EP1910373A1 - Fungicide 6-phenyl-triazolopyrimidinyl amines - Google Patents

Abstract

The invention relates to 6-phenyl-triazolopyrimidinyl amines of formula (I) wherein the substituents have the designations cited in the description. The invention also relates to methods for producing said compounds, to agents containing the same, and to the use thereof for controlling plant pathogenic fungi.

Description

Fungicides 6-phenyl-triazolopyrimidinylannines

description

The present invention relates to 6-phenyl-triazolopyrimidinylamines of the formula I,

in which the substituents have the following meanings:

L ^1, L ^2, L ³ are independently hydrogen, halogen, hydroxy, mercapto, nitro, NR ^A R ^B, Ci-Cio-alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₆ -alkyl keny I, C ₂ -C ₆ alkynyl, C ₃ -C ₆ alkoxy, phenyl, phenoxy, phenylthio, benzyloxy and benzylthio; R ^A , R ^{B are} hydrogen and C ₁ -C ₆ -alkyl;

wherein at least one group L ^1, L ² or L ³ is not hydrogen, and two adjacent groups L ^1, L ² and L ³ together form a Ci-C ₄ alkylene, C ₂ -C ₄ - oxyalkylene, Ci-C3-oxyalkyleneoxy or butadienyl group;

R ¹ is ethyl, n-propyl, Ci-C ₄ haloalkyl, C ₂ -C ₆ -alkyl keny I, C ₂ -C ₆ alkynyl, or C ₂ -C ₈ - alkoxyalkyl;

wherein the groups R ¹ , L ¹ , L ² and L ^{3 are} unsubstituted or substituted by one to four identical or different groups R ^a : R ^a halogen, cyano, hydroxy, mercapto, Ci-Cio-alkyl, Ci-Cio-haloalkyl , C ₃ -

Cβ-cycloalkyl, C ₂ -C 10 -alkenyl, C ₂ -C 10 -alkynyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio,

C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl or NR ^A R ^B ;

R ² is hydrogen, halogen, cyano, NR ^A R ^B, hydroxyl, mercapto, Ci-C ₆ alkyl, CrC logenalkyl -Ha- _6, C ₃ -C ₈ cycloalkyl, Ci-C ₆ alkoxy, Ci-C ₆ Alkylthio, C ₃ -C ₈ -cycloalkoxy, C ₃ -C ₈ -cycloalkylthio, carboxyl, formyl, C ₁ -C 10 -alkylcarbonyl, C ₁ -C 10 -alkoxycarbonyl, C ₂ -C 10 -alkenyloxycarbonyl, C ₂ -Cio -alkynyloxycarbonyl , Phenyl, phenoxy, phenylthio, benzyloxy, benzylthio and C ₁ -C ₆ -alkyl-S (O) _m -; m is 0, 1 or 2; wherein the cyclic groups in L ¹ , L ² , L ³ , R ^a and R ^{2 are} unsubstituted or substituted by one to four groups R ^b :

R ^{b is} halogen, cyano, hydroxy, mercapto, nitro, NR ^A R ^B, Ci-Cio-alkyl, -C ₆ - haloalkyl, C ₂ -C ₆ -alkyl keny I, C ₂ -C ₆ alkynyl, and Ci-C ₆ alkoxy. In addition, the invention relates to processes for the preparation of these compounds, compositions containing them and their use for controlling phytopathogenic harmful fungi.

EP-A 71 792 discloses individual fungicidally active 6-phenyltriazolopyrimidinylamines. However, their effect is in many cases unsatisfactory. On this basis, the object of the present invention is to provide compounds with improved activity and / or broadened spectrum of activity.

Accordingly, the compounds defined above were found. Furthermore, processes and intermediates for their preparation, agents containing them and methods for controlling harmful fungi using the compounds I have been found.

The compounds of the formula I differ from the compounds known from EP-A 71 792 essentially by the substitution in positions 2 and 5 of the triazolopyrimidine skeleton.

The compounds of the formula I have an over the known compounds increased activity against harmful fungi.

The compounds of the invention can be obtained in various ways. Advantageously, the compounds according to the invention are obtained by reacting substituted β-keto esters of the formula II with 3-amino-1,2,4-triazole of the formula III to give 7-hydroxytriazolopyrimidines of the formula IV. The group R ¹ and L ¹ to L ³ in formulas II and IV have the meanings as for formula I and the group R in formula II means C 1 -C ₄ -alkyl, for practical reasons, methyl, ethyl or propyl is preferred therein.

The reaction of the substituted .beta.-keto esters of the formula II with the aminotriazoles of the formula III can be carried out in the presence or absence of solvents. It is advantageous to use those solvents to which the starting materials are largely inert and in which they are completely or partially soluble. The solvents used are, in particular, alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, amides such as dimethylformamide, diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanoic acids such as formic acid, Acetic acid, propionic acid or bases, such as alkali metal and alkaline earth metal metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates and alkali metal hydrogencarbonates, organometallic compounds, in particular alkali metal alkyls, alkyl magnesium halides and alkali metal and alkaline earth metal alkoxides and dimethoxy magnesium, and also organic bases, for example tertiary amines such as Trimethylamine, triethylamine, triisopropylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines and mixtures of these solvents with water in question. Suitable catalysts are bases, as mentioned above, or acids, such as sulfonic acids or mineral acids. The reaction is particularly preferably carried out without a solvent or in chlorobenzene, xylene, dimethyl sulfoxide, N-methylpyrrolidone. Particularly preferred bases are tertiary amines such as tri-isopropylamine, tributylamine, N-methylmorpholine or N-methylpiperidine. The temperatures are between 50 and 300 ^° C., preferably 50 to 180 ^° C., when working in solution [cf. EP-A 770 615; Adv. Het. Chem. Vol. 57, p. 81ff. (1993)].

The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.

The condensation products of the formula IV thus obtained are usually precipitated from the reaction solutions in pure form and are, after washing with the same solvent or with water and subsequent drying with halogenating agents, in particular chlorinating or brominating agents, the compounds of the formula V in the US Pat Hal is chlorine or bromine, in particular chlorine, reacted. The reaction is preferably with chlorinating agents such as phosphorus oxychloride, thionyl onylchlorid or sulfuryl chloride at 50 ⁰ C to 150 ⁰ C, preferably phosphorus oxytrichloride in at reflux temperature excess. After evaporation of the excess Phosphoroxitrichlorids the residue is treated with ice water optionally with the addition of a water-immiscible solvent. The isolated from the dried organic phase optionally after evaporation of the inert solvent chlorination product is usually very pure and is then reacted with ammonia in inert solvents at 100 ⁰ C to 200 ⁰ C to the Triazolopyrimidin-7 ylaminen. The reaction is preferably carried out with 1 to 10 molar excess of ammonia under pressure of 1 to 100 bar.

The new triazolopyrimidin-7-ylamines are optionally isolated after evaporation of the solvent by trituration in water as crystalline compounds. The β-keto esters of formula II can be prepared as in Organic Synthesis Coli. Vol. 1, p. 248, or are commercially available.

Alternatively, the novel compounds of the formula I can be obtained by reacting substituted acyl cyanides of the formula VI in which R ¹ and L ¹ to L ^{3 have} the meanings indicated above, with aminotriazoles of the formula IM.

The reaction can be carried out in the presence or absence of solvents. It is advantageous to use those solvents to which the starting materials are largely inert and in which they are completely or partially soluble. The solvents used are, in particular, alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, amides such as dimethylformamide, diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanoic acids such as formic acid, Acetic acid, propionic acid or bases, as mentioned above, and mixtures of these solvents with water in question. The reaction temperatures are between 50 and 300 ⁰ C, preferably at 50 to 150 ⁰ C when working in solution.

The new triazolopyrimidin-7-ylamines are optionally isolated after evaporation of the solvent or dilution with water as crystalline compounds.

The substituted alkyl cyanides of the formula VI required for the preparation of the triazolopyrimidin-7-ylamines are known in some cases or can be prepared by known methods from alkyl cyanides and carboxylic acid esters with strong bases, e.g. Alkali metal hydrides, alkali metal alcoholates, alkali diamides or metal alkyls [cf.: J. Amer. Chem. Soc. Vol. 73, (1951) p. 3766].

If individual compounds I are not accessible in the above-described ways, they can be prepared by derivatization of other compounds I.

However, if isomer mixtures are obtained in the synthesis, separation is generally not necessary since the individual isomers may partially interconvert during preparation for use or during use (eg, under the action of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled. In the definitions of the symbols given in the above formulas, collective terms have been used that are generally representative of the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated, straight-chain or mono- or di-branched hydrocarbon radicals having 1 to 4, 6, 8 or 12 carbon atoms, e.g. C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1, 1-dimethylethyl, n-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-dimethylbutyl, 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-methylpropyl;

Haloalkyl: alkyl group as mentioned above, in which partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above: in particular chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl;

Cycloalkyl: mono- or bicyclic saturated hydrocarbon groups having 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;

Alkoxyalkyl: saturated, straight-chain or mono-, di- or tri-branched hydrocarbon chain which is interrupted by an oxygen atom, for. B. C ₅ -C ₂ alkoxyalkyl: hydrocarbon chain as described above having 5 to 12 carbon atoms, which may be interrupted by an oxygen atom at any position, such as propoxy-ethyl, butoxy-ethyl, pentoxy-ethyl, hexyloxy-ethyl , Heptyloxyethyl, octyloxyethyl, nonyloxyethyl, 3- (3-ethyl-hexyloxy) -ethyl, 3- (2,4,4-trimethyl-pentyloxy) -ethyl, 3- (1-ethyl-3-) methyl-butoxy) -ethyl, ethoxy-propyl, propoxy-propyl, butoxy-propyl, pentoxy-propyl, hexyloxy-propyl, heptyloxy-propyl, octyloxy-propyl, nonyloxy-propyl, 3- (3-ethyl-hexyloxy) propyl, 3- (2,4,4-trimethyl-pentyloxy) -propyl, 3- (1-ethyl-3-methyl-butoxy) -propyl, ethoxy-butyl, propoxy-butyl, butoxy-butyl, pentoxy-butyl , Hexyloxy-butyl, heptyloxy-butyl, octyloxy-butyl, nonyloxy-butyl, 3- (3-ethyl-hexyloxy) -butyl, 3- (2,4,4-trimethyl-pentyloxy) -butyl, 3- (1 - Ethyl 3-methyl-butoxy) -butyl, methoxy-pentyl, ethoxy-pentyl, propoxy-pentyl, butoxy-pentyl, pentoxy-pentyl, hexyloxy-pentyl, heptyl-oxy-pentyl, 3- (3-methyl-hexyloxy ) -pentyl, 3- (2,4-dimethyl-pentyloxy) -pentyl, 3- (1-ethyl-3-methyl-butoxy) -pentyl; Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in any position, for example C 2 -C 6 alkenyl, such as 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-butyl-, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl 1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-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-pe ntenyl, 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-di- methyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-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;

Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4, 6, 8 or 10 carbon atoms and one or two triple bonds in any position, for example C ₂ -C ₆ -AlkJnVl such as 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-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;

Alkylene: divalent unbranched chains, preferably from 3 to 5 CH ₂ groups, eg CH ₂ , CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ and CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ;

Oxyalkylene: divalent unbranched chains of 2 to 4 CH ₂ groups, wherein a valence is bonded to the skeleton via an oxygen atom, for example OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ and OCH ₂ CH ₂ CH ₂ CH ₂ ; Oxyalkylenoxy: divalent unbranched chains of 1 to 3 Chfe groups, both valences being bonded to the skeleton via an oxygen atom, eg OCH ₂ O, OCH ₂ CH ₂ O and OCH ₂ CH ₂ CH ₂ O.

Included within the scope of the present invention are the (R) and (S) isomers and the racemates of compounds of formula I having chiral centers.

With regard to their intended use of the triazolopyrimidinylamines of the formula I, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:

One embodiment relates to compounds I in which the 6-phenyl group is substituted by one to three halogen or Ci-C ₈ alkyl groups.

A further embodiment of the compounds of the formula I are those in which no group R ^a is present.

A further embodiment relates to the compounds of the formula I in which L ¹ and L ^{3 are} hydrogen.

A further embodiment relates to the compounds of the formula I in which L ² and L ^{3 are} hydrogen.

A further embodiment relates to the compounds of the formula I in which L ¹ and L ^{2 are} different from hydrogen and L ^{3 is} hydrogen. Particularly preferred are those compounds in which L ¹ and L ^{2 are} halogen.

A further embodiment relates to the compounds of formula I, in which the group of L ^{2 is} alkyl, in particular branched alkyl, such as tert. Butyl is and L ¹ and L ^{3 are} hydrogen.

A further embodiment relates to the compounds of the formula I in which the 6-phenyl group is substituted by one to three groups halogen, cyano, hydroxyl, mercapto, nitro, NR ^A R ^B , C ₁ -C 10 -alkyl, C ₁ -C ₆ -haloalkyl, C ₂ -C ₆ -Al keny I, C ₂ -C ₆ alkynyl and CrC ₆ - alkoxy substituted. The phenyl group particularly preferably carries two, in particular a substituent.

One embodiment relates to the compounds of the formula I in which R ^{1 is} ethyl.

A further embodiment relates to the compounds of the formula I in which R ^{1 is} n-propyl. A further embodiment relates to the compounds of formula I in which R ^{1 is} halomethyl, in particular trifluoromethyl.

A further embodiment relates to the compounds of the formula I in which R ^{1 is} alkenyl, in particular allyl.

A further embodiment relates to the compounds of the formula I in which R ¹ is alkoxyalkyl, preferably C ¹ -C 7 -alkoxymethyl, in particular methoxymethyl.

A further embodiment relates to the compounds of the formula I in which R ^{2 is} hydrogen.

In a further embodiment of the compounds I, R ^{2 is} Nhfe or C 1 -C ₄ -alkyl, preferably methyl or NH 3, in particular NH 3.

Particular preference is given to compounds of the formula I in which L ^{1 is} halogen, cyano, hydroxyl, mercapto, nitro, NR ^A R ^B , C 1 -C 6 -alkyl, halomethyl, and C 1 -C 2 -alkoxy.

In particular, with regard to their use, the compounds I compiled in the following tables are preferred. The groups mentioned in the tables for a substituent also individually, independently of the combination in which they are mentioned, represent a particularly preferred embodiment of the relevant substituent.

Table 1

Compounds of the formula I in which R ^{1 is} ethyl, R ^{2 is} hydrogen and the combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table 2

Compounds of the formula I in which R ^{1 is} ethyl, R ^{2 is} amino and the combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table 3

Compounds of the formula I in which R ^{1 is} ethyl, R ^{2 is} methyl and the combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table 4

Compounds of the formula I in which R ^{1 is} n-propyl, R ^{2 is} hydrogen and

Combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A. Table 5

Compounds of the formula I in which R ^{1 is} n-propyl, R ^{2 is} amino and the combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A corresponds to Table 6

Compounds of the formula I in which R ^{1 is} n-propyl, R ^{2 is} methyl and the combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table 7

Compounds of the formula I in which R ^{1 is} trifluoromethyl, R ^{2 is} hydrogen and the combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table 8

Compounds of the formula I in which R ^{1 is} trifluoromethyl, R ^{2 is} amino and the

Combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table 9

Compounds of the formula I in which R ^{1 is} trifluoromethyl, R ^{2 is} methyl and the

Combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table 10

Compounds of the formula I in which R ^{1 is} AlII y, R ^{2 is} hydrogen and the combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table 11

Compounds of the formula I in which R ^{1 is} AlII y, R ^{2 is} amino and the combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table 12

Compounds of the formula I in which R ^{1 is} AlII y, R ^{2 is} methyl and the combination of L ¹ , L ² and L ³ for a compound corresponds in each case to one row of Table A.

Table A

The compounds I are suitable as fungicides. They are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, Peronosporomycetes (syn. Oomycetes) and Basidiomycetes. They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.

They are particularly important for the control of a variety of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers. Beans, tomatoes, potatoes and pumpkins, as well as the seeds of these plants.

In particular, they are suitable for controlling the following plant diseases:

Alternaria species on vegetables, oilseed rape, sugar beets and fruits and rice, such as A.solani or A. altemata on potatoes and tomatoes,

• Aphanomyces species of sugar beets and vegetables,

• Ascochyta species on cereals and vegetables,

Bipolaris and Drechslera species on maize, cereals, rice and turf, e.g. D.maydis on corn,

• Blumeria graminis (powdery mildew) on cereals,

• Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines,

• Bremia lactucae on salad,

Cercospora species on corn, soybeans, rice and sugar beet,

Cochliobolus species on corn, cereals, rice, e.g. Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice,

• Colletotricum species on soybeans and cotton,

• Drechslera species, Pyrenophora species on maize, cereals, rice and turf, such as D. teres on barley or D. tritici-repentis on wheat, Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum, and Formitipora punctata (syn. Phellinus punctatus),

Exserohilum species on corn,

Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Fusarium and Verticillium species on various plants, e.g. F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of plants such as e.g. Tomatoes,

Gaeumanomyces graminis on cereals,

Gibberella species on cereals and rice (eg Gibberella fujikuroi on rice),

• Grainstaining complex on rice,

Helminthosporium species on corn and rice,

Michrodochium nivale on cereals,

Mycosphaerella species on cereals, bananas and peanuts, e.g. M. graminicola on wheat or M.fijiensis on bananas,

Peronospora species on cabbage and bulbous plants, such as P. brassicae on cabbage or P. destructor on onion,

• Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,

• Phomopsis species on soybeans and sunflowers,

• Phytophthora infestans on potatoes and tomatoes,

Phytophthora species on various plants, e.g. P.capsici on paprika,

Plasmopara viticola on grapevines,

• Podosphaera leucotricha on apple,

Pseudocercosporella herpotrichoides on cereals,

Pseudoperonospora on various plants, e.g. P. cubensis on cucumber or P. humili on hops,

Puccinia species on various plants, e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals, or P. asparagi on asparagus,

Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum, Entyloma oryzae, on rice,

• Pyricularia grisea on grass and cereals,

• Pythium spp. on turf, rice, corn, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants such as e.g. P.ultiumum on different plants, P. aphanidermatum on grass,

• Rhizoctonia species on cotton, rice, potatoes, turf, corn, oilseed rape, sugar beet, vegetables and various plants such as e.g. R.solani on turnips and various plants,

• Rhynchosporium secalis on barley, rye and triticale,

• Sclerotinia species on oilseed rape and sunflowers,

• Septoria tritici and Stagonospora nodorum on wheat,

• Erysiphe (syn. Uncinula) necator on grapevine,

• Setospaeria species on corn and turf,

• Sphacelotheca reilinia on corn, Thievaliopsis species on soybeans and cotton,

• Tilletia species of cereals,

Ustilago species on cereals, maize and sugarcane, such as U. maydis on corn,

• Venturia species (scab) on apples and pears like. e.g. V. inaequalis to apple.

In particular, they are suitable for controlling harmful fungi from the class of Peronosporomycetes (syn.Oomyceten), such as Peronospora species, Phytophthora species, Plasmopara viticola and Pseudoperonospora species.

The compounds I are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In wood preservation, particular attention is paid to the following harmful fungi: ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sciophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleu- rotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.

The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.

The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.

In seed treatment, e.g. By dusting, coating or impregnating seeds, in general, amounts of active ingredient of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of seed are needed.

When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection. The compounds of the formula I can be present in various crystal modifications, which may differ in their biological activity. They are also the subject of the present invention.

The compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

• water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), Acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used

Carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin liquors and methyl cellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, Xy- lol, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, metha- nol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell meal, cellulose powder and other solid carriers.

Seed treatment formulations may additionally contain binders and / or gelling agents and optionally dyes.

Binders can be added to increase adhesion of the active ingredients to the seed after treatment. Examples of suitable binders are EO / PO block copolymer surfactants, but also polyvinyl alcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrenes, polyethyleneamines, polyethylene amides, polyethyleneimines (Lupasol®, Polymin®), polyethers, polyurethanes, polyvinyl acetates, Tylose and Copolymers of these polymers. A suitable gelling agent is, for example, carrageenan (Satiagel®).

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

For seed treatment, the formulations in question give, after dilution of from two to ten times, active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Examples of formulations according to the invention are: 1. Products for dilution in water

A Water-soluble concentrates (SL, LS)

10 parts by weight of a compound according to the invention are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content.

B Dispersible Concentrates (DC)

20 parts by weight of a compound according to the invention are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight

C Emulsifiable Concentrates (EC)

15 parts by weight of a compound according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content.

D emulsions (EW, EO, ES)

25 parts by weight of a compound according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate in each case 5 parts by weight). This mixture is added to 30 parts by weight of water by means of an emulsifying machine (e.g., Ultraturax) and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E suspensions (SC, OD, FS)

20 parts by weight of a compound according to the invention are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

F Water-dispersible and Water-soluble Granules (WG, SG) 50 parts by weight of a compound according to the invention are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules , Dilution in water gives a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and Water-Soluble Powders (WP, SP, SS, WS) 75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H gel formulations

In a ball mill, 20 parts by weight of a compound of the invention, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent are ground to a fine suspension. Dilution with water results in a stable suspension with 20% by weight active ingredient content.

2. Products for direct application

I dusts (DP, DS)

5 parts by weight of a compound according to the invention are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content.

J Granules (GR, FG, GG, MG)

0.5 parts by weight of a compound according to the invention are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

K ULV solutions (UL)

10 parts by weight of a compound according to the invention are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with 10 wt .-% active ingredient content.

For seed treatment, water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are usually used. These formulations can be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing.

Preference is given to using FS formulations for seed treatment. Usually, such formulations contain 1 to 800 g / l of active ingredient, 1 to 200 g / l of surfactants, 0 to 200 g / l of antifreeze, 0 to 400 g / l of binder, 0 to 200 g / l of dyes and solvents, preferably water.

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, litter, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

As adjuvants in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ^® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluro- nic RPE 2035 ^® and Genapol B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ^®.

The agents according to the invention can also be present in the application form as fungicides together with other active substances, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. When mixing the compounds (I) or the agents containing them with one or more further active compounds, in particular fungicides, in many cases the activity spectrum can be widened or resistance developments can be prevented. In many cases, synergistic effects are obtained. The following list of fungicides with which the compounds according to the invention can be used together is intended to illustrate, but not limit, the possible combinations.

strobilurins

Azoxystrobin, dimoxystrobin, enestroburine, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-Chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) -carbamic acid methyl ester, 2- (ortho)

(2,5-dimethylphenyl-oxymethylene) phenyl) -3-methoxy-methyl acrylate;

carboxamides

- Carboxylic acid anilides: Benalaxyl, Benodanil, Boscalid, Carboxin, Mepronil, Fenfuram, Fenhexamid, Flutolanil, Furametpyr, Metalaxyl, Ofurace, Oxadixyl, Oxycarboxin, Penthiopyrad, Thifluzamide, Tiadinil, 4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid - (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2 -methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ' , 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4'-dichloro-5-fluoro-biphenyl-2-yl) yl) amide, 3,4-dichloro-isothiazole-5-carboxylic acid (2-cyano-phenyl) -amide;

- Carboxylic acid morpholides: Dimethomorph, Flumorph;

Benzoic acid amides: flumetover, fluopicolide (picobenzamide), zoxamide;

Other carboxamides: carpropamide, diclocymet, mandipropamide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino 3-methyl-butyramide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl) -ethyl) -2-ethanesulfonyl-amino-3-methyl- butyramide;

azoles

- Triazoles: Bitertanol, Bromuconazole, Cyproconazole, Difenoconazole, Diniconazole, Enilconazole, Epoxiconazole, Fenbuconazole, Flusilazole, Fluquinconazole, Flutriafol, Hexaconazole, Imibenconazole, Ipconazole, Metconazole, Myclobutanil, Penconazole, Propiconazole, Prothioconazole, Simeconazole, Tebuconazole, Tetraconazole, Triadimenol, Triadimefon , Triticonazole;

- imidazoles: cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole;

Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;

- Other: Ethaboxam, Etridiazole, Hymexazole;

Nitrogen-containing heterocyclyl compounds

Pyridines: fluazinam, pyrifenox, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine; Pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil;

- Piperazines: triforins,

- Pyrroles: fludioxonil, fenpiclonil;

- Morpholines: aldimorph, dodemorph, fenpropimorph, tridemorph;

Dicarboximides: iprodione, procymidone, vinclozolin;

- others: acibenzolar-S-methyl, anilazine, captan, captafol, dazomet, diclomethine, fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, octhilinone, probenazole, proquinazide, pyroquilone, quinoxyfen, tricyclazole, 5-chloro-7- (4- methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 2-butoxy-6-iodo-3 propyl-chromen-4-one, 3- (3-bromo-6-fluoro-2-methyl-indole-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide;

Carbamates and dithiocarbamates

Dithiocarbamates: Ferbam, Mancozeb, Maneb, Metiram, Metam, Propineb, Thiram, Zineb, Ziram;

Carbamates: diethofencarb, flubenthiavalicarb, iprovalicarb, propamocarb, 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino) -propionic acid methyl ester, N- (1 - (1 - (4- cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid (4-fluorophenyl) ester;

Other fungicides

- guanidines: dodine, iminoctadine, guazatine;

- Antibiotics: Kasugamycin, Polyoxins, Streptomycin, Validamycin A;

Organometallic compounds: fentin salts;

Sulfur-containing heterocyclyl compounds: isoprothiolanes, dithianone;

Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and their salts;

Organochlorine compounds: thiophanates methyl, chlorothalonil, dichlofluanid, toluylfluanid, flusulfamides, phthalides, hexachlorobenzene, pencycuron, quintozene;

Nitrophenyl derivatives: binapacryl, dinocap, dinobuton;

- Inorganic active substances: Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulphate, sulfur;

- Other: Spiroxamine, Cyflufenamid, Cymoxanil, Metrafenone.

synthesis Examples

The procedure given in the synthesis example below was used with appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the following table with physical data. Synthesis of 5-ethyl-6- (p-ethylphenyl) -7-aminotriazolopyrimidine [1-5]

A suspension of 0.20 g (1 mmol) of 1- (4-ethylphenyl) -2-oxo-butane-1-nitrile, 0.09 g (1 mmol) of 3-amino-1, 2,4-triazole and 0, sitylen 04 g (0.2 mmol) of p-toluenesulfonic acid in 2.5 ml of metal was heated at for about 12.5 hrs. to 160 ⁰ C on a water separator. The mesitylene was then distilled off and the residue was digested from dichloromethane / water. The residue was filtered off, dried and recrystallized from diisopropyl ether. This gave 120 mg of the title compound as colorless crystals.

applications

The fungicidal action of the compounds according to the invention was demonstrated by the following experiments:

The active compounds were prepared as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent-emulsifier from 99 to 1 ad 10 ml. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.

Use Example 1 - Efficacy against tomato blight caused by Alternaria solani

Leaves of potted tomato plants were sprayed to drip point with aqueous suspension in the drug concentration below. The following day, the leaves were infected with an aqueous spore suspension of Alternaria solani in 2% biomalt solution having a density of 0.17 x 10 ⁶ spores / ml. Subsequently, the plants are placed in a water vapor-saturated chamber at temperatures between 20 and 22 ° C. After 5 days, the disease on the untreated, but infected control plants had developed so strongly that the infestation could be determined visually in%.

In this test, the plants treated with 250 ppm of the active ingredient 1-1 showed a maximum of 5% infestation, while the untreated plants were 90% infected.

Use Example 2 - Efficacy against vine peronospora caused by Plasmopara viticola at 7 days of protective use

Leaves of pot fry were sprayed to drip point with aqueous suspension in the concentration of active compound given below. In order to be able to assess the lasting effect of the substances, the plants were placed in the greenhouse for 7 days after the spray coating had dried on. Only then were the leaves inoculated with an aqueous zoospore suspension of Plasmopara viticola. Thereafter, the vines were first set up for 48 hours in a water vapor-saturated chamber at 24 ° C and then for 5 days in the greenhouse at temperatures between 20 and 30 ⁰ C. After this time, the plants were again placed in a moist chamber for 16 hours to accelerate the sporangiophore outbreak. Then the extent of infestation on the undersides of the leaves was visually determined.

In this test, the plants treated with 250 ppm of the active compounds I-2 or I-3 showed a maximum of 1% infestation, while the untreated plants were 90% infected.

Use Example 3 - Efficacy against vine peronospora caused by Plasmopara viticola

Leaves of pot fry were sprayed to drip point with aqueous suspension in the concentration of active compound given below. The following day, the undersurfaces of the leaves were inoculated with an aqueous sporangia suspension of Plasmopara viticola. Thereafter, the vines were first set up for 48 hours in a water vapor-saturated chamber at 24 ⁰ C and then for 5 days in the greenhouse at temperatures between 20 and 30 ⁰ C. After this time, the plants were again placed in a humid chamber for 16 hours to accelerate the sporangiopathic outbreak. Then the extent of infestation on the undersides of the leaves was visually determined.

In this test, the plants treated with 250 ppm of the active ingredient I-4 showed 10% infestation, while the untreated plants were 90% infected. Use Example 4 - Activity against tomato late blight on tomatoes caused by Phytophthora infestans at 3 days of protective treatment

Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. 3 days after application, the leaves were infected with an aqueous sporangia suspension of Phytophthora infestans. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 18 and 20 ⁰ C. After 6 days, the late blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.

In this test, the plants treated with 250 ppm of the active compounds I-5 or I-6 showed a maximum of 10% infestation, while the untreated plants were 90% infected.

Use Example 5 - Activity against tomato late blight on tomatoes caused by Phytophthora infestans at 1 day of protective treatment

Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. One day after application, the leaves were infected with an aqueous sporangia suspension of Phytophthora infestans. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 18 and 20 ⁰ C. After 6 days, the late blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.

In this test, the plants treated with 250 ppm of the active compounds I-6 or I-7 showed 1% infestation, while the untreated plants were 90% infected.

Claims

claims

1. 6-phenyl-triazolopyrimidinylamine of the formula I.

in which the substituents have the following meanings:

L ^1, L ^2, L ³ are independently hydrogen, halogen, hydroxy, mercapto, nitro, NR ^A R ^B, Ci-Cio-alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₆ -alkyl keny I, C ₂ -C ₆ - alkinyl, C3-C ₆ -alkoxy, phenyl, phenoxy, phenylthio, benzyloxy and benzyl zylthio; R ^A , R ^{B are} hydrogen and C ₁ -C ₆ -alkyl;

wherein at least one group L ¹ , L ² or L ^{3 is} not hydrogen and two adjacent groups of L ¹ , L ² and L ³ together a CrC ₄ -AlkV- len, C ₂ -C ₄ -Oxyalkylen, Ci-C3-Oxyalkylenoxy or butadienyl group;

R ¹ is ethyl, n-propyl, Ci-C ₄ haloalkyl, C ₂ -C ₆ -alkyl keny I, C ₂ -C ₆ alkynyl, or C ₂ - Cβ-alkoxyalkyl;

wherein the groups R ¹ , L ¹ , L ² and L ^{3 are} unsubstituted or substituted by one to four identical or different groups R ^a : R ^a halogen, cyano, hydroxy, mercapto, Ci-Cio-alkyl, Ci-Cio-halogen - alkyl, C ₃ -C ₈ cycloalkyl, C ₂ -Cio-alkenyl, C ₂ -Cio-alkynyl, Ci-C ₆ alkoxy, Ci-Ce-alkylthio, Ci-C ₆ alkoxy-C ₆ - alkyl or NR ^A R ^B ;

R ² is hydrogen, halogen, cyano, NR ^A R ^B, hydroxyl, mercapto, Ci-C ₆ alkyl, d- C ₆ haloalkyl, C ₃ -C ₈ cycloalkyl, Ci-C ₆ alkoxy, Ci-C ₆ alkylthio, C ₃ -C ₈ - cycloalkoxy, C ₃ -C ₈ cycloalkylthio, carboxyl, formyl, Ci-Cio-alkylcarbonyl, Ci-Cio-alkoxycarbonyl, C ₂ -Cio-alkenyloxycarbonyl, C ₂ -Cio-alkynyloxy carbonyl , Phenyl, phenoxy, phenylthio, benzyloxy, benzylthio and C ₁ -C ₆ -alkyl-S (O) _m -; m is 0, 1 or 2; wherein the cyclic groups in L ¹ , L ² , L ³ , R ^a and R ^{2 are} unsubstituted or substituted by one to four groups R ^b :

R ^{b is} halogen, cyano, hydroxy, mercapto, nitro, NR ^A R ^B, Ci-Cio-alkyl, d- C ₆ haloalkyl, C ₂ -C ₆ -alkyl keny I, C ₂ -C ₆ alkynyl, and Ci C ₆ alkoxy.

2. Compounds of formula I according to claim 1, in which R ^{1 is} trifluoromethyl, ethyl or methoxymethyl.

3. Compounds of formula I according to claim 1 or 2, wherein R ^{2 is} hydrogen.

4. Compounds of formula I according to any one of claims 1 to 3, wherein L ^{3 is} hydrogen.

5. Process for the preparation of compounds of the formula I according to one of claims 1 to 4, characterized in that β-ketoesters of the formula II,

in which R stands for C 1 -C ₄ -alkyl, with an aminotriazole formula

to 7-hydroxytriazolopyrimidines of the formula IV

which converts to compounds of the formula V,

in the Hal for chlorine or bromine, are halogenated, and V is reacted with ammonia.

6. Compounds of formula IV and V according to claim 5.

7. A process for the preparation of compounds of the formula I according to claim 1, which comprises reacting acyl cyanides of the formula VI with an aminotriazole of the formula IM according to claim 5.

8. A fungicidal composition containing a solid or liquid carrier and a compound of formula I according to claim 1.

9. seed, containing a compound of formula I according to claim 1 in an amount of 1 to 1000 g per 100 kg.

10. A method for controlling phytopathogenic harmful fungi, characterized in that treating the fungi, or to be protected from fungal attack materials, plants, the soil or seeds with an effective amount of a compound of formula I according to claim 1.