EP1895844A1 - Bicyclic 5-hydroxypyrazolines, method for producing the same and agents comprising the same - Google Patents

Abstract

The invention relates to the novel 5-hydroxypyrazolines of formula (I), wherein the substituents are defined as follows: B represents phenyl, naphthyl or 5- or 6-membered hetaryl having one to four hetero atoms from the group including O, N or S; A represents C=O, C=S or SO2; R1 represents alkyl, alkyl halide, alkenyl, alkenyl halide, alkinyl or alkinyl halide, cycloalkyl, cycloalkenyl, cycloalkinyl, phenyl, 5- or 6-membered heterocyclyl or hetaryl, having one to four hetero atoms from the group including O, N or S; R2 together with R1 or R4 represents C3-C4 alkyls or C3-C4 alkenyls, which groups can be defined as in the description; R3 represents hydrogen, nitro, cyano, NR''2, alkyl, alkyl halide, alkoxy, halogenalkoxy, alkenyl, alkenyl halide, alkinyl or alkinyl halide, wherein R'' independently represents hydrogen or alkyl; R4 represents hydrogen, halogen, nitro, cyano, NR''2, alkyl, alkyl halide, COOR'' or 5- or 6-membered hetaryl or heterocyclyl; wherein the aforementioned variables may be substituted as defined in the description. The invention also relates to a method for producing the inventive compounds, to their use for controlling parasitic fungi and to agents comprising the same.

Description

Use of bicyclic 5-hydroxypyrazolines, new 5-hydroxypyrazolines, processes for their preparation, and agents containing them

description

The present invention relates to the use of bicyclic 5-hydroxypyrazolines of the formula I.

in which the substituents have the following meaning:

B is phenyl, naphthyl or 5- or 6-membered hetaryl containing one to four heteroatoms from the group O, N or S;

AC = O, C = S or SO ₂ ;

R ¹ d-Cio-alkyl, d-Cio-haloalkyl, C ₃ -C ₀ alkenyl, C ₃ -C ₀ haloalkenyl, C ₃ -C ₀ - alkynyl, or C ₃ -C ₀ haloalkynyl,

C ₃ -C ₀ cycloalkyl, C ₃ -C ₀ cycloalkenyl, C ₈ -C ₀ cycloalkynyl, phenyl, 5- or 6-membered heterocyclyl or hetaryl, containing one to four heteroatoms from the

Group O, N or S;

R ² together with R ¹ or R ⁴ C ₃ -C ₄ -alkylene or C ₃ -C ₄ -alkenylene, which groups may be substituted by one or two groups R ',

R 'is hydrogen, halogen, nitro, cyano, Ci-Ci _θ -alkyl, Ci _θ haloalkyl, C ₂ - C _θ alkenyl, C ₂ -C ₀ haloalkyl, C ₃ -C ₀ alkynyl, C ₃ -Ci ₀ -haloalkynyl; C ₃ - C _θ cycloalkyl, C ₃ -C ₀ cycloalkenyl, C ₃ -C ₀ cycloalkynyl, aryl, hetaryl, heterocyclyl; COOR ", NR"₂;

R ³ is hydrogen, nitro, cyano, NR _{"2, Ci-C4-alkyl,} Ci-C ₄ haloalkyl, dC ₄ alkoxy, Ci-C ₄ haloalkoxy, C ₂ -C ₄ -alkyl keny I, C ₂ -C ₄ -haloalkenyl, C ₂ -C ₄ -alkynyl or C ₂ -C ₄ -haloalkynyl, wherein

R "independently of one another are hydrogen or C 1 -C ₄ -alkyl;

R ⁴ is hydrogen, halogen, nitro, cyano, NR _{"2, Ci-C4-alkyl,} Ci-C ₄ haloalkyl,

COOR ', hetaryl or heterocyclyl; wherein the abovementioned variables can be partially or completely halogenated and / or can carry one to four groups R ^a

R ^{a is} halogen, cyano, nitro, amino, hydroxy, Ci-C ₆ alkyl, Ci-C ₆ haloalkyl, Ci-C ₆ -

Alkylcarbonyl, C ₃ -C ₆ cycloalkyl, Ci-C ₆ alkoxy, Ci-C ₆ haloalkoxy, -C ₆ - alkoxycarbonyl, formyl, Ci-C6-alkylthio, Ci-C6-alkylamino, di-Ci-C6-alkylamino .

C2-C8-alkenyl, C2-C8-haloalkenyl, Cs-Cβ cycloalkenyl, C2-C6-alkenyloxy, _C3 - Ce-haloalkenyloxy, C ₂ -C ₆ -alkyl kinyl, C2-C ₆ haloalkynyl, C ₃ - C ₆ alkynyloxy, C ₃ -C ₆ haloalkynyloxy, C ₃ -C ₆ cycloalkoxy, C ₃ -C ₆ cycloalkenoxy, C ₁ -C ₃ oxyalkyleneoxy, phenyl, naphthyl, five to ten membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S, CFF = NOR ¹ ", wherein

R "is hydrogen, alkyl, cycloalkyl and aryl, and R ^{iv is} alkyl, alkenyl, haloalkenyl, alkynyl and arylalkyl, or NR ^v -CO-DR ^vi , where

R ^v is hydrogen, hydroxy, Ci-C ₆ alkyl, C ₂ -C ₆ -alkyl keny I, C ₂ -C ₆ kinyl -alkyl, -C ₆ - alkoxy, C ₂ -C ₆ alkenyloxy, C ₂ -C _{6 is} alkynyloxy, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkoxy and C ₁ -C ₆ -alkoxycarbonyl, R ^{vi is} hydrogen, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkynyl, C ₂ -C ₆ -alkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkenyl, phenyl, phenyl-C ₁ -C ₆ -alkyl, hetaryl and hetaryl-C ₁ -C ₆ -alkynyl; C ₆ alkyl and D is a direct bond, oxygen or nitrogen, where the nitrogen can carry one of the groups mentioned in R ^vi ,

where the aliphatic, alicyclic or aromatic groups R ^{a are in} turn partially or completely halogenated or may carry one to three groups R ^b :

R ^{b is} halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, Alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, where the alkyl groups in these radicals contain 1 to 6 carbon atoms and said alkenyl or alkynyl groups in these radicals contain 2 to 8 carbon atoms;

and / or one to three of the following radicals:

Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, the cyclic systems containing 3 to 10 ring members; Phenyl, phenoxy, phenylthio, phenyl-C ₁ -C ₆ -alkoxy, phenyl-C ₁ -C ₆ -alkyl, hetaryl, hetaryloxy, heterothylthio, where the hetaryl groups contain 5 or 6 ring members, and the cyclic systems may be partially or completely halogenated or substituted by alkyl or haloalkyl groups;

for controlling plant pathogenic harmful fungi.

In addition, the invention relates to novel 5-hydroxypyrazolines, processes for their preparation, their use for controlling harmful fungi, and agents containing them.

Substituted pyrazolin-5-ones with herbicidal and fungicidal activity are known from DE-A

37 28 278, fungicidally effective 3-aryl-pyrazoles are disclosed in WO-A 94/29276 and WO 00/20399.

However, their effect is in many cases unsatisfactory. It was therefore an object to find compounds with improved effectiveness.

Accordingly, the new 5-hydroxypyrazoles of the formula I were found.

Compounds of the formula I are present in a tautomeric equilibrium with the open-chain form Ia [cf.: J. Org. Chem. USSR, p. 2037 (1983); Ibid., p. 1247 (1984)].

The invention thus relates to both forms, even if only the ring shape I is always called for reasons of clarity.

Compounds of the formula I in which A is C =O (formula IA) can be obtained, for example, in the following way:

This reaction is usually carried out at temperatures of 0 ⁰ C to 200 ⁰ C, preferably 20 ⁰ C to 100 ⁰ C, in an inert organic solvent [J. Org. Chem. USSR (Engl. Transl.), Vol. 16, p. 371 (1980); ibid., Vol. 21, p. 2279 (1985); Ibid., Vol. 22, p. 250 (1986); Ibid., Vol. 23, p. 1291 (1987); Indian J. Chem. Sect. B, vol. 29, p. 887 (1990); Soc. Soc. Chem. Jp., Vol. 62, p. 3409 (1989)].

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably methanol, Ethanol and tetrahydrofuran. It is also possible to use mixtures of the abovementioned solvents.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use III in an excess based on II.

The hydrazides of the formula II required for the preparation of the compounds I are known in the literature [cf. J. Heterocycl. Chem. Vol. 16, p. 561 (1976); Helv. Chim. Acta, Vol. 27, p. 883 (1944); J. Chem. Soc. (1943) p. 413] or can be prepared according to the cited literature.

Hydrazides of the formula II are usually prepared from the corresponding carboxylic acid esters of the formula V by reaction with hydrazine hydrate. In formula V, R 'is C 1 -C ₄ -alkyl.

This reaction is usually carried out at temperatures from 0 ^° C. to 150 ^° C., preferably from 20 ^° C. to 100 ^° C., in an inert organic solvent [cf. J. Heterocycl. Chem. Vol. 16, p. 561 (1976); Helv. Chim. Acta, Vol. 27, p. 883 (1944); J. Chem. Soc. (1943) p. 413].

The diketones of the formula III required for the preparation of the compounds I are likewise known in the literature [Organikum, VEB Verlag der Wissenschaften, 15th ed. P. 584ff., Berlin 1976] or can be prepared according to the cited literature.

Compounds of formula I in which A represents SO 2 (formula I.B1) are preferred on

This reaction is advantageously carried out under the conditions specified for the preparation of the compounds IA.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to incorporate IM in an excess relative to IV. put.

The sulfonylhydrazides of the formula IV required for the preparation of the compounds I are known in the literature [J. Chem. Soc. Chem. Commun. (1972) p. 1132; J. Chem. Soc. (1949) p. 1148; Helv. Chim. Acta, Vol. 42, p. 996 (1962)] or can be prepared according to the cited literature.

The compounds of the formula I in which A is C = S (formula I.B2) are accessible from the corresponding compounds of the formula I.A by reaction with a sulphurizing agent.

The sulfurization of LA is carried out under known conditions, it is usually carried out at temperatures from 0 ⁰ C to 180 ⁰ C, preferably 20 ⁰ C to 140 ⁰ C, in an inert organic solvent [see. Liebigs Ann Chem., P. 177 (1989)].

Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide, particularly preferably toluene and tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.

Suitable sulfurizing agents are, for example, phosphorus pentasulfide or Lawes- son's reagent.

The reaction mixtures are worked up in the usual way, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products. The intermediate and end products are z.T. in the form of colorless or pale brownish, viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature from volatile constituents. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.

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 branched hydrocarbon radicals having 1 to 4, 6, 8 or 10 carbon atoms, for example C ₁ -C ₆ -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1 Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-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: straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above), wherein in these groups, partially or completely, the hydrogen atoms may be replaced by halogen atoms as mentioned above, e.g. C 1 -C 2 -haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6, 8 or 10 carbon atoms and a double bond 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-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-penteny 1, 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; Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and a double bond in any position (as mentioned above), wherein in these groups the hydrogen atoms are partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine can;

Alkynyl: straight or branched hydrocarbon groups having 2 to 4, 6, 8 or 10 carbon atoms and a triple bond in any position, e.g. C 2 -C 6 -alkynyl, 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-yl 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;

Haloalkynyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and a triple bond in any position (as mentioned above), wherein in these groups the hydrogen atoms are partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine can;

Cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 to 6, 8, 10 or 12 carbon ring members, for example C ₃ -C ₈ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;

Heterocyclyl: 5- or 6-membered heterocycles containing, in addition to carbon ring members, one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, eg 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2 Tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1, 2,4-oxadiazolidin-3-yl, 1, 2, 4-oxadiazolidin-5-yl, 1, 2,4-thiadiazolidin-3-yl, 1, 2,4-thiadiazolidin-5-yl, 1, 2,4-triazolidin-3-yl, 1, 3, 4-oxadiazolidin-2-yl, 1, 3,4-thiadiazolidin-2-yl, 1, 3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-ol yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydro-thien-2-yl, 2,3-dihydro-thien-3-yl, 2,4-dihydrothi en-2-yl, 2,4-dihydro-thien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2 Isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazoline 5-yl, 3-isoxazolin-5-yl, 4-isoxa zolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolinone 4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-Dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazole-3 yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazole-4 yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazole 5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydro-oxazol-5-yl, 3,4- Dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1, 3-dioxan-5-yl, 2 tetrahydropyranyl,

4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1, 3,5-hexahydro-triazin-2-yl and 1, 2,4-hexahydrotriazine-3-yl;

heteroaryl:

5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-membered heteroaryl groups, which besides carbon atoms can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members. eg 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2,4- Oxadiazol-3-yl, 1, 2,4-oxadiazol-5-yl, 1, 2,4-thiadiazol-3-yl, 1, 2,4-thiadiazol-5-yl, 1, 2,4-triazole 3-yl, 1, 3,4-oxadiazol-2-yl, 1, 3,4-thiadiazol-2-yl and 1, 3,4-triazol-2-yl; benzo-fused 5-membered heteroaryl containing one to three nitrogen atoms or a nitrogen atom and an oxygen or sulfur atom: 5-membered heteroaryl groups which may contain, besides carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-1,3-diene-1,4-diyl group; nitrogen-bonded 5-membered heteroaryl containing one to four nitrogen atoms or nitrogen-bonded benzo-fused 5-membered heteroaryl containing one to three nitrogen atoms: 5-membered heteroaryl groups which contain one to four nitrogen atoms or one to three nitrogen atoms in addition to carbon atoms may contain as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member may be bridged by a buta-1, 3-diene-1, 4-diyl group, these rings via one of the nitrogen ring members to the skeleton are bound;

6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-membered ring heteroaryl groups which, in addition to carbon atoms, one to three or one to may contain four nitrogen atoms as ring members, eg 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3,5- Triazin-2-yl and 1,2,4-triazin-3-yl.

Generally, alkyl groups in the various substituents preferably have 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and said alkenyl or alkynyl groups contain 2 to 8 carbon atoms.

With regard to their intended use of the 5-hydroxypyrazolines of the formula I, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:

In particular, compounds LA are preferred.

In another embodiment of the compounds of the formula I, A is SO 2.

In another embodiment of the compounds of the formula I, A is C = S.

In a further embodiment of the compounds I, R ¹ and R ² together represent a propylene chain which may be substituted by one or two groups R '. These compounds correspond to the formula 1.1 in which the variables have the meaning given for formula I and n is zero, 1 or 2.

In a further embodiment of the compounds I, R ² and R ⁴ together represent a propylene chain which may be substituted by one or two groups R '. These compounds correspond to the formula 1.2, in which the variables have the meaning given for formula I and n is zero, 1 or 2.

In a further embodiment of the compounds I, R ¹ and R ² together represent a butylene chain which may be substituted by one, two or three groups R '. These compounds correspond to the formula 1.3 in which the variables have the meaning given for formula I and n is zero, 1, 2 or 3.

In a further embodiment of the compounds I, R ² and R ⁴ together represent a butylene chain, which may be substituted by one, two or three groups R '. These compounds correspond to the formula 1.4 in which the variables have the meaning given for formula I and n is zero, 1, 2 or 3.

In a further embodiment of the compounds I, R ¹ and R ² together represent a propylene chain which may be substituted by one or two groups R '. These compounds correspond to the formula 1.5 in which the variables have the meaning given for formula I and n is zero, 1 or 2.

In a further embodiment of the compounds I, R ² and R ⁴ together represent a propylene chain which may be substituted by one or two groups R '. These compounds correspond to the formula 1.6 or 1.7, in which the variables have the meaning given for formula I and n is zero, 1 or 2.

In a further embodiment of the compounds I, R ¹ and R ² together represent a butylene chain which may be substituted by one, two or three groups R '. These compounds correspond to the formula 1.8 or 1.9, in which the variables which for formula I n are zero, 1, 2 or 3.

| .9

In a further embodiment of the compounds I, R ² and R ⁴ together represent a butylene chain, which may be substituted by one, two or three groups R '. These compounds correspond to the formulas 1.10, 1.11 or 1.12, in which the variables

In a further embodiment of the compounds I, R ² and R ⁴ together represent a butadienylene chain which may be substituted by one, two or three groups R '. These compounds correspond to the formula 1.13 in which the variables are the Bede 3 given for formula I.

Furthermore, particular preference is given to compounds I in which R ^{1 is} C ² -C ⁴ -alkyl.

In addition, compounds I are particularly preferred in which R ^{1 is} C ¹ -C 4 -haloalkyl.

In particular, compounds I are preferred in which R ^{1 is} C ₃ F ₇ or C ₂ F ₅ .

In addition, compounds I are particularly preferred in which R ^{1 is} optionally para-substituted phenyl.

Also particularly preferred are compounds I in which B is phenyl which carries a substituent in the 3-position.

Particular preference is furthermore given to compounds I in which B is phenyl which carries a substituent in the 4-position.

Particular preference is furthermore given to compounds I in which B is phenyl which carries substituents in the 3,4-position. In addition, compounds I are particularly preferred in which B is heteroaryl.

Furthermore, compounds I are particularly preferred in which R ³ is hydrogen.

In addition, compounds I are particularly preferred in which R ^{4 is} hydrogen or methyl.

Equally particularly preferred are compounds I in which R ^{4 is} trifluoromethyl.

In particular, compounds I are also preferred in which R ^{4 is} cyano, C ² -C ⁴ -alkyl or C ² -C ⁴ -haloalkyl.

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 general formula 1.1A in which n is zero, R ^{3 is} hydrogen, R ^{4 is} methyl and B is one of Table A.

Table 2

Compounds of the general formula I.1A in which (R ') _{n is} 4-methyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponds in each case to one row of Table A.

Table 3

Compounds of general formula I.1A in which (R ') _{n is} 4-methyl, R ^{3 is} hydrogen, R ^{4 is} ethyl and B is a compound corresponds in each case to one row of Table A.

Table 4

Compounds of the general formula I.1A in which (R ') _{n is} 5-methyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound in each case one row of Table A speaks

Table 5

Compounds of the general formula I.1A in which (R ') _{n is} 5-methyl, R ^{3 is} hydrogen, R ^{4 is} ethyl and B is a compound corresponding to one row of Table A.

Table 6

Compounds of general formula I.2A in which R ^{1 is} methyl, n is zero, R ^{3 is}

Table 7

Compounds of the general formula I.2A in which R ^{1 is} methyl, (R ') _{n is} 4-methyl, R ^{3 is} hydrogen and B is a compound corresponding to one row of Table A.

Table 8

Compounds of general formula I.2A in which R ^{1 is} ethyl, (R ') _{n is} 4-methyl, R ^{3 is} hydrogen and B is a compound corresponds to one row of Table A.

Table 9

Compounds of general formula I.2A in which R ^{1 is} methyl, (R ') _{n is} 5-methyl, R ^{3 is} hydrogen and B is a compound corresponds to one row of Table A.

Table 10

Compounds of general formula I.2A in which R ^{1 is} ethyl, (R ') _{n is} 5-methyl, R ^{3 is} hydrogen and B is a compound corresponds to one row of Table A.

Table 11

Compounds of general formula I.2A in which R ^{1 is} methyl, (R ') _{n is} 6-methyl, R ^{3 is} hydrogen and B is a compound corresponds in each case to one row of Table A.

Table 12

Compounds of general formula I.2A in which R ^{1 is} ethyl, (R ') _{n is} 6-methyl, R ^{3 is} hydrogen and B is a compound corresponds in each case to one row of Table A. Table 13

Compounds of the general formula I.3A in which n is zero, R ^{3 is} hydrogen, R ^{4 is} methyl and B for a compound corresponds in each case to one row of Table A.

Table 14

Compounds of general formula I. 3A, in which (R ') _{n is} 4-methyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponds to one row of Table A.

Table 15

Compounds of the general formula I.3A in which (R ') _{n is} 4-methyl, R ^{3 is} hydrogen, R ^{4 is} ethyl and B is a compound corresponds in each case to one row of Table A.

Table 16

Compounds of general formula I.3A in which (R ') _{n is} 5-methyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponds in each case to one row of Table A.

Table 17

Compounds of the general formula I.3A, in which (R ') _{n is} 5-methyl, R ^{3 is} hydrogen, R ^{4 is} ethyl and B for a compound corresponds in each case to one row of Table A.

Table 18 Compounds of the general formula I.3A, in which (R ') _{n is} 6-methyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound in each case corresponds to one row of Table A.

Table 19 Compounds of general formula I.3A, in which (R ') _{n is} 6-methyl, R ^{3 is} hydrogen, R ^{4 is} ethyl and B is a compound corresponding to one row of Table A.

Table 20

Compounds of the general formula I.4A, in which R ^{1 is} methyl, n is zero, R ^{3 is} hydrogen and B for a compound corresponds in each case to one row of Table A.

Table 21

Compounds of general formula I.4A in which R ^{1 is} methyl, (R ') _{n is} 4-methyl, R ^{3 is} hydrogen and B is a compound corresponds in each case to one row of Table A.

Table 22

Compounds of general formula I.4A in which R ^{1 is} ethyl, (R ') _{n is} 4-methyl, R ^{3 is} hydrogen and B is a compound corresponds to one row of Table A.

Table 23

Compounds of the general formula I.4A, in which R ^{1 is} methyl, (R ') _{n is} 5-methyl, R ^{3 is} hydrogen and B is a compound corresponding in each case to one row of Table A.

Table 24

Compounds of general formula I.4A in which R ^{1 is} ethyl, (R ') _{n is} 5-methyl, R ^{3 is} hydrogen and B is a compound corresponds to one row of Table A.

Table 25

Compounds of general formula I.4A in which R ^{1 is} methyl, (R ') _{n is} 6-methyl, R ^{3 is} hydrogen and B is a compound corresponds to one row of Table A.

Table 26

Compounds of the general formula I.4A in which R ^{1 is} ethyl, (R ') _{n is} 6-methyl, R ^{3 is} hydrogen and B is a compound corresponding to one row of Table A.

Table 27

Compounds of general formula I.4A in which R ^{1 is} methyl, (R ') _{n is} 7-methyl, R ^{3 is} hydrogen and B is a compound corresponds in each case to one row of Table A.

Table 28

Compounds of general formula I.4A, in which R ^{1 is} ethyl, (R ') _{n is} 7-methyl, R ^{3 is} hydrogen and B is a compound corresponding 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 plant pathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, 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 large number of fungi on various crops such as wheat, rye, barley, oats, rice, maize, 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.

Specifically, 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. alternata on potatoes and tomatoes,

• Aphanomyces species of sugar beets and vegetables,

• Ascochyta species on cereals and vegetables, • Bipolaris and Drechslera species on corn, cereals, rice and turf, such as D.maydis on corn,

• Blumeria graminis (powdery mildew) on cereals,

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

• 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, 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 maize,

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, e.g. Tomatoes, • Gaeumanomyces graminis on cereals,

Gibberella species on cereals and rice (e.g., 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 grass, rice, maize, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants such as P.ultiumum on various plants, P. aphanidermatum on grass,

• Rhizoctonia species on cotton, rice, potatoes, turf, maize, oilseed rape, potato, sugar beets, vegetables and on 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 on cereals, • Ustilago species on cereals, maize and sugarcane, e.g. 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, Pseudoperonospora species and Pythium 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 the seed treatment, 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 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), 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 non-ionic and anionic emulsifiers (e.g., 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 glycol 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, ethoxylated polyoxypropylene, Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, 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 flour, cellulose powder and other solid carriers.

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

Examples of formulations are: 1. Products for dilution in water

A Water-soluble concentrates (SL, LS)

10 parts by weight of the active ingredients 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 the active compounds are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution in water results in a dispersion. The active ingredient content is 20% by weight C Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds 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 the active compounds 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 water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight 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 the active compounds are comminuted with the addition of 10 parts by weight of dispersing and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to give 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 the active compounds are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example 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 the active compounds are ground in a rotor-stator mill with the 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 (GF) In a ball mill 20 parts by weight of the active ingredients, 10 parts by weight

Dispersing agent, 1Gew.-Part swelling agent ("gelling agent") and 70 parts by weight of water or an organic solvent to a fine suspension milled .. When diluted with water results in a stable suspension with 20 wt .-% active ingredient content. 2. Products for direct application

I dusts (DP, DS)

5 parts by weight of the active ingredients 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 the active ingredients 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 the active ingredients 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.

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 purposes of 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 (spray powders, oil dispersions) by addition of 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. However, it is also possible to prepare concentrates which are active substance, adhesion, dispersant or emulsifier and, if appropriate, solvent or oil, concentrates which are suitable for dilution with water. 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.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, possibly also just immediately 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 an adjuvant 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, in the form of application as fungicides, may also be present together with other active substances, e.g. with herbicides, insecticides, growth regulators, fungicides or with fertilizers. When mixing the compounds (I) or the agents containing them with one or more further active compounds, in particular fungicides, for example, in many cases, the activity spectrum can be broadened or development of resistance 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, 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, 3,4-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, Bromuconazoles, Cyproconazole, Difenoconazole, Diniconazole, Enilconazole, Epoxiconazole, Fenbuconazole, Flusilazole, Fluquinconazole, Flutriafol, Hexaconazole, Imibenconazole, Ipconazole, Metconazole, Myclobutanil, Penconazole, Propiconazole, Prothioconazole, Simeconazole, Tebuconazole, Tetraconazole, Triadimenol Triadicon, 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-chloro-phenyl) -2,3-dimethyl-isoxazolidin-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-methylindol-1-sulfonyl) - [1, 2,4] tazazole-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.

Example 1 - Preparation of (2-chlorophenyl) - (6a-hydroxy-3-methyl-4,5,6,6a-tetrahydro-3aH-cyclopentapyrazol-1-yl) -methanone

A solution of 0.68 g of 2-Chlorbenzoesäurehydrazid and 0.51 g of 2-Acetylcyclopenta- non in 20 ml ethyl acetate was 8 hrs. At 80 ⁰ C and then 72 h. Stirred at 20 to 25 ° C. The reaction mixture was freed from solvent and purified by chromatography on silica gel. Was obtained while 0.7 g of the title compound as colorless crystals of melting point 147-150 ⁰ C. Table I

# denotes the bond to the pyrazoline ring

OO

Examples of the effect against harmful fungi

The fungicidal activity of the compounds of the formula I 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 alkylphenol Ie) 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 - Curative activity against wheat brown rust caused by Puccinia recondita

Leaves of potted wheat seedlings of the variety "Chancellor" were inoculated with a spore suspension of the brown rust (Puccinia recondita). Thereafter, the pots were placed in a high humidity chamber (90-95%) and 20-22 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The infected plants were sprayed the next day with the above-described active ingredient solution in the drug concentration indicated below to drip point. After the spray coating had dried on, the test plants were cultivated in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70% relative atmospheric humidity for 7 days. Then the extent of rust fungus development on the leaves was determined.

In this test, the plants treated with 250 ppm of the active ingredient I-8 showed 1% infestation, while the untreated plants were 90% infected.

Use Example 2 - Efficacy against tomato blight caused by Alternaria solani

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 infected with an aqueous spore suspension of Alternaria solani in 2% biomalt solution with a density of 0.17 x 10 ⁶ spores / ml. Subsequently, the plants were 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 1000 ppm of the active ingredient I-2 showed 3% infestation, while the untreated plants were 90% infected.

Use Example 3 - Efficacy against barley spot disease caused by Pyrenophora teres at 1 day of protective application

Leaves of potted barley seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. 24 hours after the spray coating had dried on, the test plants were incubated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch inoculation. Subsequently, the test plants were placed in the greenhouse at temperatures between 20 and 24 ° C and 95 to 100% relative humidity. After 6 days, the extent of disease development was determined visually as% of total leaf area.

In this test, the plants treated with 1000 ppm of the active ingredient 1-11 showed 15% infestation, while the untreated plants were 90% infected.

Claims

claims

1. Use of the formula I

in which the substituents have the following meanings:

B is phenyl, naphthyl or 5- or 6-membered hetaryl containing one to four heteroatoms from the group O, N or S;

AC = O, C = S or SO ₂ ;

R ¹ Ci-Cio-alkyl, Ci-Cio-haloalkyl, C ₃ -C ₀ alkenyl, C ₃ -C ₀ haloalkenyl, C ₃ -Cio-alkynyl, or C ₃ -Cio-haloalkynyl,

C ₃ -Cio-cycloalkyl, C ₃ -Cio-cycloalkenyl, C ₈ -Cio-cycloalkynyl, phenyl, 5- or

6-membered heterocyclyl or hetaryl containing one to four heteroatoms from the group O, N or S;

R ² together with R ¹ or R ⁴ C ₃ -C ₄ -alkylene or C ₃ -C ₄ -alkylene, which groups may be substituted by one or two groups R ',

R 'is hydrogen, halogen, nitro, cyano, Ci-Cio-alkyl, Ci-Ci _θ halo-alkyl, C ₂ -Cio-alkenyl, C ₂ -Cio-haloalkyl, C ₃ -Cio-alkynyl, C ₃ -C ₀ -haloalkynyl; C ₃ -C ₀ cycloalkyl, C ₃ -C ₀ cycloalkenyl, C ₃ -C ₀ -CyCIo- alkynyl, phenyl, naphthyl, hetaryl, heterocyclyl; COOR ", NR"₂;

R ³ is hydrogen, nitro, cyano, NR _{"2, Ci-C4-alkyl, Ci-C4-haloalkyl,} -C ₄ - alkoxy, C ₄ haloalkoxy, C ₂ -C ₄ -alkyl keny I, C ₂ -C ₄ haloalkenyl, C ₂ -C ₄ alkynyl or C ₂ -C ₄ haloalkynyl, wherein

R "independently of one another are hydrogen or C 1 -C ₄ -alkyl;

R ⁴ is hydrogen, halogen, nitro, cyano, NR _{"2, Ci-C4-alkyl,} Ci-C ₄ haloalkyl,

COOR ", 5- or 6-membered heterocyclyl or hetaryl, containing one to four heteroatoms from the group O, N or S;

wherein the abovementioned variables can be partially or completely halogenated and / or carry one to four groups R ^a R ^a halogen, cyano, nitro, hydroxy, amino, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkylcarbonyl , C ₃ -C ₆ cycloalkyl, Ci-C ₆ alkoxy, Ci-C ₆ haloalkoxy, Ci-C6-alkoxycarbonyl, formyl, Ci-C ₆ alkylthio, Ci-C6-alkylamino, di-Ci-C ₆ - alkylamino, C2-C8-alkenyl, C2-C8-haloalkenyl, Cs-Cβ cycloalkenyl, C ₂ C ₆ alkyloxy, C ₃ -C ₆ haloalkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ alkynyloxy, C ₃ -C ₆ haloalkynyloxy, C ₃ -C ₆ -CyCIo alkoxy, C ₃ -C ₆ cycloalkenoxy, Ci-C3-oxyalkyleneoxy, phenyl, naphthyl, five- to ten-membered saturated, partially unsaturated or aromatic heterocycle, containing one to four heteroatoms from the group O, N or S, CIV = NOR ¹ *, where

R "is hydrogen, alkyl, cycloalkyl and aryl and R ^{iv is} alkyl, alkenyl, haloalkenyl, alkynyl and arylalkyl, or

NR ^v -CO-DR ^vi , where

R ^v is hydrogen, hydroxy, Ci-C ₆ alkyl, C ₂ -C ₆ -alkyl keny I, C ₂ -C ₆ -alkyl kiny I, Ci-Ce alkoxy, C ₂ -C ₆ -alkyl keny loxy, C ₂ -C ₆ -alkyl kiny loxy, _Ci-C6 alkoxy-Ci- _C6 alkyl, Ci-C ₆ alkoxy alkoxy-Ci-C ₆ and C-C is ₆ alkoxycarbonyl, R ^vi is hydrogen , C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkynyl, C ₂ -C ₆ -alkynyl, C ₃ -C ₆ -

Cycloalkyl, C ₃ -C ₆ cycloalkenyl, phenyl, phenyl-Ci-C ₆ -alkyl, hetaryl and hetaryl-Ci-C ₆ alkyl and D is a direct bond, oxygen or nitrogen, where the nitrogen in one of the R can carry ^vi mentioned groups,

where the aliphatic, alicyclic or aromatic groups R ^{a are in} turn partially or completely halogenated or may carry one to three groups R ^b :

R ^{b is} halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, amino carbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, Alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, the alkyl groups in these radicals containing from 1 to 6 carbon atoms and said alkenyl or alkynyl groups in these radicals containing from 2 to 8 carbon atoms;

and / or one to three of the following radicals:

Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, the cyclic systems containing 3 to 10 ring members; Phenyl, phenoxy, phenylthio, phenyl-C ₁ -C ₆ -alkoxy, phenyl-C ₁ -C ₆ -alkyl, hetaryl, hetaryl-oxy, hetarylthio, where the hetaryl groups contain 5 or 6 ring members, and the cyclic systems may be partially or completely halogenated or substituted by alkyl or haloalkyl groups;

for the control of phytopathogenic harmful fungi.

2. Use of compounds of the formula I according to claim 1, which correspond to the formula LA

3. Compounds of formula I according to claim 1 or 2, which correspond to the formula 1.1

in which n is zero, 1 or 2, where A is not carbonyl, when B is phenyl, n is zero and R ³ and R ^{4 are} hydrogen or methyl, and

A is not carbonyl when B is phenyl which carries a bromo, chloro or hydroxy substituent, n is zero and R ³ and R ^{4 are} hydrogen.

4. Compounds of formula I according to claim 1 or 2, which correspond to the formula 1.2

where n is zero, 1 or 2

A is not carbonyl when B is 3-pyridyl or phenyl which carries a nitro substituent, n is zero, R ^{1 is} trifluoromethyl and R ^{3 is} hydrogen.

5. Compounds of formula I according to claim 1 or 2, which correspond to the formula 1.3

where n is zero, 1, 2 or 3.

6. Compounds of the formula I according to claim 1 or 2, which correspond to the formula 1.3

in which n is zero, 1, 2 or 3, where R ^{1 is} not trifluoromethyl.

7. A process for the preparation of compounds of the formula I. A according to claim 2, characterized in that hydrazines of the formula II

in which B is defined according to claim 1, with a diketone of the formula III

in which the substituents are defined according to claim 1, reacted.

8. A fungicidal composition containing a solid or liquid carrier and a compound of formula I according to any one of claims 1 to 6.

9. A fungicidal composition containing a solid or liquid carrier, a compound of formula I according to any one of claims 1 to 6 and a further active ingredient.

10. A composition according to claim 8, comprising a compound of the formula I according to one of claims 3 to 6.

11. Seed containing a compound of formula I according to any one of claims 1 to 6 in an amount of 1 to 1000 g per 100 kg.

12. A method for controlling phytopathogenic harmful fungi, characterized in that treating the fungi, or to be protected against fungal attack materials, plants, the soil or seeds with an effective amount of a compound of formula I according to any one of claims 1 to 6.

13. Use of the compounds of the formula I according to any one of claims 1 to 6 for the preparation of a fungicidal composition according to claim 8 or 9.