quinomethionate (qinomethionate), quinoxyfen (quinoxyfen), quintozene, RH
-7281, silthiopham (MON-
65500), spiroxamine, SSF
-126, SSF-129, streptomycin (strep
tomycin), sulfur, tebuconazole, tecloftalame, technazene,
Tetraconazole, thiabendazole
(thiabendazole), thifluzamide, thiophanate-methyl, thiram (thi
ram), tolclofosmethyl, tolylfluanid, triadimefon
efon), triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph
h), trifloxystrobin, triflumizole, triforin
e), tritonazole, validamycin A
(validamycin A), vinclozolin, XR
D-563, zarilamid, zineb,
And ziram.

Furthermore, the co-formulations according to the invention comprise at least one compound of the formula I and biological regulators of the type described below, such as viruses, bacteria, nematodes, fungi and insects, weeds or fungi. Other microorganisms suitable for controlling plant disease or inducing host resistance in plants,
May be contained. Examples of such biological modulators are
Bacillus thuringiensi
s), Verticillium lecani
i), Autografica California NPV (Autogra
phica californica NPV), View Barrier Basiana (Bea
uvaria bassiana), Amperomises quisqualis (Amp
elomyces quisqualis), Bacilis subtilis
subtilis) and Pseudomonas chlororaffis (Pseudom
onas chlororaphis, Pseudomonas fluorescens, Steptomyces griseoviridis and Trichoderma harzianum.

In addition, the compositions according to the invention are characterized by at least one compound of the formula I and a chemical agent which induces systemic acquired resistance in plants, such as isonicotinic acid or its derivatives, 2,2-dichloro- It may contain 3,3-dimethylcyclopropylcarboxylic acid or BION.

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

The invention furthermore relates to the use of the compounds of the formula I as fungicides, or to the compositions as defined above, and to a method of controlling certain places with such compounds or compositions ( This includes, for example, the treatment of plants that have been or have been attacked by fungi, the seeds of such plants, or the places where such plants are growing or are the medium to be grown. ) Is also provided.

The invention has wide application in the protection of crops and decorative plants against fungal and fungal attack. Typical crops that can be protected are grapes, grain crops such as wheat and barley, rice, sugar beet, top fruits (top fru
it), peanuts, potatoes, vegetables and tomatoes. The duration of protection generally depends on the particular compound chosen and various external factors, such as climate, the effects of which can be reduced by the use of suitable formulations.

The following examples further illustrate the invention. However, it should be understood that the invention is not limited to the specific embodiments described below.

[0070]

EXAMPLE 1 Preparation of 1-bromo-2,6-dichloro-4-fluoro-benzene Bromine (0.6 mol) was converted to 1,3-dichloro-5-fluoro-benzene.
It is added within 2 hours to a mixture of benzene (0.6 mol) and iron powder. The brown reaction mixture is stirred at room temperature for 16 hours and subsequently washed with dichloromethane and water. The organic layer is separated, washed with sodium hydrogen carbonate solution and dried with anhydrous sodium sulphate. The solvent is evaporated under reduced pressure. The raw product is recrystallized in ethanol to give 61 g of the product as a white powder with a melting point of 83 ° C.

Example 2 Preparation of diethyl (2,6-dichloro-4-fluoro-phenyl) -malonate Diethyl malonate (0.49 mol) was converted to sodium hydride (0.51 mol) and 1,4-dioxane (140m
Add to the mixture of 1) at 55-60 ° C within 2 hours. The mixture is stirred at 55 ° C. for 10 minutes and copper (I) bromide (0.05 mol) is added. After 15 minutes, 1-bromo-2,6-dichloro-4-fluoro-benzene (0.
25 mol) and a mixture of 1,4-dioxane (10 ml). The reaction mixture is heated at 100 ° C. for 15 hours and cooled to 15 ° C. Hydrochloric acid (12N, 35ml) is added slowly at 15-20 ° C. The precipitate is filtered off. The filtrate is extracted with diethyl ether. The organic phase is separated off, dried with anhydrous sodium sulphate and filtered. The filtrate is evaporated under reduced pressure to give 44 g of the product as yellow crystals with a melting point of 170.degree. Similarly, (2-chloro-4,
This gives diethyl 6-difluoro-phenyl) -malonate.

Example 3 5,7-Dihydroxy-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] -triazolo [1.5α]
Preparation of pyrimidine 3-amino-1,2,4-triazole (0.15 mol), (2,6-dichloro-4-fluoro-phenyl)-
A mixture of diethyl malonate (0.15 mol, obtained from Example 2) and tributylamine (0.15 mol) is heated at 180 ° C. under reflux for 6 hours. Cool the reaction mixture to 70 ° C. Aqueous sodium hydroxide (13.6
g / 200 ml of H ₂ O) are added and the reaction mixture is
Stir for 0 minutes. The organic phase is separated off and the aqueous phase is extracted with diethyl ether. The aqueous phase is acidified with concentrated hydrochloric acid. The white precipitate was collected by filtration and dried to give 40.6 g of 26.
This gives a product with a melting point of 7 ° C.

Example 4 Preparation of 5,7-dichloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] -triazolo [1.5α] pyrimidine 5,7-dihydroxy -6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] -triazolo [1.5α]
A mixture of pyrimidine (0.14 mol, obtained from Example 3) and phosphorus oxychloride (110 ml) is heated at reflux at 120 ° C. for 8 hours. The phosphorus oxychloride is partially distilled off. The residue is poured into a mixture of dichloromethane and water. The organic layer is separated, dried with anhydrous sodium sulfate and filtered. The filtrate is concentrated in vacuo and then applied on flash column chromatography. The column is continuously eluted with diethyl ether / petroleum ether (1: 2 v / v) to yield 17 g of a yellow powder with a melting point of 149 ° C. Similarly, 5,7-dichloro- (2-chloro-4,6-difluoro-phenyl) -1,2,4-triazolo [1.5α] pyrimidine having a melting point of 124 ° C. is obtained.

Example 5 5-chloro-6- (2,6-dichloro-4-fluoro-phenyl) -7- (4-methyl-piperidin-1-yl)-
Preparation of [1,2,4] triazolo [1,5-α] pyrimidine 4-methylpiperidine (3.0 mmol), triethylamine (3.0 mmol) and dichloromethane (10 mmol)
ml) of 5,7-dichloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] -triazolo [1.5α] pyrimidine (3.0 mmol) and dichloromethane (30 ml) to the mixture with stirring. The reaction mixture is stirred at room temperature for 16 hours and subsequently washed with 1N hydrochloric acid. The organic layer is separated, dried with anhydrous sodium sulfate and filtered. The filtrate is evaporated under reduced pressure to give 1.05 g of a yellow powder with a melting point of 169 ° C.

Examples 6 to 20 In the same manner as in Example 5, the following Examples (Table 1; structure and melting point) are synthesized.

[0076]

[Table 1] Example 21 Preparation of diethyl 2,4,6-trichlorophenylmalonate Diethyl malonate (6.21 mol) was treated with sodium hydride (5.13 mol) and 1,4-dioxane (1400 m
Add to the mixture of 1) at 55-60 ° C within 3 hours. The mixture is stirred at 55 ° C. for 10 minutes and copper (I) bromide (0.5 mol) is added. A mixture of 2,4,6-trichlorobromobenzene (2.50 mol) and 1,4-dioxane (600 ml) is added. Add 10 reaction mixtures
Heat to 0 ° C for 14 hours and cool to 15 ° C. Hydrochloric acid (12N, 350ml) is slowly added at 15-20 ° C. The organic phase was separated and the aqueous phase was extracted with ethyl acetate (250 m
l) and extract with toluene (200 ml). The combined organic phases are concentrated in vacuo. The residue is filtered over silica gel, washed with petroleum ether / ethyl acetate (15: 1) and the solvent is distilled off. The residue is distilled in vacuo to give 540 g of the product as a white solid, 144-150 ° C. at 0.4 mbar.

Example 22 5,7-Dichloro- (2,4,6-trichlorophenyl)-
Preparation of 1,2,4-triazolo [1.5a] pyrimidine 3-amino-1,2,4-triazole (0.15 mol), diethyl 2,4,6-trichlorophenylmalonate (0.15 mol, A mixture of (obtained from Example 21) and tributylamine (0.15 mol) is heated to 170 ° C. and the ethanol formed during the reaction is distilled off. Subsequently, the reaction mixture is cooled to 130 ° C. and phosphorus oxychloride (0.45 mol) is added within 30 minutes.
The reaction mixture is heated at reflux for 6 hours. A mixture of water and toluene (1.5 liter, 6: 5) is added slowly. The organic phase is separated, washed with dilute hydrochloric acid and water, dried and concentrated in vacuo to give a brown sticky oil (45 g) containing 85% of the title product.

Example 23 N, N-diethylamine (1.4 mmol), triethylamine (1.4 mmol) and dichloromethane (10 mmol)
ml) of 5,7-dichloro- (2,4,6-trichlorophenyl) -1,2,4-triazolo [1.5a] pyrimidine (1.4 mmol) and dichloromethane (30 ml).
Add to the mixture of l) with stirring. The reaction mixture is stirred at room temperature for 16 hours and subsequently washed twice with 1N hydrochloric acid and once with water. The organic layer is separated, dried using anhydrous sodium sulfate and the solvent is evaporated under reduced pressure. The resulting light brown oil was washed with tert.-butyl methyl ether (50
ml) to give beige crystals with a melting point of 199-201 ° C.

Examples 24-33 In the same manner as in Example 23, the following Examples (Table II; structure and melting point) are synthesized.

[0080]

[Table 2] Minimum Growth Inhibitory Concentration by Test Compound in Biological Research Serial Dilution Test
MIC showing the lowest concentration of active ingredient in the growth medium which causes a total growth inhibition of measuring mycelial growth every (minimum growth inhibitory concentration)
Values are determined by serial dilution tests using microtiter plates having 24 or 48 wells per plate. Dilution of the test compound in the nutrient solution and distribution to the wells is performed by TECAN RSP 5000 Robotic.
It is performed by a sample processor (Robotic Sample Processor). The following test compound concentrations are used:
0.04, 0.10, 0.20, 0.39, 0.78, 1.5
6, 3.13, 6.25, 12.50, 25.00, 50.
00 and 100.00 μg / ml (or a starting concentration of 5.00 ppm was used in 12 serial dilutions). For the production of nutrient solutions, V8 vegetable juice (333
ml) with calcium carbonate (4.95 g), centrifuge, dilute the supernatant (200 ml) with water (800 ml) and autoclave at 121 ° C. for 30 minutes.

Each inoculum (Alternaria solani, ALTESO; Botrytis
Cinerea (Botrytis cinerea), BOTRCI; Cochliobulus sativus, COCHS
A: Magnapolse grisea f.sp. orizae (Magnapo
rthe grisea f.sp. Oryzae), PYRIOR; Rhizoctonia solani (RHIZSO) in a well, a spore suspension of an agar culture of fungi and mold (50).
ml; 5 × 10 ⁵ / ml) or agar flakes (6 mm).

At an appropriate temperature (18-25 ° C.)
After 12 days of incubation, MIC values are determined by visual inspection of the boards (Tables III and IV).

[0083]

[Table 3]

[0084]

[Table 4] The main features and aspects of the present invention are as follows.

1. Formula I

[0086]

Embedded image [Wherein R ¹ and R ² are each independently a hydrogen atom or optionally substituted alkyl, alkenyl,
An alkynyl, alkadienyl, haloalkyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl group, or R ¹ and R ² together with an intermediate nitrogen atom, optionally substituted heterocycle R ³ , R ⁴ and R ⁵ each independently represent a fluorine or chlorine atom, provided that at least one of R ³ , R ⁴ and R ⁵ is a chlorine atom, and X is A halogen atom].

2. R¹Is a linear or branched C₁−
C₆-Alkyl, C₁-C₆-Haloalkyl, or C_Two-C
₆-Alkenyl, or C_Three-C₆-Cycloalkyl, also
Is C _Five-C₉-Bicycloalkyl and R^TwoIs hydrogen
Or C₁-C₆-Represents alkyl or R¹And R
^TwoTogether with an intermediate nitrogen atom may optionally have 1
Or two Cs₁-C₆-Substituted by an alkyl group
Represents a heterocyclic ring having 5 or 6 carbon atoms which may be
The compound of claim 1.

3. The compound of the above 1 or 2, wherein R ² represents a hydrogen atom.

4. The compound of any one of the above 1, 2 or 3, wherein one of R ³ , R ⁴ and R ⁵ is a fluorine atom and the other two are chlorine atoms.

5. The compound according to the above 4, wherein R ³ and R ⁵ represent a chlorine atom.

6. The compound of any of the above 1, 2 or 3, wherein R ³ represents a chlorine atom and R ⁴ and R ⁵ represent a fluorine atom.

7. [5-Chloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] triazolo
[1,5-α] pyrimidin-7-yl] -cyclopentyl-
Amine, [5-chloro-6- (2,6-dichloro-4-fluoro-phenyl) -7- (4-methyl-piperidine-1
-Yl)-[1,2,4] triazolo [1,5-α] pyrimidine, [5-chloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] triazolo [1,5-α] pyrimidin-7-yl]-(2,2,2-trifluoro-ethyl) -amine, [5-chloro-6- (2,6-dichloro-4)
-Fluoro-phenyl)-[1,2,4] triazolo [1,5
-Α] pyrimidin-7-yl]-(1,1,1-trifluoro-prop-2-yl) -amine, [5-chloro-6-
(2,6-dichloro-4-fluoro-phenyl)-[1,2,
4] triazolo [1,5-α] pyrimidin-7-yl] -diethyl-amine, [5-chloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] triazolo
[1,5-α] pyrimidin-7-yl] -isopropyl-amine, sec-butyl- [5-chloro-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] Triazolo [1,5-α] pyrimidin-7-yl] -amine, bicyclo [2.2.1] hept-2-yl- [5-chloro-6-
(2,6-dichloro-4-fluoro-phenyl)-[1,2,
4] triazolo [1,5-α] pyrimidin-7-yl] -amine, [5-chloro-6- (2-chloro-4,6-difluoro-phenyl)-[1,2,4] triazolo [1 , 5-α] pyrimidin-7-yl] -cyclopentyl-amine, [5-
Chloro-6- (2-chloro-4,6-difluoro-phenyl) -7- (4-methyl-piperidin-1-yl)-[1,
2,4] triazolo [1,5-α] pyrimidine, [5-chloro-6- (2-chloro-4,6-difluoro-phenyl)-
[1,2,4] triazolo [1,5-α] pyrimidin-7-yl]-(2,2,2-trifluoro-ethyl) -amine, [5
-Chloro-6- (2-chloro-4,6-difluoro-phenyl)-[1,2,4] triazolo [1,5-α] pyrimidine-
7-yl]-(1,1,1-trifluoro-prop-2-yl) -amine, [5-chloro-6- (2-chloro-4,6-
Difluoro-phenyl)-[1,2,4] triazolo [1,5
-Α] pyrimidin-7-yl] -diethyl-amine, [5
-Chloro-6- (2-chloro-4,6-difluoro-phenyl)-[1,2,4] triazolo [1,5-α] pyrimidine-
7-yl] -isopropyl-amine, sec-butyl-
[5-chloro-6- (2-chloro-4,6-difluoro-
Phenyl)-[1,2,4] triazolo [1,5-α] pyrimidin-7-yl] -amine, bicyclo [2.2.1] hept-
2-yl- [5-chloro-6- (2-chloro-4,6-difluoro-phenyl)-[1,2,4] triazolo [1,5-
α] 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, [5-chloro-6- (2,4,6-trichloro-phenyl) -7-
(3-Methyl-piperidin-1-yl)-[1,2,4] triazolo [1,5-α] 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-trichloro-phenyl) -7- (4-methyl-piperidin-1-yl]-
[1,2,4] triazolo [1,5-α] pyrimidine, diethyl- [5-chloro-6- (2,4,6-trichlorophenyl)-[1,2,4] triazolo [1,5-] a] Pyrimidine-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] pyrimidine-
7-yl] -amine, N-ethyl-N-2-methylallyl- [5-chloro-6- (2,4,6-trichlorophenyl)-[1,2,4] triazolo [1,5-a] Pyrimidine-7
-Yl] -amine, and 1,1,1-trifluoroprop-2-yl- [5-chloro-6- (2,4,6-trichlorophenyl)-[1,2,4] triazolo [1, Selected from the group consisting of 5-a] pyrimidin-7-yl] -amine,
The compound of 1 above.

8. Formula II

[0094]

Embedded image Wherein R ³ , R ⁴ , R ⁵ and X are as defined in any of the above embodiments, with a compound of formula III

[0095]

Embedded image A compound of formula I according to any of the above 1-7, comprising reacting with an amine of the formula wherein R ¹ and R ² are as defined in any of the above embodiments. Manufacturing method.

9. Formula II

[0097]

Embedded image Wherein R ³ , R ⁴ , R ⁵ and X are as defined in any of the above 1-7.

10.5,7-Dihydroxy-6- (2,4,
6-trichlorophenyl)-[1,2,4] triazolo [1,
5-α] pyrimidine, 5,7-dihydroxy-6- (2,6
-Dichloro-4-fluoro-phenyl)-[1,2,4] triazolo [1,5-α] pyrimidine and 5,7-dihydroxy-6- (2-chloro-4,6-difluoro-phenyl)-[ A compound selected from [1,2,4] triazolo [1,5-α] pyrimidine.

11. The above 1 as a carrier and an activator
A fungicidal composition comprising at least one compound of formula I according to any of -7.

12. A method for controlling fungi and molds at a location, comprising treating the location with a compound of formula I according to any of the above 1-7.

13. The fungus or the fungus is Pyriculariaoryzae f.sp. grise
The method according to the above item 12, which is a).

14. The above 1-7 as a disinfectant / fungicide
Use of a compound of formula I according to any of the preceding claims.

Claims (7)

[Claims] 1. A compound of the formula I [Wherein R ¹ and R ² are each independently a hydrogen atom or optionally substituted alkyl, alkenyl,
An alkynyl, alkadienyl, haloalkyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl group, or R ¹ and R ² together with an intermediate nitrogen atom, optionally substituted heterocycle Represents a formula ring, wherein R ³ , R ⁴ and R ⁵ each independently represent a fluorine or chlorine atom, provided that at least one of R ³ , R ⁴ and R ⁵ is a chlorine atom, and X is A halogen atom]. 2. A compound of formula II Wherein R ³ , R ⁴ , R ⁵ and X are as defined in claim 1 with a compound of formula III [In the formula, R ¹ and R ² are as defined in claim 1] comprises reacting an amine of preparation of compounds of formula I according to claim 1. 3. A compound of formula II Wherein R ³ , R ⁴ , R ⁵ and X are as defined in claim 1. 4. The method according to claim 1, wherein the 5,7-dihydroxy-6- (2,4,6-
Trichlorophenyl)-[1,2,4] triazolo [1,5-
α] pyrimidine, 5,7-dihydroxy-6- (2,6-dichloro-4-fluoro-phenyl)-[1,2,4] triazolo [1,5-α] pyrimidine and 5,7-dihydroxy-6 -(2-chloro-4,6-difluoro-phenyl)-
A compound selected from [1,2,4] triazolo [1,5-α] pyrimidine. 5. A fungicidal composition comprising a carrier and at least one compound of formula I according to claim 1 as an active agent. 6. A method for controlling fungi at a location, comprising treating the location with a compound of formula I according to claim 1. 7. Use of a compound of formula I according to claim 1 as a fungicide.