EP1895845A1

EP1895845A1 - Fungicidal 5-hydroxypyrazolines, method for producing the same and agents comprising the same

Info

Publication number: EP1895845A1
Application number: EP06763256A
Authority: EP
Inventors: Markus Gewehr; Jochen Dietz; Thomas Grote; Andreas Gypser; Matthias NIEDENBRÜCK
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-05-31
Filing date: 2006-05-24
Publication date: 2008-03-12
Also published as: JP2008542330A; US20080194405A1; WO2006128817A1; KR20080016693A; CN101184394A; BRPI0610964A2

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 represents alkyl, alkyl halide, alkenyl, alkyl halide, alkinyl, alkinyl halide, cycloalkyl, cycloalkenyl, cycloalkinyl, phenyl, 5- or 6-membered hetaryl or heterocyclyl having one to four hetero atoms from the group including O, N or S; R3 represents hydrogen, nitro, cyano, alkyl, alkyl halide, alkoxy, halogenalkoxy, alkenyl, alkenyl halide, alkinyl, alkinyl halide or NR'2, 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

Fungicidal 5-hydroxypyrazolines, process for their preparation, and agents containing them

description

The present invention relates to novel 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 is} C ₂ -Cio-alkyl, Ci-Cio-haloalkyl, C ₃ -Cio-alkenyl, C ₃ -Cio-haloalkenyl, C ₃ -C ₀ - alkynyl, or C ₃ -C ₀ haloalkynyl,

C ₃ -C ₀ cycloalkyl, C ₃ -C ₀ cycloalkenyl, Cs-Cio-cycloalkynyl, phenyl, 5- or 6-membered heterocyclyl or hetaryl, containing one to four heteroatoms from the group O, N or S;

R ² Ci-Ci alkyl _θ, _θ CRCI haloalkyl, C ₂ -C _o alkenyl, _C2 -Cio-haloalkyl, C ₃ -C ₀ - alkynyl, C ₃ -C ₀ haloalkynyl, C ₃ -C ₀ cycloalkyl, C ₃ -C ₀ cycloalkenyl, C ₃ -C ₀ - cycloalkynyl, phenyl, 5- or 6-membered hetaryl or heterocyclyl containing one to four heteroatoms from the group O, N or S;

R ³ is hydrogen, nitro, cyano, Ci-C ₄ alkyl, _{Ci-C4-haloalkyl,} _Ci-C4 alkoxy, -C ₄ - haloalkoxy, C ₂ -C ₄ alkenyl, C ₂ -C ₄ haloalkenyl, C ₂ -C ₄ -alkynyl, C ₂ -C ₄ -halo-genalkinyl or NR ' ₂ , wherein

R 'is independently hydrogen or Ci-C4-alkyl;

R ⁴ is hydrogen, halogen, nitro, cyano, NR _'2, Ci-C ₄ alkyl, dC ₄ haloalkyl,

COOR 'or 5- or 6-membered 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, hydroxy, Ci-C ₆ alkyl, Ci-C ₆ haloalkyl, Ci-C ₆ alkyl carbonyl, C ₃ -C 6 cycloalkyl, Ci-Cβ-alkoxy, Ci-C ₆ Haloalkoxy, C ₁ -C ₆ -alkoxycarbonyl, formyl, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylamino, C ₁ -C ₆ -alkylamino, C ₂ -C 6 -alkylthio, Alkenyl, C ₂ -C 8 -haloalkenyl, C ₁ -C ₆ -cycloalkenyl, C ₂ -C ₆ -alkenyloxy, 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 cycloalkoxy, C ₃ -C ₆ cycloalkenoxy, C ₁ -C ₃ oxyalkyleneoxy, phenyl, naphthyl, five to ten membered saturated, partially unsaturated or aromatic heterocycle containing to four heteroatoms from the

Group O, N or S, CR ^{III =} NOR ^IV , where

R '"is hydrogen, alkyl, cycloalkyl and aryl and R ^ιv alkyl, alkenyl, ^haloalkenyl , alkynyl and arylalkyl, or NR ^V -CO-DR ^VI , wherein

R ^v is hydrogen, hydroxy, Ci-C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₆ - alkoxy, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ Alkynyloxy, C ₁ -C ₆ -alkoxy-dC ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkoxy and C ₁ -C ₆ -alkoxycarbonyl,

R ^{vι 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 -alkyl and D denotes a direct bond, oxygen or nitrogen, it being possible for the nitrogen to carry one of the groups mentioned for R ^vι ,

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, hetarylio, where the hetaryl groups contain 5 or 6 ring members, and the cyclic systems partially or completely halogenated or substituted by alkyl or haloalkyl groups. Moreover, the invention relates to 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 active 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. The novel compounds differ from those known from WO 00/20399 by the substitution in the 4-position.

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 upstream 20 ° C to 100 ° 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 propio - Nitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and Dimethyisulfoxid, dimethylformamide and dimethylacetamide, more preferably methanol, ethanol and tetrahydrofuran. It is also possible to use mixtures of the be called solvent used.

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.

ON ₂ H ₄ xH ₂ OO

B ^Λ O ' ^R ''B ^Λ N ^{' NH} _{2 π} ^V

This reaction is usually carried out at temperatures of 0 ⁰ C to 15O ⁰ C, preferably 2O ⁰ C to 100 ⁰ C, in an inert organic solvent [see. 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 the formula I in which A is SO 2 (formula I.B1) are preferably accessible in the following way:

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 use III in an excess based on IV.

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 obtainable from the corresponding compounds of the formula LA by reaction with a sulfurizing agent.

The sulfurization of LA is carried out under known conditions, it is usually carried out at temperatures of ^{0 0} C to 180 ° C, preferably 20 ° C to 14O 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 d-Ce-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1 , 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methyl butyl butyl, 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, for example Ci-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, i-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;

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-chain or branched hydrocarbon groups having 2 to 4, 6, 8 or 10 carbon atoms and a triple bond in any position, for example C ₂ -Ce-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-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, e.g. Ca-Cs-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-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-dihydrothie n-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-isoxazoline-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolinone 4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-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-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4, 5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydro- oxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4- Dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-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-hexahydropyri dazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1, 3,5-hexahydro-triazin-2-yl, and 1, 2,4-hexahydrotriazin-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 contain, besides carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members may contain, for example 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 one nitrogen atom and one oxygen or sulfur atom: 5-membered heteroaryl groups which may contain, in addition to 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-linked 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 containing, besides carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms, respectively

May contain 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 being bonded to the skeleton via one of the nitrogen ring members; 6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-membered ring heteroaryl groups which may contain, in addition to carbon atoms, one to three or one to four nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 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, be

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.

Compounds of formula I in which R ^{1 is} not methyl are preferred. Particular preference is given to compounds I in which R ^{1 is} C ₂ -C ₄ -alkyl, in particular C ₃ -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} C3F ₇ or C ₂ F ₅ .

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

Particular preference is furthermore given to compounds I in which B is phenyl which carries a substituent in the 3-position.

Also particularly preferred are compounds I in which B is phenyl which carries a substituent in the 4-position.

Particular preference is furthermore given to compounds I ₁ 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.

Compounds of the formula I in which R ^{2 is} C 1 -C ₄ -alkyl, in particular methyl or ethyl, represent a preferred subject of the invention.

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 summarized 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 IA, in which R ^{1 is} C ² F 5, R ^{2 is} 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 2

Compounds of the general formula IA, in which R ^{1 is} C ² F 5, R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound corresponding to one row of Table A.

Table 3

Compounds of the general formula IA, in which R ^{1 is} C 3 F 7, R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponding to one row of Table A.

Table 4

Compounds of general formula IA in which R ^{1 is} C 3 F 7, R ^{2 is} methyl, R ^{3 is} Hydrogen, R ⁴ for trifluoromethyl and B for a compound corresponds in each case to one row of Table A.

Table 5 Compounds of the general formula LA, in which R ^{1 is} C 4 F 9, R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponding to one row of Table A.

Table 6 Compounds of the general formula LA in which R ^{1 is} C 4 F 9, R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound corresponds in each case to one row of Table A.

Table 7 Compounds of the general formula LA in which R ^{1 is} 4-CI-CeHe, R ^{2 is} 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 8 Compounds of the general formula LA in which R ¹ corresponds to 4-CI-CeHs, R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound corresponding to one row of Table A.

Table 9 Compounds of the general formula LA in which R ^{1 is} 4-F-CeHs, R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponding to one row of Table A.

Table 10 Compounds of the general formula LA in which R ^{1 is} 4-FC ₆ H ₅ , R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound corresponding to one row of Table A.

Table 11 Compounds of the general formula LA in which R ^{1 is} 4-Br-CeH ₅ , R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponding to one row of Table A.

Table 12 Compounds of the general formula LA in which R ^{1 is} 4-Br-CeH ₅ , R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound corresponding to one row of Table A. Table 13

Compounds of the general formula LA in which R ^{1 is} 4-CH 3 -C 6 H 5, R ^{2 is} 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 14

Compounds of the general formula LA in which R ^{1 is} 4-CH 3 -C 6 H 5, R ^{2 is} methyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound corresponds in each case to one row of Table A.

Table 15

Compounds of the general formula LA in which R ^{1 is} C ² F 5, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponds in each case to one row of Table A.

Table 16

Compounds of the general formula LA in which R ^{1 is} C ² F 5, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound corresponding to one row of Table A.

Table 17

Compounds of the general formula LA in which R ^{1 is} C 3 F 7, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponds in each case to one row of Table A.

Table 18

Compounds of the general formula LA in which R ^{1 is} C 3 F 7, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound corresponds in each case to one row of Table A.

Table 19

Compounds of the general formula LA in which R ^{1 is} C 4 F 9, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound corresponds in each case to one row of Table A.

Table 20

Compounds of the general formula LA in which R ^{1 is} C 4 F 9, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound corresponds in each case to one row of Table A. Table 21

Compounds of the general formula IA in which R ^{1 is} 4-CI-C 6 H 5, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound of one row of the table

A corresponds

Table 22

Compounds of the general formula IA, in which R ^{1 is} 4-Cl-CeHs, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound of one line each

Table A corresponds

Table 23

Compounds of general formula IA in which R ^{1 is} 4-F-CeHs, R ^{2 is} ethyl, R ^{3 is}

Is hydrogen, R ^{4 is} methyl and B for a compound corresponds in each case to one row of Table A.

Table 24

Compounds of general formula IA in which R ^{1 is} 4-F-CeH ₅ , R ^{2 is} ethyl, R ^{3 is}

Hydrogen, R ^{4 is} trifluoromethyl and B is a compound of one row of each

Table A corresponds

Table 25

Compounds of the general formula IA, in which R ^{1 is} 4-Br-CeHs, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound of one row of the table

A corresponds

Table 26

Compounds of the general formula IA in which R ^{1 is} 4-Br-CeHs, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound of one line each

Table A corresponds

Table 27

Compounds of the general formula IA, in which R ^{1 is} 4-CH 3 -C 6 H 5, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} methyl and B is a compound of one row of the table

A corresponds

Table 28

Compounds of the general formula IA in which R ^{1 is} 4-CH 3 -C 6 H 5, R ^{2 is} ethyl, R ^{3 is} hydrogen, R ^{4 is} trifluoromethyl and B is a compound of one line of each

Table A corresponds Table A

The compounds I are suitable as fungicides. They are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, 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. altemata on potatoes and tomatoes,

• Aphanomyces species of sugar beets and vegetables,

• Ascochyta species on cereals and vegetables,

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

• Blumeria graminis (powdery mildew) on cereals,

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

• Bremia lactucae on lettuce, • 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 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, e.g. Tomatoes,

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

• Grainstaining complex on rice,

Helminthosporium species on corn and rice,

Michrodochium nivale on cereals, Mycosphaerella species on cereals, bananas and peanuts, e.g.

M. graminicola on wheat or M.fijiensis on bananas,

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

• Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans, • Phomopsis species on soybeans and sunflowers,

• Phytophthora infestans on potatoes and tomatoes,

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

Plasmopara viticola on grapevines,

• Podosphaera leucotricha on apple, • Pseudocercosporella herpotrichoides on cereals,

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

Puccinia species on various plants, e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals, or P. asparagi on asparagus, • Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. lateuatum,

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, potatoes, sugar beet, vegetables and various plants such as e.g. R.solani on turnips and various plants,

• Rhynchosporium secalis on barley, rye and triticale, • Sclerotinia species on oilseed rape and sunflowers,

• Septoria tritici and Stagonospora nodorum on wheat,

• Erysiphe (syn. Uncinula) necator on grapevine,

• Setospaeria species on corn and turf,

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

• Tilletia species of cereals,

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

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

In particular, they are suitable for controlling harmful fungi from the class of Peronosporomycetes (syn.Oomyceten), such as Peronospora species, Phytophthora species, Plasmopara viticola, Pseudoperonospora species and Pythium species. The compounds I are also suitable for controlling harmful fungi in the protection of materials (eg 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 protective material, 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 purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or excipients, if desired using fertilizer of 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 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 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, for example coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate , Ammonium nitrate, ureas and vegetable products, such as tree meal, 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 the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. 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 ingredients are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight. F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active ingredients are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water 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, 1 part by weight of swelling agent ("gelling agent") and 70 parts by weight of water or of an organic solvent to a fine suspension when diluted with water to give a stable suspension with 20 wt .-% active ingredient content 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 compounds 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 can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or Pouring be applied. 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.

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 may also be present in the form of use as fungicides 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 others Active ingredients, in particular fungicides, for example, in many cases, the spectrum of action can be broadened or resistance developments are 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-Chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) -carbamic acid methyl ester, 2- (ortho- (2,5-dimethylphenyl-oxymethylene) phenyl) -3 methoxy-methyl acrylate;

carboxamides

- Carboxylic acid anilides: Benalaxyl, Benodanil, Boscalid, Carboxin, Mepronil, Fenfuram, Fenhexamid, Flutolanil, Furametpyr, Metalaxyl, Ofurace, Oxadixyl, Oxycarboxin, Penthiopyrad, Thifluzamide, Tiadinil, 4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid - (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid

(4'-trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluoro-biphenyl-2-yl) -amide , 3-Difluoromethyl-1-ni- methyl-pyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide, 3,4-dichloro-isothiazole-5-carbon - 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, 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-yl 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,

Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionate, 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 reproduced in the synthesis example below was carried out with appropriate modification of the starting compounds to obtain further compounds. I used bonds. The compounds thus obtained are listed in the following table with physical data.

Example 1 - Preparation of (4-ethyl-5-hydroxy-3,5-dimethyl-4,5-dihydropyrazol-1-yl) phenylmethanone

A solution of 0.55 g of benzoic hydrazide and 0.51 g of ethylpentane-2,4-dione in 40 ml of ethanol was stirred for about 50 hours at 20 to 25 ⁰ C. The reaction mixture was freed from the solvent and purified by chromatography on silica gel. This gave 0.4 g of the title compound product as a colorless oil.

table

# denotes the bond to the pyrazoline ring

,

27 examples of the action 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 - 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 250 ppm of the active ingredient I-2 showed 20% infestation, while the untreated plants were 90% infected.

Claims

claims

1. Use of

in which the substituents have the following meanings:

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 -C ₀ -CyClOaIkVl, C ₃ -Cio-cycloalkenyl, _C8 -Cio-cycloalkynyl, phenyl, 5- or

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

R ² Ci-Cio-alkyl, d-Cio-haloalkyl, C ₂ -Cio-alkenyl, C ₂ -Cio-haloalkyl, _C3 - Cio-alkynyl, C ₃ -Cio haloalkynyl, C ₃ -Cio cycloalkyl, C _3- Cio-cycloalkenyl,

C ₃ -C 10 -cycloalkynyl, phenyl, 5- or 6-membered hetaryl or heterocyclyl containing one to four heteroatoms from the group O, N or S;

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

R ^{a is} halogen, cyano, nitro, hydroxy, Ci-C ₆ alkyl, Ci-C ₆ haloalkyl, Ci-C ₆ kylcarbonyl -Al-, C ₃ -C 6 cycloalkyl, Ci-Cβ-alkoxy, Ci-Cβ- Haloalkoxy, C ₁ -C ₆ -alkoxycarbonyl, formyl, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylamino, C ₁ -C -alkylamino, C ₂ -C -alkynyl I, C ₂ -C 8 -alkyl haloalkenyl, C ₃ -C 8 cycloalkenyl, C ₂ -C ₆ kenyloxy -Al-, C ₃ -C ₆ haloalkenyloxy, C ₂ -C ₆ -alkyl kiny I, C ₂ -C ₆ haloalkynyl, C3-C6-alkynyloxy, _C3-C6 haloalkynyloxy, C3-C6-cycloalkoxy, C3-C6 Cycloalkenoxy, Ci-C3-oxyalkyleneoxy, phenyl, naphthyl, a five- to zehnglied- saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group O, N or S, OV = 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 -alkynyloxy, C ₁ -C ₆ -alkoxy-ci

C ₆ alkyl, Ci-C ₆ alkoxy-C ₆ -alkoxy and Ci-C ₆ alkoxycarbonyl, R ^vi is hydrogen, Ci-C ₆ alkyl, C ₂ -C ₆ -alkyl keny I, C -Al ₂ -C ₆ kiny I, 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 an direct bond, oxygen or nitrogen, where the nitrogen can carry one of the groups mentioned in R ^vi ,

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, 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, hetaryl-oxy, hetarylthio, where the hetaryl groups contain 5 or 6 ring members, and the cyclic systems are partially or fully halogenated or by alkyl or Haloalkyl groups may be substituted,

for the control of phytopathogenic harmful fungi.

2. Compounds of formula I according to claim 1, which correspond to the formula I. A

in which R ^{1 is} methyl, and R ^{1 is} not phenyl or bromomethyl, if B is unsubstituted or methyl-substituted phenyl, R ² , R ³ and R ^{4 are} methyl, and R ^{1 is} not tert. Butyl is when B is phenyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen.

3. Compounds of formula I according to claim 1, which correspond to the formula I. B1

4. Compounds of formula I according to claim 1, which correspond to the formula I.B2

where R ^{1 is} not methyl.

5. Compounds of formula I according to any one of claims 2 to 4, wherein R ^{2 is} Ci- Cio-alkyl or Ci-Cio-haloalkyl.

6. 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.

7. A fungicidal composition containing a solid or liquid carrier and a compound of formula I according to any one of claims 1 to 4.

8. Seed containing a compound of formula I according to any one of claims 1 to 4 in an amount of 1 to 1000 g per 100 kg.

9. 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 4.

10. Use of the compounds of the formula I according to any one of claims 1 to 4 for the preparation of a fungicidal composition according to claim 7.