EP1910371A1 - Fungicidal 5-methyl-6-phenylpyrazolopyrimidin-7-ylamines - Google Patents

Abstract

5-Methyl-6-phenylpyrazolopyrimidin-7-ylamines of the formula (I) in which the substituents are defined as in the description, processes for preparing these compounds, compositions comprising them, and their use for controlling phytopathogenic fungi.

Description

Fungicides 5-methyl-6-phenyl-pyrazolopyrimidin-7-ylamine

description

The present invention relates to 5-methyl-6-phenyl-pyrazolopyrimidin-7-ylamines of the formula I,

in which the substituents have the following meanings:

L ¹ , L ^{3 are} independently hydrogen, halogen, hydroxy, mercapto, nitro,

NR ^A R ^B , C ₁ -C 10 -alkyl, CHF ₂ , C ₂ -C ₆ -alkynyl, 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;

L ^{2 is} hydrogen, halogen, hydroxyl, mercapto, nitro, NR ^A R ^B , CH ₂ -C-C ₉ -alkyl, CHF ₂ , CF 3, C ₂ -C ₆ -alkylene I, C ₂ -C ₆ -alkyl I, phenyl, phenoxy, phenylthio, benzyloxy and benzylthio;

wherein two adjacent groups of L ^1, L ² and L ³ together are a CrC ₄ len -AIkV-, C ₂ -C ₃ may represent -Oxyalkylenoxy or butadienyl ₄ oxyalkylene, C;

wherein at least one group L ¹ , L ² or L ^{3 is} not hydrogen and the groups L ¹ , L ² or L ^{3 are} unsubstituted or substituted by one to four identical or different groups R ^a :

R ^{a is} halogen, cyano, hydroxy, mercapto, C ₁ -C 10 -alkyl, C ₁ -C 10 -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 ¹ 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, Ci-Cio-alkylcarbonyl, Ci-Cio-alkoxy carbonyl, C ₂ -Cio-alkenyloxycarbonyl, C ₂ -Cio-alkynyloxycarbonyl, Phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, C ₁ -C ₆ -alkyl-S (O) _m - and five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S; m is 0, 1 or 2; wherein the cyclic groups in L ¹ , L ² , L ³ , R ^a and / or R ^{1 are} unsubstituted or substituted by one to four groups R ^b : R ^{b is} halogen, cyano, hydroxy, mercapto, nitro, NR ^A R ^B, d-Cio-alkyl, -C ₆ - haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Cβ alkoxy, and five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S, which may be unsubstituted or substituted by one or more groups halogen and / or CrC ₄ -AlkVl.

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 5-methyl-6-phenylpyrazolopyrimidinylamines. However, their effect is in many cases unsatisfactory. On this basis, the object of the present invention is to provide compounds with improved action and / or broadened spectrum of action.

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 position 2 and 5, or the substitution of the phenyl ring in position 6 of the pyrazolopyrimidine 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 aminopyrazoles of the formula III to give 7-hydroxypyrazolopyrimidines of the formula IV. The groups L ¹ to L ³ and R ¹ in formulas II and IV have the meanings as for formula I and the group R in formula II means Ci-C ₄ -AlkVl, for practical reasons, methyl, ethyl or propyl is preferred therein.

NH _n The reaction of the substituted .beta.-keto esters of the formula II with the aminopyrazoles 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 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 Alkalimetal- lalkyle, alkylmagnesium halides and alkali metal and alkaline earth metal alkoxides and Dimethoxymagnesium, 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-Dimet Hyl- aminopyridine 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 in excess phosphorus oxytrichloride at reflux temperature. After evaporation of the excess Phosphoroxitrichlorids the residue is optionally with ice water Addition of a water-immiscible solvent treated. 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 7-amino-pyrazolo- pyrimidinen. The reaction is preferably carried out with 1 to 10 molar excess of ammonia under pressure of 1 to 100 bar.

The new pyrazolopyrimidin-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 L ¹ to L ^{3 have} the meanings given above, with aminopyrazoles 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 pyrazolopyrimidin-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 pyrazolopyrimidin-7-ylamines are known in some cases or can be prepared by known methods from alkyl cyanides and carboxylic esters with strong bases, for example alkali metal hydrides, alkali metal alkoxides, alkali metal amides or metal alkyls [cf.: J. Chem 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, unless isomeric mixtures are involved in the synthesis, separation is not necessarily required because the individual isomers can partially interconvert during processing for use or in use (e.g., under light, acid, or base action). 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 or 8 carbon atoms, e.g. C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 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-tri methylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methyl-propyl;

Haloalkyl: alkyl group as mentioned above, in which partially or completely the hydrogen atoms can 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. Cs-Ci2-alkoxyalkyl: carbon hydrogen 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, e.g. C2-C6 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-Butenyl, 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-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-butenyl, 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;

Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4 or 6 carbon atoms and one or two triple bonds in any position, C ₂ -C ₆ -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3 Butinyl, 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- butinyl, 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 Chfe 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 Chfe 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 CH ₂ 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 pyrazolopyrimidinylamines of the formula I, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:

Compounds I are preferred in which the 6-phenyl group is substituted by one to three halogen or CH 2-Ci-C4-alkyl groups.

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

A further preferred embodiment relates to the compounds of the formula I in which L ¹ and L ^{3 are} hydrogen. Particular preference is given to those compounds in which L ^{2 is} halogen or alkyl, in particular alkyl.

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

A further preferred 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 signify halogen.

A further preferred embodiment relates to the compounds of the formula I in which the 6-phenyl group is replaced by one to three identical or different groups halogen, CHF ₂ , CH ₂ -Ci-C ₈ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl is substituted. The phenyl group particularly preferably carries two, in particular a substituent. A further preferred embodiment relates to the compounds of the formula I in which R ^{1 is} not hydrogen.

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

Particular preference is given to compounds of the formula I in which L ^{1 is} 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} 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 2

Compounds of the formula I in which R ^{1 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 A

The compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, Peronosporomycetes (= syn. Oomycetes) and Basidiomycetes, in particular from the class of the Peronosporomycetes. 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 of 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, such as Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice,

• Colletotricum species on soybeans and cotton,

• Drechslera species, Pyrenophora species on maize, cereals, rice and turf, e.g. D.teres to barley or D. tritici-repentis to 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 onion plants, such as e.g. P. brassicae

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 maize,

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 Wall quantities are in the material protection, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of treated material.

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 application; 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), Acetate

(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 non-ionic and anionic emulsifiers (for example polyoxyethylene

Fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin liquors and methylcellulose.

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, mineral oil fractions of medium to high boiling point, such as or diesel oil, coal tar oils and oils of plant or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, 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 the 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 added with the addition of 10

Parts by weight of dispersing and wetting agents and 70 parts by weight of water or an organic solvent are comminuted in a stirred ball mill to a fine suspension of active ingredient. 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 added with the addition of 50% by weight of Parts of dispersants and wetting agents finely ground and produced by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in 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. Typically, such formulations contain 1 to 800 g / l active ingredient, 1 to 200 g / l surfactants, 0 to 200 g / l antifreeze, 0 to 400 g / l binder, 0 to 200 g / l 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, Enestroburin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Picoxystrobin, Pyraclostrobin, Trifloxystrobin, Orysastrobin, (2-Chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2 Ethyl chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) carbamic acid, 2- (ortho- (2,5-dimethylphenyl-oxymethylene) -phenyl) -3-methoxy- methyl acrylate;

carboxamides

- Carboxylic acid anilides: benalaxyl, benodanil, boscalid, carboxin, mepronil, fenfuram, fenhexamide, 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'-fluoro-biphenyl-2-yl) - amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide, 3-difluoromethyl-1-methylpyrazole 4-carboxylic acid (3 ', 4'-dichloro-5-fluoro-biphenyl-2-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;

- Other: 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 2-methyl-5-methyl-6- (p-ethylphenyl) -7-aminopyrazolopyrimidine [1-1]

A suspension of 0.30 g (1.6 mmol) of 1- (p-ethylphenyl) -2-oxo-butyro-1-nitrile, 0.19 g (2 mmol) of 3-amino-5-methyl-1, 2 pyrazole and 0.06 g (0.32 mmol) of p-toluenesulfonic acid in 10 ml Mesitylen was heated for 12 hrs. At 180 ⁰ C on a water. Thereafter, the Mesitylen was distilled off and the residue taken up with dichloromethane / water. After phase separation, the org. Dried phase, then freed from the solvent. There remained 300 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 on the basis of ethoxylated alkylphenols) in the volume ratio solvent-emulsifier from 99 to 1 ad 10 ml. was filled. 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 - Activity against tomato late blight caused by Phytophthora infestans in protective treatment

Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. The following day, the leaves were sprayed with an aqueous suspension of Sporangia

Phytophthora infestans infected. The plants were then 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 ingredient I-6 showed 5% infestation, while the untreated plants were 100% infested.

Claims

claims

1. 5-methyl-6-phenyl-pyrazolopyrimidin-7-ylamines of the formula I.

in which the substituents have the following meanings:

L ¹ , L ³ independently of one another are hydrogen, halogen, hydroxyl, mercapto, nitro, NR ^A R ^B , C ₁ -C 10 -alkyl, C ₂ -C ₂ , C ₂ -C ₆ -alkynyl, 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;

L ^{2 is} hydrogen, halogen, hydroxy, mercapto, nitro, NR ^A R ^B , CH ₂ -C-C ₉ alkyl, CHF ₂ , CF ₃ , C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkylene I , Phenyl, phenoxy, phenylthio, benzyloxy and benzylthio;

wherein two adjacent groups of L ^1, L ² and L ³ together form a -C ₄ - alkylene, C ₄ oxyalkylene, C may represent ₄ -Oxyalkylenoxy or butadienyl;

wherein at least one group L ¹ , L ² or L ^{3 is} not hydrogen and the groups L ¹ , L ² or L ^{3 are} unsubstituted or substituted by one to four identical or different groups R ^a :

R ^{a is} 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, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl or NR ^A R ^B ;

R ¹ 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, C ₁ -C ₆ -alkyl-S (O) _m - and five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S. ; m is 0, 1 or 2; wherein the cyclic groups in L ¹ , L ² , L ³ , R ^a and / or R ^{1 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-Ce-haloalkyl, C ₂ -C ₆ -alkyl keny I, C ₂ -C ₆ -alkyl kiny I, Ci-C ₆ alkoxy, and five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S, which may be unsubstituted or substituted by one or more groups halogen and / or CrC ₄ -AlkVl.

2. Compounds of formula I according to claim 1, in which R ^{1 is} methyl or amino.

3. Compounds of formula I according to claim 1 or 2, wherein L ¹ and L ³ mean hydrogen.

4. Compounds of formula I according to any one of claims 1 to 3, wherein L ^{3 is} hydrogen and L ¹ and L ² are different from hydrogen.

5. A process for preparing compounds of the formula I according to any one of claims 1 to 4, ß-ketoester of the formula II,

in which R is C 1 -C ₄ -alkyl, with an aminopyrazole of the formula

to

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 aminopyrazole 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 the fungi, or to be protected against fungal infection materials, plants, the soil or seeds with an effective amount of

Treated compound of formula I according to claim 1.