JP2007514682A - 6-Pentafluorophenyl-triazolopyrimidine, process for its production, its use for controlling pathogenic fungi and medicaments containing these substances - Google Patents

Abstract

（式中の置換基は以下のように定義される：
R¹は、アルキル、ハロアルキル、シクロアルキル、ハロシクロアルキル、アルケニル、ハロアルケニル、シクロアルケニル、ハロシクロアルケニル、アルキニル、ハロアルキニルまたはフェニル、ナフチル、あるいは、Ｏ、ＮおよびＳからなる群からの１〜４個のへテロ原子を含む５または６員の飽和、部分的不飽和もしくは芳香族複素環であり；
R²は、水素、またはR¹について挙げた基の１つであり；
R¹とR²は、それらが結合する窒素原子と一緒に、Ｎを介して結合する５または６員へテロシクリルまたはヘテロアリールを形成しても、環員としてＯ、ＮおよびＳからなる群からの１〜３個のさらに別のへテロ原子を含んでもよく；
R¹および／またはR²は、本文の記載内容に従って置換することができ；
Ｘは、シアノ、アルキル、アルコキシ、アルケニルオキシ、ハロアルコキシ、もしくはハロアルケニルオキシである）。本発明はまた、前記化合物を製造する方法、該化合物を含む薬剤、ならびに植物病原性真菌を防除するためのそれらの使用にも関する。6-Pentafluorophenyl-triazolopyrimidine of formula I:
[Chemical 1]

(Substituents in the formula are defined as follows:
R ¹ is alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, cycloalkenyl, halocycloalkenyl, alkynyl, haloalkynyl or phenyl, naphthyl, or 1 to 3 from the group consisting of O, N and S 5 or 6 membered saturated, partially unsaturated or aromatic heterocycles containing 4 heteroatoms;
R ² is hydrogen or ^one of the groups listed for R ¹ ;
R ¹ and R ² , together with the nitrogen atom to which they are attached, form a 5- or 6-membered heterocyclyl or heteroaryl attached through N, but from the group consisting of O, N and S as ring members Of 1 to 3 further heteroatoms;
R ¹ and / or R ² can be substituted according to the description in the text;
X is cyano, alkyl, alkoxy, alkenyloxy, haloalkoxy, or haloalkenyloxy). The invention also relates to methods for producing said compounds, medicaments containing said compounds and their use for controlling phytopathogenic fungi.

Description

The present invention relates to 6-pentafluorophenyltriazolopyrimidines of formula I:

(Substituents in the formula are defined as follows:
R ¹ is C ₁ -C ₈ -alkyl, C ₁ -C ₈ -haloalkyl, C ₃ -C ₈ -cycloalkyl, C ₃ -C ₈ -halocycloalkyl, C ₂ -C ₈ -alkenyl, C _2- C ₈ -haloalkenyl, C ₃ -C ₆ -cycloalkenyl, C ₃ -C ₆ -halocycloalkenyl, C ₂ -C ₈ -alkynyl, C ₂ -C ₈ -haloalkynyl or phenyl, naphthyl or O, A 5- or 6-membered saturated, partially unsaturated or aromatic heterocycle containing 1 to 4 heteroatoms from the group consisting of N and S;
R ² is hydrogen or ^one of the groups mentioned for R ¹ ,
R ¹ and R ² together with the nitrogen atom to which they are attached may form a 5- or 6-membered heterocyclyl or heteroaryl attached through N, the group consisting of O, N and S as ring members 1 to 3 further heteroatoms from and / or halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ - haloalkenyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - haloalkoxy, C ₃ -C ₆ - alkenyloxy, C ₃ -C ₆ - haloalkenyloxy, (exo) -C ₁ -C ₆ May carry one or more substituents from the group consisting of -alkylene and oxy-C ₁ -C ₃ -alkyleneoxy;
R ¹ and / or R ² may carry 1 to 4 identical or different groups R ^a ;
R ^a is halogen, cyano, nitro, hydroxyl, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkylcarbonyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - haloalkoxy, C ₁ -C ₆ - alkoxycarbonyl, C ₁ -C ₆ - alkylthio, C ₁ -C ₆ - alkylamino, di -C ₁ -C ₆ - alkylamino, C ₂ -C ₆ -alkenyl, C ₂ -C ₈ -haloalkenyl, C ₂ -C ₆ -alkenyloxy, C ₂ -C ₈ -alkynyl, C ₂ -C ₈ -haloalkynyl, C ₃ -C ₆ -alkynyl 5- or 6-membered containing 1 to 4 heteroatoms from the group consisting of oxy, oxy-C ₁ -C ₃ -alkyleneoxy, C ₃ -C ₈ -cycloalkenyl, phenyl, naphthyl, O, N and S Saturated, partially unsaturated or aromatic heterocycles, wherein these aliphatic, alicyclic or aromatic groups are partially or partially Completely may be halogenated;
X is cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₃ -C ₄ -alkenyloxy, C ₁ -C ₂ -haloalkoxy, C ₃ -C ₄ -haloalkenyloxy ).

  Furthermore, the present invention relates to methods for producing these compounds, compositions comprising these compounds, and their use for controlling phytopathogenic harmful fungi.

  5-halo-6-pentafluorotriazolopyrimidine is known from European Patent Application No. 834,513. 5-Cyano and 5-alkoxytriazolopyrimidines are disclosed in WO 02/083677. Triazolopyrimidines with an optically active amino substituent at the 7-position have been generally proposed in WO 02/83565.

  The compounds described in the aforementioned publications are suitable for controlling harmful fungi.

  However, the action is not always completely satisfactory. Using this as a base, the object of the present invention is to provide improved activity and / or a broader spectrum of activity.

  Accordingly, the inventors have found the compounds described at the beginning. Furthermore, the present inventors have found a method for producing these compounds, a composition containing them, and a method for controlling harmful fungi using Compound I.

  The compounds according to the invention differ from those described in the aforementioned publications by substitution at the 5-position of the triazolopyrimidine skeleton.

  Compared to known compounds, the compounds of formula I have an enhanced activity against harmful fungi and / or a broader spectrum of activity.

The compounds according to the invention can be obtained by various methods. These are advantageously obtained from 5-halo-6-pentafluorotriazolopyrimidines of formula II, which are well known from European patent application 834,513, by reaction with compound MX (formula III). Depending on what group X is to be introduced, compound III is either an inorganic cyanide or an alkoxide. The reaction is advantageously carried out in the presence of an inert solvent. The cation M of formula III is not critical, but for practical reasons, ammonium, tetraalkylammonium, or alkali metal or alkaline earth metal salts are usually preferred.

  The reaction temperature is usually 0 to 120 ° C., preferably 10 to 40 ° C. [See J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].

When R ² is hydrogen, it is advantageous to introduce a removable protecting group prior to reaction with III [see Greene, Protective Groups in Organic Chemistry, J. Wiley & Sons, (1975). ].

  Suitable solvents include ethers (eg dioxane, diethyl ether, preferably tetrahydrofuran), alcohols (eg methanol or ethanol), halogenated hydrocarbons (eg dichloromethane), and aromatic hydrocarbons (eg toluene or Acetonitrile).

Compounds of formula I in which X is C ₁ -C ₄ -alkyl can be advantageously obtained by the synthetic method shown below:

Starting with 2-aminotriazole IV and ketoester V (wherein R is C ₁ -C ₄ -alkyl), 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidine VI is obtained. In formulas V and VI, X ¹ is C ₁ -C ₄ -alkyl. Using 2-phenylacetoacetic acid ester (V: where X ¹ = CH ₃ ) which can be easily obtained, 5-methyl-7-hydroxy-6-phenyltriazolopyrimidine, which is a preferred material of the present invention, Obtained [see Chem. Pharm. Bull., 9, 801, (1961)]. 2-Aminotriazole IV is commercially available. The starting material V is advantageously prepared under the conditions described in European Patent Application No. 10 02 788.

Under the conditions well known from WO-A 94/20501, the resulting 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidine is halopyrimidine of formula VII with a halogenating agent [HAL] (where Hal is a halogen) Atoms, preferably bromine or chlorine atoms, in particular chlorine atoms). The halogenating agent [HAL] used is advantageously a chlorinating or brominating agent such as phosphorus oxybromide, phosphorus oxychloride, thionyl chloride, thionyl bromide or sulfuryl chloride.

The reaction is usually carried out at 0 to 150 ° C., preferably 80 to 150 ° C. [see EP-A 770 615].

The reaction of VII with amine VIII (wherein R ¹ and R ² are as defined in formula I) is carried out at 0-70 ° C., preferably 10-35 ° C., in an inert solvent such as ether (eg dioxane). , Diethyl ether, or especially tetrahydrofuran), halogenated hydrocarbons (eg dichloromethane), or aromatic hydrocarbons (eg toluene) [see WO-A 98/46608] .

  Preference is given to using a base, for example a tertiary amine (eg triethylamine) or an inorganic amine (eg potassium carbonate); it is also possible to use an excess amine of the formula VIII as the base.

Alternatively, a compound of formula I (wherein X is C ₁ -C ₄ -alkyl) is prepared from compound I (where X is a halogen, especially chlorine) and a malonate of formula IX. You can also In formula IX, X ″ is hydrogen or C ₁ -C ₃ -alkyl and R is C ₁ -C ₄ -alkyl. These are converted to compounds of formula X and decarboxylated to give a compound of formula I The compound is obtained [see US 5 994 360].

  Malonate IX is described in the literature [J. Am. Chem. Soc., 64, 2714 (1942); J. Org. Chem., 39, 2172 (1974); Helv. Chim. Acta, 61, 1565 (1978). And can be prepared according to the literature cited.

  The hydrolysis of ester X is then carried out under conventional conditions, but it is advantageous to carry out an alkaline or acidic hydrolysis of compound X, depending on various structural elements. Complete or partial decarboxylation is performed under conditions of ester hydrolysis to give I.

  The decarboxylation is usually carried out at a temperature of 20 ° C. to 180 ° C., preferably 50 ° C. to 120 ° C., in an inert solvent, if necessary, in the presence of an acid.

  Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid. Suitable solvents include water, aliphatic hydrocarbons (eg pentane, hexane, cyclohexane and petroleum ether), aromatic hydrocarbons (eg toluene, o-, m- and p-xylene), halogenated hydrocarbons (eg , Methylene chloride, chloroform and chlorobenzene), ethers (eg diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetraidrofuran, nitriles (eg acetonitrile and propionitrile), ketones (eg acetone, Methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone), alcohols (eg methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol), and dimethyl sulfoxide, dimethyl Tylformamide and dimethylacetamide are mentioned, but it is particularly preferred to carry out the reaction in hydrochloric acid or acetic acid, and it is also possible to use mixtures of the solvents mentioned.

Compounds of formula I wherein X is C ₁ -C ₄ -alkyl can also be prepared by combining a 5-halotriazolopyrimidine of formula I where X is a halogen with an organometallic reagent of formula XI. In one embodiment of this method, the reaction is performed with a transition metal catalyst (eg, a Ni or Pb catalyst).

In formula XI, M is a metal ion of valence y, such as B, Zn or Sn, and “X” is C ₁ -C ₃ -alkyl. This reaction can be performed, for example, in the same manner as described in the following literature: J. Chem. Soc. Perkin Trans. 1, 1187 (1994), ibid., 2345 (1996); WO-A 99 / 41255; Aust. J. Chem., 43, 733 (1990); J. Org. Chem., 43, 358 (1978); J. Chem. Soc. Chem. Commun. 866 (1979); Tetrahedron Lett., 34, 8267 (1993); ibid. 33, 413 (1992).

  The reaction mixture is prepared in the usual manner, for example by mixing with water, separating the phases and, if necessary, carrying out chromatographic purification of the crude product. Some intermediates and final products are obtained in the form of colorless or slightly brownish viscous oils that are either purified or removed of volatile components at moderately elevated temperatures under reduced pressure. If the intermediate and final product are obtained in solid form, purification can also be carried out by recrystallization or digestion.

  If an individual compound I cannot be obtained by the method described above, it can be prepared by derivatization of another compound I.

  When obtaining a mixture of isomers by synthesis, the individual isomers may be converted during preparation or use (eg, under the action of light, acid or base) Separation is not always necessary. Such conversions may also occur after use, for example, in the treatment of plants to be treated or harmful fungi to be controlled.

Collective terms were used in the definitions of the symbols set forth in the above formulas, and these terms generally represent the substituents listed below:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: a saturated straight or branched hydrocarbon group having _{1 to 4, 6} or 8 carbon atoms, for example C ₁ -C ₆ -alkyl, for example methyl, ethyl, propyl, 1-methylethyl, Butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1 -Dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethyl Butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 -Ethyl-1-methylpropyl and 1-ethyl-2-mes Rupuropiru;
Haloalkyl: a straight-chain or branched alkyl group having 1 to 2, 4, 6 or 8 carbon atoms (as described above), wherein some or all of the hydrogen atoms in these groups May be substituted with the above halogen atoms; in particular, C ₁ -C ₂ -haloalkyl, eg chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoro Methyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1- Rifuruoropuropu 2-yl;
Alkenyl: an unsaturated straight or branched hydrocarbon group having 2 to 4, 6, 8 or 10 carbon atoms and 1 or 2 double bonds in any position, for example C _2- C ₆ -alkenyl, eg ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1 -Methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3 -Butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-eth -2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4 -Methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl -3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4 -Pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3 -Butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 -Butenyl, 2,3-dimethyl-2-bute 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1- Ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl- 2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
Haloalkenyl: an unsaturated straight chain or branched hydrocarbon group (as described above) having 2 to 8 carbon atoms and 1 or 2 double bonds in any position (in these groups, Some or all of the hydrogen atoms may be replaced by the aforementioned halogen atoms, in particular fluorine, chlorine and bromine);
Alkynyl: a straight or branched hydrocarbon group having 2 to 4, 6 or 8 carbon atoms and 1 or 2 triple bonds in any position, for example C ₂ -C ₆ -alkynyl, Examples: ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1- Methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1- Hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl Tyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3- Dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
Cycloalkyl: mono- or bicyclic saturated hydrocarbon group having 3 to 6 or 8 carbon ring members, for example C ₃ -C ₈ -cycloalkyl, eg cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl And cyclooctyl;
A 5 or 6 membered saturated, partially unsaturated or aromatic heterocycle containing 1 to 4 heteroatoms from the group consisting of O, N and S;
-5- or 6-membered heterocyclyl containing 1 to 3 nitrogen atoms and / or 1 oxygen or sulfur atom, or 1 or 2 oxygen and / or sulfur atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuran Nyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3- 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxane-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl;
-1 to 4 nitrogen atoms or 5-membered heteroaryl containing 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom: as ring members, in addition to carbon atoms, 1 to 4 nitrogen atoms or 1 5-membered heteroaryl groups which may contain up to 3 nitrogen atoms and 1 sulfur or oxygen atom, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3 -Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl and 1,3,4-triazole 2-yl;
-6-membered heteroaryl groups containing 1 to 3 or 1 to 4 nitrogen atoms: 6-membered heteroaryl groups which can contain 1 to 3 or 1 to 4 nitrogen atoms in addition to carbon atoms as ring members For example, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;
Alkylene: a saturated straight-chain or branched hydrocarbon group having 1 to 4 or 6 carbon atoms bonded to the skeleton through a double bond, for example, = CH ₂ , = CH-CH ₃ And = CH-CH ₂ -CH ₃ ;
Oxyalkyleneoxy: a divalent unbranched chain consisting of 1 to 3 CH ₂ groups, where both valences are linked to the skeleton via one oxygen atom, for example OCH ₂ O , OCH ₂ CH ₂ O and OCH ₂ CH ₂ CH ₂ O;
The scope of the present invention includes the (R)-and (S) -isomers and racemic mixtures of compounds of formula I having chiral centers.

  For the intended use of the triazolopyrimidines of the formula I, it is particularly preferred that the substituents have the meanings indicated below, in which case these substituents are used alone or in combination depending on the respective case.

Preferred are compounds I, wherein R ¹ is C ₁ -C ₄ -alkyl, C ₂ -C ₆ -alkenyl or C ₁ -C ₈ -haloalkyl.

Preferred compounds I in which R ¹ is a group A are preferred:

(Where
Z ¹ is hydrogen, fluorine or C ₁ -C ₆ -fluoroalkyl,
Z ² is hydrogen or fluorine, or
Z ¹ and Z ² together form a double bond;
q is 0 or 1;
R ³ is hydrogen or methyl).

Also preferred are compounds I in which R ¹ is C ₃ -C ₆ -cycloalkyl, which may be substituted with C ₁ -C ₄ -alkyl.

Particularly preferred are compounds I in which R ² is hydrogen.

Preference is likewise given to compounds I in which R ² is methyl or ethyl.

When R ¹ and / or R ² are haloalkyl or haloalkenyl groups having a chiral center, the (S) -isomers of these groups are preferred. In the case of halogen-free alkyl or alkenyl groups having a chiral center at R ¹ or R ² , the (R) -configured isomers are preferred.

A preferred embodiment of the present invention relates to a compound of formula I.1:

(Where
G is C ₂ -C ₆ -alkyl, especially ethyl, n- and isopropyl, n-, sec-, tert-butyl, and C ₁ -C ₄ -alkoxymethyl, especially ethoxymethyl, or C ₃ -C _6- Cycloalkyl, in particular cyclopentyl or cyclohexyl;
R ² is hydrogen or methyl;
X is as described in formula I, in particular cyano, methoxy or ethoxy).

Another preferred embodiment of the present invention relates to a compound of formula I.2:

(Where
Y is hydrogen or C ₁ -C ₄ -alkyl, in particular methyl and ethyl, X is as defined in formula I, in particular cyano, methoxy or ethoxy).

Another preferred embodiment of the present invention is a compound wherein R ¹ and R ² together with the nitrogen atom to which they are attached form a 5 or 6 membered heterocyclyl or heteroaryl attached through N, Including further heteroatoms from the group consisting of O, N and S as ring members and / or halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₂ -C _6- alkenyl, C ₂ -C ₆ - haloalkenyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - haloalkoxy, C ₃ -C ₆ - alkenyloxy, C ₃ -C ₆ - haloalkenyloxy, C ₁ - It relates to a compound as described above which may bear one or more substituents from the group consisting of C ₆ -alkylene and oxy-C ₁ -C ₃ -alkyleneoxy. Such compounds correspond in particular to formula I.3:

(Where
D together with the nitrogen atom forms a 5- or 6-membered heterocyclyl or heteroaryl linked through N, and also adds another heteroatom from the group consisting of O, N and S as ring members. And / or halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -haloalkenyl, C ₁ -C ₆ -alkoxy, C _{From 1} -C ₆ -haloalkoxy, C ₃ -C ₆ -alkenyloxy, C ₃ -C ₆ -haloalkenyloxy, (exo) -C ₁ -C ₆ -alkylene and oxy-C ₁ -C ₃ -alkyleneoxy May carry one or more substituents from the group;
X is as described in formula I, in particular cyano, methoxy or ethoxy).

In addition, R ¹ and R ² together with the nitrogen atom to which they are attached, a piperidinyl, morpholinyl or thiomorpholinyl ring, in particular a piperidinyl ring (which optionally comprises 1 to 3 halogens, C ₁ -C ₄ -alkyl Also preferred are compounds I which are substituted with C ₁ -C ₄ -haloalkyl. Particularly preferred are compounds in which R ¹ and R ² together with the nitrogen atom to which they are attached form a 4-methylpiperidine ring.

Furthermore, the present invention preferably provides that R ¹ and R ² together with the nitrogen atom to which they are attached, a pyrazole ring (optionally one or two halogen, C ₁ -C ₄ -alkyl or C ₁ Also provided is Compound I, which is substituted with —C ₄ -haloalkyl, in particular substituted with 3,5-dimethyl or 3,5-di (trifluoromethyl).

In addition, R ¹ is CH (CH ₃ ) -CH ₂ CH ₃ , CH (CH ₃ ) -CH (CH ₃ ) ₂ , CH (CH ₃ ) -C (CH ₃ ) ₃ , CH (CH ₃ )- CF ₃ , CH ₂ C (CH ₃ ) ═CH ₂ , CH ₂ CH═CH ₂ , cyclopentyl or cyclohexyl; R ² is hydrogen or methyl; or R ¹ and R ² together are — (CH ₂ ) ₂ CH (CH ₃ ) (CH ₂ ) ₂ -,-(CH ₂ ) ₂ CH (CF ₃ ) (CH ₂ ) _2- , or-(CH ₂ ) ₂ O (CH ₂ ) _2- Compound I is also particularly preferred.

  Furthermore, compounds I in which X is cyano, methoxy or ethoxy, especially cyano or methoxy are also preferred.

  In another preferred embodiment of Formula I, X is methyl.

  In particular for its use, the compounds I listed in the table below are preferred. Furthermore, the groups mentioned for the substituents in the table are themselves particularly preferred embodiments of the relevant substituents, independent of the combination in which they are described.

Table 1
A compound of formula I wherein X is cyano and the combination of R ¹ and R ² corresponds to one row of Table A for each compound.

Table 2
A compound of formula I wherein X is methoxy and the combination of R ¹ and R ² corresponds to one row of Table A for each compound.

Table 3
A compound of formula I wherein X is ethoxy and the combination of R ¹ and R ² corresponds to one row of Table A for each compound.

Table 4
A compound of formula I wherein X is methyl and the combination of R ¹ and R ² corresponds to one row of Table A for each compound.

Table A

  Compound I is suitable as a fungicide. They are characterized by very good efficacy against a broad spectrum of phytopathogenic fungi, in particular fungi from the class of ascomycetes, imperfect fungi, oomycetes and basidiomycetes. Some of them are effective for the whole plant and can therefore be used for plant protection as foliar and soil fungicides.

  The compounds are various cultivated plants such as wheat, rye, barley, oats, rice, corn, lawn, banana, cotton, soybeans, coffee, sugarcane, grapes, fruits and ornamental plants, and vegetables such as cucumber, legumes. Particularly important for the control of various fungi on the seeds of tomatoes, potatoes and cucumbers, and even these plants.

Said compounds are particularly suitable for controlling the following plant diseases:
・ Alternaria species for fruits and vegetables,
・ Bipolaris and Drexerella species for cereals, rice and lawn,
-Powdery mildew (Blumeria graminis) (dusty mildew) on grains
-Botrytis cinerea (gray mold) against strawberries, vegetables, ornamental plants and grapes,
・ Erysiphe cichoracearum and Sphaerotheca fuliginea against cucurbitaceae,
-Fusarium and Verticillium species for various plants,
-Mycos Farrera seeds for cereals, bananas and peanuts,
・ Phytophtora infestans for potatoes and tomatoes,
・ Plasmopara viticola against grapes,
・ Podosphaera leucotricha against apples
・ Pseudocercosporella herpotrichoides for wheat and barley,
Root-knot species for hops and cucumbers,
・ Sabikin seeds for grains,
・ Pyricularia oryzae against rice,
-Rhizoctonia species for cotton, rice and lawn,
-Wheat leaf blight fungus (Septoria tritici) and Stagonospora nodorum against wheat,
・ Uncinula necator against grapes,
・ Kerobokin species for cereals and sugarcane,
• Venturia (red mold disease) against apples and pears.

  Compound I is also used to control harmful fungi such as Paecilomyces variotii in the protection of materials (eg wood, paper, paint dispersions, fibers or textiles) and in the protection of stored products. Is suitable.

  Compound I is used by treating fungi or a plant, seed, material or soil to be protected from fungal infestation with a fungicidally effective amount of the active compound. This use can be carried out both before and after infection of the fungal material, plant or seed.

  Fungicidal compounds generally comprise from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90%.

  When used for plant protection, the amount used is 0.01 to 2.0 kg of active compound per hectare, depending on the type of effect desired.

  When treating seed, an amount of active compound of 1 to 1,000 g, preferably 5 to 100 g, per 100 kg of seed is generally required.

  When used for the protection of materials or stored products, the amount of active compound varies depending on the field of use and the desired effect. The amounts normally used for protecting the material are, for example, 0.001 g to 2 kg, preferably 0.005 to 1 kg of active compound per cubic meter of material to be treated.

  Compound I can be converted into conventional formulations such as solutions, emulsions, suspensions, fines, powders, pastes and granules. The use forms depend on the specific purpose, but in each case it must ensure a fine and homogeneous distribution of the compounds according to the invention.

The formulations are prepared in a known manner, for example by extending the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries mainly include the following:
-Water, aromatic compounds (eg: Solvesso formulation, xylene), paraffin (eg: mineral oil fraction), alcohol (eg: methanol, butanol, pentanol, benzyl alcohol), ketones (eg: cyclohexanone, γ-butyrolactone), pyrrolidone (NMP, NOP), acetate (glycol diacetate), glycol, fatty acid dimethylamide, fatty acid and fatty acid ester. In principle, solvent mixtures may be used;
-Carriers such as ground natural minerals (eg kaolin, clay, talc, chalk) and ground synthetic minerals (eg highly dispersed silica, silicates); emulsifiers such as nonions and anionic emulsifiers (eg polyoxy) Ethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates), and dispersants such as lignosulfite waste liquor and methylcellulose.

  Suitable surfactants include: lignosulfonic acid, naphthalene sulfonic acid, phenol sulfonic acid, dibutyl naphthalene sulfonic acid, alkyl aryl sulfonate, alkyl sulfate, alkyl sulfonate, sulfated fatty alcohol, fatty acid and sulfated fat. Alkali metal salts, alkaline earth metal salts and ammonium salts of alcohol glycol ethers; Further, condensates of sulfonated naphthalene and naphthalene derivatives with formaldenide; condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldenide; poly Oxyethylene octylphenol ether; ethoxylated isooctylphenol, octylphenol, nonylphenol; alkylphenol polyglycol ether; Tristearyl phenyl polyglycol ether; Tristearyl phenyl polyglycol ether; Alkyl aryl polyether alcohol; Alcohol and fatty alcohol / ethylene oxide condensate; Ethoxylated castor oil; Polyoxyethylene alkyl ether; Ethoxylated polyoxypropylene; Lauryl alcohol polyglycol ether Acetal; sorbitol ester; lignosulfite waste liquor and methylcellulose.

  Suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are medium to high boiling mineral oil fractions such as kerosene or diesel oil, as well as coal tar oil, and plant or animal origin Oils, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polarity Solvents such as dimethyl sulfoxide, N-methylpyrrolidone and water.

  Powders, dusting materials and dusting formulations can be prepared by mixing the solid carrier and the active substance or by grinding together.

  Granules (eg coated granules, impregnated granules and homogeneous granules) can be prepared by binding the active ingredient to a solid carrier. Examples of solid supports include: inorganic earths such as silica gel, silicates, talc, kaolin, activated clay (attaclay), limestone, lime, chalk, ball clay, loess, clay, dolomite, Diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and plant-derived products such as grain food, bark food, tree food (wood meal) ) And husk food, cellulose powder and other solid carriers.

  In general, the formulations comprise from about 0.01 to 95% by weight of active compound, preferably from about 0.1 to 90%. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

Examples of formulations are given below:
1. Formulation diluted with water
A Water-soluble concentrate (SL)
10 parts by weight of a compound according to the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants may be added. When diluted with water, the active compound dissolves.

B Dispersible concentrate (DL)
20 parts by weight of a compound according to the invention are dissolved in cyclohexanone, with a dispersant, for example polyvinylpyrrolidone, being added. Dilution with water gives a dispersion.

C Emulsifiable concentrate (EL)
15 parts by weight of the compound according to the invention are dissolved in xylene, with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). Dilution with water gives an emulsion.

D Emulsion (EW, EO)
40 parts by weight of the compound according to the invention are dissolved in xylene, with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). Using an emulsifier (Ultraturrax), the mixture is introduced into water and made into a homogeneous emulsion. Dilution with water gives an emulsion.

E Suspension (SC, OD)
In a stirred ball mill, a fine active compound suspension is obtained by finely grinding 20 parts by weight of a compound of the invention while adding a dispersant, a wetting agent and water or an organic solvent. Dilution with water gives a stable suspension of the active compound.

F Water-dispersible granules and water-soluble granules (WG, SG)
Using industrial equipment (eg extrusion, spray tower, fluidized bed), 50 parts by weight of a compound of the invention is pulverized while adding dispersant and wetting agent to produce water-dispersible or water-soluble granules. obtain. Dilution with water gives a stable dispersion or solution of the active compound.

G Water-dispersible powder and water-soluble powder (WP, SP)
In a rotor-starter mill, 75 parts by weight of the compound of the invention are ground while adding the dispersant, wetting agent and silica gel. Dilution with water gives a stable dispersion or solution of the active compound.

2. Formulation H to be used undiluted Spray powder (DP)
5 parts by weight of a compound of the invention are pulverized and mixed homogeneously with 95% pulverized kaolin. Thereby, a spray formulation is obtained.

I Granule (GR, FG, GG, MG)
0.5 part by weight of a compound of the invention is pulverized and combined with 95.5% carrier. Current methods are extrusion, spray drying or fluidized bed. This gives granules to be used undiluted.

J ULV solution (UL)
10 parts by weight of a compound according to the invention are dissolved in an organic solvent, for example xylene. Thereby, the formulation to be used without dilution is obtained.

  The active compound by itself is in the form of its preparation or use form prepared therefrom, for example directly sprayable solutions, powders, suspensions or dispersions, emulsions, oily dispersions, pastes, spray formulations, spraying It can be used in the form of materials or granules by means of spraying, spraying, sprinkling, spreading or pouring. The use form depends entirely on the intended purpose, but in each case it should ensure the finest possible distribution of the active compounds according to the invention.

  Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. In order to prepare emulsions, pastes or oil dispersions, the substances are dissolved as such or dissolved in oil or solvent and homogenized in water using wetting agents, tackifiers, dispersants or emulsifiers. Alternatively, a concentrate composed of the active substance, wetting agent, tackifier, dispersant or emulsifier and optionally a solvent or oil can be prepared, such concentrate being diluted with water. It is suitable for.

  The concentration of active compound in ready-to-use formulations can vary within a relatively wide range. In general, the concentration is 0.0001 to 10%, preferably 0.01 to 1%.

  The active compounds can also be used favorably in the ultra-low-volume method (ULV), whereby it is possible to use active compounds in excess of 95% by weight or to use active compounds without additives. is there.

  Various oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides or fungicides may be added to the active compound (possibly just before use) (tank mix). These agents can be added to the agents of the present invention in a weight ratio of 1:10 to 10: 1.

  The compositions of the present invention can also be provided in the form of fungicides and together with other active compounds such as herbicides, insecticides, growth regulators, fungicides, or fertilizers. Combining a compound I, or a composition containing the compound in the form of use of a fungicide, with another fungicide will, in many cases, expand the resulting active fungicidal spectrum.

Listed below are fungicides that can be used with the compounds of the present invention, but are intended to illustrate, but not limit, possible combinations:
Acylalanine, such as benalaxyl, metalaxyl, off-race or oxadixyl,
Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctazine, spiroxamine or tridemorph,
Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil,
Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,
Azoles such as viteltanol, brumoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, hexaconazole, imazalyl, metconazole, microbutanyl, penconazole , Propiconazole, prochloraz, prothioconazole, tebuconazole, triazimephone, triazimenol, triflumizole or triticonazole,
Dicarboximides such as iprodione, microzoline, procymidone or vinclozolin,
Dithiocarbamates, such as felbam, nabam, maneb, mancozeb, metham, methylam, propineb, polycarbamate, thiram, dilam or dineb,
Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamide, dazometh, dithianon, famoxadone, fenamidone, phenalimol, fuberidazole, flutolanil, furametopyr, isoprothiolane, mepronil, nuarimol, probenazole, Proquinazide, pyrifenox, pyroxylone, quinoxyphene, silthiofam, thiabendazole, tifluzamide, thiophanate-methyl, thiazinyl, tricyclazole or trifolin,
Copper fungicides, such as Bordeaux mixtures, copper acetate, copper acid chloride or basic copper sulfate,
Nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone or nitrophthal-isopropyl,
Phenylpyrrole, for example fenpiclonyl or fludioxonil,
·sulfur,
Other fungicides, such as acibenzoral-S-methyl, benzavalicarb, carpropamide, chlorothalonil, cyflufenamide, simoxanil, dazometh, diclomedin, diclocimet, dietofencarb, edifenfos, ethaboxam, fenhexamide, fentin acetate, Phenoxanyl, ferrimzone, fluazinam, focetyl, focetyl-aluminum, iprovaricarb, hexachlorobenzene, metolaphenone, pencyclon, propamocarb, phthalide, torquelophos-methyl, quintozene or zoxamide,
Strobilurin, such as azoxystrobin, dimoxystrobin, fluoxastrobin, cresoxime-methyl, metminostrobin, orisatrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,
Sulfenic acid derivatives, such as captafol, captan, dichlorofluanide, forpeto or tolylfluanide,
Cyanamide and similar compounds, such as dimethomorph, flumetovel or fulmorph.

Synthetic Examples Another compound I was prepared by appropriate modification of the starting compound using the procedure described in the synthetic examples below. The compounds thus obtained are listed in the table below together with physical data.

Example 1: Preparation of 5-cyano-6-pentafluorophenyl-7-diethylamino-1,2,4-triazolo [1,5a] pyrimidine
3.4 g (8.6 mmol) 5-chloro-6-pentafluorophenyl-7-diethylamino-1,2,4-triazolo [1,5a] pyrimidine and 3.2 in 30 ml dimethylformamide at 20-25 ° C. g (20 mmol) of tetraethylammonium cyanide was stirred for about 45 minutes. After diluting the reaction mixture with water, the aqueous phase was extracted with t-butyl ether, the combined organic phases were dried and the solvent was removed. After chromatography using silica gel (cyclohexane / acetic acid mixture), 0.7 g of the title compound was obtained as colorless crystalline material from the residue, and its melting point was 153-158 ° C.

¹ H-NMR (CDCl ₃ , δ ppm): 8.55 (s, 1H); 3.55 (q, 4H); 1.2 (t, 6H)
Example 2: Preparation of 5-methyl-6- (pentafluorophenyl) -7- (4-methylpiperidinyl) -1,2,4-triazolo [1,5a] pyrimidine
Step 2a: Ethyl 2-pentafluorophenyl acetoacetate (formula V)
A solution of 14.1 g (0.102 mmol) potassium carbonate, 13 g (0.1 mmol) ethyl acetoacetate and 20 g (0.108 mmol) hexafluorobenzene in 100 ml dimethylformamide (DMF) at 60 ° C. for about 5 hours. Stir. The reaction mixture was then cooled to 20-25 ° C. and then poured into a mixture of 30 ml concentrated hydrochloric acid and 700 ml water. The aqueous phase was extracted with methyl t-butyl ether (MTBE), the combined organic phases were dried and the solvent was removed. After chromatography on silica gel (cyclohexane), 7.3 g of the title compound was obtained as a pale oil.

¹ H-NMR (CDCl ₃ , δ ppm): 13.4 (s, 1H); 4.2 (q, 2H); 1.9 (s, 3H); 1.2 (t, 3H)
Step 2b: 5-Methyl-6- (pentafluorophenyl) -7-hydroxy-1,2,4-triazolo [1,5a] pyrimidine (formula VI)
A solution of 20 g (67 mmol) of ethyl 2-pentafluorophenylacetoacetate (from Example 2a) and 5.7 g (67 mmol) of aminotriazole in 67 ml of propionic acid was heated at reflux for about 15 hours. The mixture was then cooled to 20-25 ° C., after which volatile components were removed by distillation and the residue was digested with water. The resulting precipitate was filtered and then dissolved in ethyl acetate. The organic phase was washed with dilute hydrochloric acid and dried to remove the solvent. The residue was crystallized and digested with hexane. Thus, the title compound: 5-methyl-6- (pentafluorophenyl) -7-hydroxy-1,2,4-triazolo [1,5a] pyrimidine and the isomeric 7-methyl-6- (pentafluorophenyl) There was obtained 8 g of a colorless solid containing) -5-hydroxy-1,2,4-triazolo [1,5a] pyrimidine in a 1: 2 ratio (by ¹ H-NMR).

¹ H-NMR (DMSO-d ₆ , δ ppm):
5-methyl, 7-hydroxy isomers: 8.4 (s, 1H); 2.25 (s, 3H)
5-hydroxy, 7-methyl isomers: 8.25 (s, 1H); 2.5 (s, 3H)
Step 2c: 5-Methyl-6- (pentafluorophenyl) -7-chloro-1,2,4-triazolo [1,5a] pyrimidine (formula VII)
7 g of the product mixture from Example 2b and 3 drops of DMF in 24 ml of phosphorus oxychloride were heated under reflux for about 4 hours. After cooling, volatile components were removed from the reaction mixture. The residue was dissolved in 70 ml methylene chloride and 30 ml water and methylene chloride began to boil. After phase separation, the aqueous phase was extracted with methylene chloride. The combined organic phases were dried and the solvent was removed. Chromatography on silica gel (MTBE) gave the title compound: 5-methyl-6- (pentafluorophenyl) -7-chloro-1,2,4-triazolo [1,5a] pyrimidine and the isomeric 7-methyl 4.7 g of a white solid containing -6- (pentafluorophenyl) -5-chloro-1,2,4-triazolo [1,5a] pyrimidine in a ratio of 4: 1 (by ¹ H-NMR) was obtained.

¹ H-NMR (DMSO-d ₆ , δ ppm):
5-methyl, 7-chloro isomers: 8.9 (s, 1H); 2.75 (s, 3H)
5-chloro, 7-methyl isomers: 8.85 (s, 1H); 2.5 (s, 3H)
Step 2d: 5-methyl-6- (pentafluorophenyl) -7- (4-methylpiperidinyl) -1,2,4-triazolo [1,5a] pyrimidine (formula I)
Of 1 g 5-methyl-6- (pentafluorophenyl) -7-chloro-1,2,4-triazolo [1,5a] pyrimidine (from Example 2c) and 0.33 g 4-methylpiperidine in 6 ml butanol The solution was stirred at 90 ° C. for about 1 hour. After cooling to 20-25 ° C, volatile components were removed by distillation. The residue was dissolved in ethyl acetate and the organic phase was extracted with water and dried before removing the solvent. After chromatography on silica gel (cyclohexane / ethyl acetate mixture) 0.9 g of the title compound: 5-methyl-6- (pentafluorophenyl) -7- (4-methylpiperidinyl) -1,2,4- Triazolo [1,5a] pyrimidine and the isomeric 7-methyl-6- (pentafluorophenyl) -5- (4-methylpiperidinyl) -1,2,4-triazolo [1,5a] pyrimidine : 1 ratio (by ¹ H-NMR).

¹ H-NMR (DMSO-d ₆ , δ ppm): 8.3 (s, 1H); 3.7 (d, wide area, 2H); 2.8 (t, wide area, 2H); 2.55 (s, 3H); 1.6 (m, 2H) ); 1.35 (m, 1H); 1.0 (m, 2H); 0.9 (d, 3H)
Table I-Compounds of Formula I

Example of action against harmful fungi The fungicidal action of the compounds of formula I was demonstrated by the following experiments:
The active compound was prepared as a stock solution containing 0.25 wt% active compound in acetone or DMSO. 1% by weight of the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenol) was added to the solution and the mixture was diluted with water to the desired concentration.

Example of Use 1-Activity against barley net blotch caused by Pyrenophora teres, used for prevention The leaves of potted barley seedlings of the cultivar "Hanna" contain aqueous compounds containing the following concentrations of active compounds: The turbid liquid was sprayed to the pour point. 24 hours after the spray coating had dried, the test plants were inoculated with an aqueous suspension of Pyrenophora teres, a pathogen of net blotch [Pyrenophora teres]. The test plants were then placed in a greenhouse at 20-24 ° C. and 95-100% relative atmospheric humidity. After 6 days, the extent of disease development was visually determined as percent infection of the total leaf area.

  In this test, plants treated with 250 ppm of compound I-3 showed only 5% infection, whereas untreated plants were 90% infected.

Example of Use 2- After two to three leaves have fully developed on green pepper seedlings of the variety "Neusiedler Ideal Elite" used for activity and prevention of peppers caused by gray mold fungus (Botrytis cinerea) An aqueous suspension containing the active compound at the following concentration was sprayed to the pour point. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 × 10 ⁶ spores / ml in a 2% strength aqueous biomalt solution. Next, the test plants were placed in an air-conditioned dark room at 22-24 ° C. and high relative atmospheric humidity. After 5 days, the extent of fungal infection in the leaves could be visually determined in%.

  In this study, plants treated with 63 ppm of compounds I-1, I-3, or I-4 were not infected, but untreated plants were 90% infected.

Use Example 3-An aqueous suspension containing the active compound at the following concentration in the leaves of potted wheat seedlings of "Riband", a prophylactically active cultivar "Riband" against wheat zeptria leap spot caused by wheat leaf blight fungus (Septoria tritici) Was sprayed to the pour point. 24 hours after the spray coating had dried, the test plants were inoculated with an aqueous spore suspension of Septoria tritici. The suspension contained 2.0 × 10 ⁶ spores / ml. The test plants were then placed in a greenhouse at a temperature of 18-22 ° C. and near 100% relative atmospheric humidity. Two days later, the extent of disease development was visually determined as percent infection of the total leaf area.

  In this study, plants treated with 63 ppm of compounds I-1, I-2, I-3, I-4 or I-5 showed less than 5% infection, whereas no treatment Of the plants were 80% infected.

Claims (14)

Formula I:

(Substituents in the formula are defined as follows:
R ¹ is C ₁ -C ₈ -alkyl, C ₁ -C ₈ -haloalkyl, C ₃ -C ₈ -cycloalkyl, C ₃ -C ₈ -halocycloalkyl, C ₂ -C ₈ -alkenyl, C _2- C ₈ -haloalkenyl, C ₃ -C ₆ -cycloalkenyl, C ₃ -C ₆ -halocycloalkenyl, C ₂ -C ₈ -alkynyl, C ₂ -C ₈ -haloalkynyl or phenyl, naphthyl or O, A 5- or 6-membered saturated, partially unsaturated or aromatic heterocycle containing 1 to 4 heteroatoms from the group consisting of N and S;
R ² is hydrogen or ^one of the groups mentioned for R ¹ ,
R ¹ and R ² together with the nitrogen atom to which they are attached may form a 5 or 6 membered heterocyclyl or heteroaryl attached via N, and the group consisting of O, N and S as ring members 1 to 3 further heteroatoms from and / or halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ - haloalkenyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - haloalkoxy, C ₃ -C ₆ - alkenyloxy, C ₃ -C ₆ - haloalkenyloxy, (exo) -C ₁ -C ₆ May carry one or more substituents from the group consisting of -alkylene and oxy-C ₁ -C ₃ -alkyleneoxy;
R ¹ and / or R ² may carry 1 to 4 identical or different groups R ^a ;
R ^a is halogen, cyano, nitro, hydroxyl, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkylcarbonyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ - haloalkoxy, C ₁ -C ₆ - alkoxycarbonyl, C ₁ -C ₆ - alkylthio, C ₁ -C ₆ - alkylamino, di -C ₁ -C ₆ - alkylamino, C ₂ -C ₆ -alkenyl, C ₂ -C ₈ -haloalkenyl, C ₂ -C ₆ -alkenyloxy, C ₂ -C ₈ -alkynyl, C ₂ -C ₈ -haloalkynyl, C ₃ -C ₆ -alkynyl 5- or 6-membered containing 1 to 4 heteroatoms from the group consisting of oxy, oxy-C ₁ -C ₃ -alkyleneoxy, C ₃ -C ₈ -cycloalkenyl, phenyl, naphthyl, O, N and S Saturated, partially unsaturated or aromatic heterocycles, wherein these aliphatic, alicyclic or aromatic groups are partially or partially Completely may be halogenated;
X is cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₃ -C ₄ -alkenyloxy, C ₁ -C ₂ -haloalkoxy, or C ₃ -C ₄ -haloalkenyloxy is there)
6-pentafluorophenyl triazolopyrimidine. X is cyano, C ₁ -C ₄ - alkoxy, C ₃ -C ₄ - alkenyloxy, C ₁ -C ₂ - haloalkoxy or C ₃ -C ₄ - halo alkenyloxy, according to claim 1 A compound of formula I.   A compound of formula I according to claim 1 or 2, wherein X is cyano.   3. A compound of formula I according to claim 1 or 2, wherein X is methoxy. X is C ₁ -C ₄ - alkyl, a compound of formula I according to claim 1. R ¹ and R ² are:
R ¹ is CH (CH ₃ ) -CH ₂ CH ₃ , CH (CH ₃ ) -CH (CH ₃ ) ₂ , CH (CH ₃ ) -C (CH ₃ ) ₃ , CH (CH ₃ ) -CF ₃ , CH ₂ C (CH ₃ ) ═CH ₂ , CH ₂ CH═CH ₂ , cyclopentyl or cyclohexyl;
R ² is hydrogen or methyl;
R ¹ and R ² together are-(CH ₂ ) ₂ CH (CH ₃ ) (CH ₂ ) ₂ -,-(CH ₂ ) ₂ CH (CF ₃ ) (CH ₂ ) _2- , or-(CH ₂ ) ₂ O (CH ₂ ) ₂ -is formed;
6. A compound of formula I according to any of claims 1-5, defined as Formula I.1:

(Where
G is C ₂ -C ₆ -alkyl, C ₁ -C ₄ -alkoxymethyl, or C ₃ -C ₆ -cycloalkyl;
R ² is hydrogen or methyl;
X is cyano, methyl, methoxy or ethoxy)
Compound. Formula I.2:

(Where
Y is hydrogen or C ₁ -C ₄ -alkyl and X is cyano, methyl, methoxy or ethoxy)
Compound. Formula I.3:

(Where
D together with the nitrogen atom forms a 5- or 6-membered heterocyclyl or heteroaryl linked through N, and also adds another heteroatom from the group consisting of O, N and S as ring members. And / or halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -haloalkenyl, C ₁ -C ₆ -alkoxy, C _{From 1} -C ₆ -haloalkoxy, C ₃ -C ₆ -alkenyloxy, C ₃ -C ₆ -haloalkenyloxy, (exo) -C ₁ -C ₆ -alkylene and oxy-C ₁ -C ₃ -alkyleneoxy May carry one or more substituents from the group;
X is cyano, methyl, methoxy or ethoxy)
Compound. Formula II:

(Where Hal is a halogen atom)
Of 5-halo-6- (2,4,6-trifluorophenyl) triazolopyrimidine of formula III:
MX III
(Wherein M is ammonium, tetraalkylammonium, or an alkali metal or alkaline earth metal cation, and X is as defined in claim 2).
A process for preparing a compound of formula I according to claim 2 by reacting with a compound of Formula IV:

2-aminotriazole of formula V:

(Wherein R and X ¹ are independently of each other C ₁ -C ₄ -alkyl, and L ¹ , L ² and L ³ are as defined in claim 1)
By reacting with a keto ester of

To obtain a 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidine of formula VII by halogenating VI with a halogenating agent:

(Where Hal is a halogen atom)
After obtaining the halopyrimidine of VII, formula VIII:

(Wherein R ¹ and R ² are as defined in formula I)
A process for preparing a compound of formula I according to claim 5 by reacting with an amine of   A composition comprising a solid or liquid carrier and a compound of formula I according to claim 1 or 2.   A seed comprising the compound of formula I according to claim 1 or 2 in an amount of 1 to 1,000 g / 100 kg.   A method for controlling phytopathogenic harmful fungi, comprising an effective amount of a compound of formula I according to claim 1 or 2 to protect against fungi or fungal infestations, plants, soil or seeds A method comprising the steps of: