EP1117650A2 - Use of substituted 5-hydroxypyrazoles, novel 5-hydroxypyrazoles, methods for the production thereof and agents containing the same - Google Patents

Abstract

The invention relates to the use of substituted 5-hydroxypyrazoles of formula (I) in which the substituents have the following meanings: B represents aryl or heteroaryl; A represents C=O, C=S or SO2; R1 represents alkyl, alkyl halide, alkenyl, alkenyl halide, alkynyl or alkynyl halide, cycloalkyl, C¿3?-C10-cycloalkenyl, cycloalkynyl, or aryl, heterocyclyl or heteroaryl; R?2¿ represents hydrogen; R3 represents hydrogen, nitro, cyano, N(R')¿2?, alkyl, alkyl halide, alkoxy, alkoxy halide, alkenyl, alkenyl halide, alkynyl or alkynyl halide, whereby R', independent of one another, represents hydrogen or alkyl; or R?2 and R3¿, together, represent a group =O, =S or =N-O-R5, whereby R5 represents hydrogen, alkyl, alkyl halide, alkenyl, alkenyl halide, alkynyl or alkynyl halide; R4 represents hydrogen, halogen, nitro, cyano N(R')¿2?, alkyl, alkyl halide, COOR', heteroaryl or heterocyclyl. The invention also relates to the use of said compounds for combating harmful fungi, to agents containing the compounds, to novel 5-hydroxypyrazoles and to methods for the production thereof.

Description

Use of substituted 5-hydroxypyrazoles, new 5-hydroxypyrazoles, processes for their preparation and agents containing them

description

The present invention relates to the use of 5-hydroxy-pyrazolines of the formula I.

in which the substituents have the following meaning:

B if necessary subst. Aryl or optionally subst. Hetaryl;

AC = 0, C = S or S0 ₂ ;

R ^{1 is} C ₂ -C ₀ -alkyl, -C-Cιo-haloalkyl, C ₃ -Cι ₀ -alkenyl, C ₃ -Cι ₀ -haloalkenyl, C ₃ -Cχo-alkynyl or C ₃ -Cιo-haloalkynyl,

if necessary subst. C ₃ -Cι ₀ cycloalkyl, optionally subst. C ₃ -Cι ₀ cycloalkenyl, optionally subst. C ₃ -Cιo-cycloalkynyl, or

if necessary subst. Aryl, if necessary subst. Heterocyclyl or subst. Hetaryl;

R ^{2 is} hydrogen;

R ^{3 is} hydrogen, nitro, cyano, N (R ') ₂ , -CC alkyl, C _! -C ₄ halo alkyl, -C -C alkoxy, -C -C haloalkoxy, C ₂ -C alkenyl, C -C haloalkenyl, C -C alkynyl or C ₂ -C haloalkynyl, where

R 'independently of one another is hydrogen or -CC alkyl;

or R ² and R ³ together form a group

= 0, = S or = N-0-R ⁵ , where R ^{5 is} hydrogen, Cχ-C ₄ alkyl, -C-C haloalkyl,

C ₃ -C ₆ alkenyl, C ₃ -C ₆ haloalkenyl, C ₃ -C ₆ ~ alkynyl or C ₃ -C ₆ ~ haloalkynyl;

R ^{4 is} hydrogen, halogen, nitro, cyano, N (R '), Cι _. -C ₄ alkyl, -C-C ₄ haloalkyl, COOR ', hetaryl or heterocyclyl;

to combat harmful fungi, and agents containing them.

The invention also relates to new 5-hydroxypyrazoles and processes for their preparation.

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.

However, their effect is unsatisfactory in many cases. Therefore, the task was to find compounds with improved effectiveness.

Accordingly, the use of substituted 5-hydroxypyrazoles of the formula I as a fungicide and agents containing them were found.

Individual l-benzoyl-5-hydroxy-pyrazolines are from Acta Chem.

Scand., Vol. 24, pp. 1744 (1970); Zh. Org. Khim. , Vol. 15, p. 1100 (1979); ibid., vol. 16, p. 415 and p. 2235 (1980); ibid., vol. 17, p. 284 (1981); ibid., vol. 18, p. 762 (1982); ibid., vol. 20, p. 1371 (1984); ibid., vol. 21, p. 2493 (1985); ibid., vol. 22, p. 286 and p. 2043 (1986); ibid., vol. 23, p. 1433 (1987); Khim. Geterotski Soedin, Vol. 9, p. 1210 (1987); Indian J. Chem. Sect B, Vol. 29B, p. 887 (1990); Inorg. Chem., Vol. 31, p. 598 (1992); J. Fluorine Chem. Vol. 65, p. 21 (1993) and tetrahedron. 50, p. 11447 (1994). However, the biological activity of these compounds is unknown in the prior art.

Compounds of the formula I are in a tautomeric equilibrium with the open-chain form in general [cf. J. Org. Chem. ÜSSR, p. 2037 (1983); ibid. p. 1247 (1984)].

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

Compounds of the formula I in which A is C = 0 (formula IA) can be obtained, for example, in the following way:

This reaction usually takes place at temperatures from 0 ° C. to 200 ° C., preferably 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); Bull. 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 dirnethylacetamide, particularly preferably methanol, ethanol and tetrahydrofuran. Mixtures of the solvents mentioned can also be used.

The starting materials are generally reacted with one another in equimolar amounts. It can 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 literature cited.

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 usually takes place at temperatures from 0 ° C. to 150 ° C., preferably 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 also known in the literature [Organikum, VEB Verlag der Wissenschaften, 15th edition, pp. 584ff., Berlin 1976] or can be prepared in accordance with the literature cited .

Compounds of the formula I in which A is S0 (formula IB.1) are preferably accessible in the following way:

IV III IB.l 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 literature cited.

The compounds of the formula I in which A is C = S (formula IB.2) can be obtained from the corresponding compounds of the formula IA by reaction with a sulfurization agent.

The sulfurization of IA takes place under conditions known per se, it usually takes place at temperatures from 0 ° C. to 180 ° C., preferably 20 ° C. to 140 ° C., in an inert organic solvent [cf. 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, Di - Oxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, as well as dimethyl sulfoxide, particularly preferably toluene and tetrahydrofuran. Mixtures of the solvents mentioned can also be used.

Examples of suitable sulfurizing agents are phosphorus pentasulfide or Lawesson's reagent.

The reaction mixtures are worked up in a conventional manner, e.g. by mixing with water, separating the phases and, if necessary, purifying the crude products by chromatography. The intermediate and end products fall partly in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or purified under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting.

In the definitions of the symbols given in the formulas above, collective terms were used which 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-methylpropyl, 2- Methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dirnethylpropyl, 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 with 1 to 10 carbon atoms (as mentioned above), it being possible for part or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, for example Cχ-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-di-fluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2 -fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl and pentafluoroethyl;

Alkoxy: straight-chain or branched alkyl groups with 1 to 10 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-);

Haloalkoxy: straight-chain or branched haloalkyl groups with 1 to 10 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-);

Alkylthio: straight-chain or branched alkyl groups with 1 to 10 or 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a sulfur atom (-S-);

Alkylamino: a straight-chain or branched alkyl group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the structure via an amino group (- H-);

Dialkylamino: two independent, straight-chain or branched alkyl groups each having 1 to 10 carbon atoms (as mentioned above), which are bonded to the skeleton via a nitrogen atom;

Alkylcarbonyl: a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-C0-);

Alkoxycarbonyl: an alkoxy group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);

Alkylt iocarbonyl: an alkylthio group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-); Alkylsulfonyl: a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-S0-);

Dialkylaminosulfonyl: a dialkylamino group (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-S0 ₂ -);

Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals with 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, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, l-dimethyl-2-propenyl, 1, 2- Dimethyl-l-propenyl, 1,2-dirnethyl-2-propenyl, 1-ethyl-lpropenyl, l-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, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl , 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl , 1, l-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-l-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, l -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), the hydrogen atoms in these groups being partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine can;

Alkenyloxy: unsaturated, straight-chain or branched hydrocarbon radicals with 3 to 10 carbon atoms and a double bond in any position not adjacent to the hetero atom. sition (as mentioned above) which are bonded to the structure via an oxygen atom (-0-);

Alkenylcarbonyl: unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 10 carbon atoms and a double bond in any position (as mentioned above) which are bonded to the skeleton via a carbonyl group (-CO-);

Alkynyl: straight-chain or branched hydrocarbon groups with 2 to 4, 6, 8 or 10 carbon atoms and a triple bond in any position, e.g. C-Ce-alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4- Pentinyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2- propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 1-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl- 3-pentinyl, 2-methyl-4-pentinyl, 3-methyl-l-pentinyl, 3-methyl-4-pentinyl, 4-methyl-l-pentinyl, 4-methyl-2-pentinyl, 1, l-dimethyl- 2-butynyl, 1, l-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2, 2-dimethyl-3-butynyl, 3, 3-dimethyl-l-butynyl, 1-ethyl-1 2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-l-methyl-2-propynyl;

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

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

Cycloalkoxy: monocyclic, saturated hydrocarbon groups with 3 to 12 carbon ring members (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-);

Cycloalkylamino: monocyclic, saturated hydrocarbon groups with 3 to 12 carbon ring members (as mentioned above) which are attached to the skeleton via an amino group (-NH-); 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, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolididinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5- Pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-0xazolidinyl, 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-thia-diazolidin-3-yl, 1,2, 4-thiadiazolidin-5-yl, 1, 2, 4-triazolinidine-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-dihydrothien-2-yl, 2,3-dihydrothia n-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-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-isoxazoline-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4- yl, 4-isoxazoline-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazoline-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin 3-yl, 4-isothiazoline-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazoline-4-yl, 2-isothiazolin-5-yl, 3- Isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-l-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3- Dihydropyrazol-4-yl, 2, 3-dihydropyrazol-5-yl, 3, 4-dihydropyrazol-l-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-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-di-hydrooxazole 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, -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, -hexahydrotriazin-3-yl;

Aryl: a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. Phenyl, naphthyl and anthraceny1;

Aryloxy: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via an oxygen atom (-0-); Arylthio: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a sulfur atom (-S-);

Arylamino: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via an amino group (-NH-);

Arylcarbonyl: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonyl group (-C0-);

Aryloxycarbonyl: a mono- to trinuclear aryloxy group (as mentioned above) which is bonded to the skeleton via a carbonyl group (-C0-);

Arylthiocarbonyl: a mono- to trinuclear arylthio group (as mentioned above) which is bonded to the skeleton via a carbonyl group (-C0-);

Arylaminocarbonyl: a mono- to trinuclear arylamino group (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);

Arylcarbonyloxy: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonyloxy group (-C0 ₂ -);

Arylcarbonylthio: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonylthio group (-COS-);

Arylcarbonylamino: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonylamino group (-CONH-);

Arylsulfonyl: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-S0 ₂ -);

Aryloxysulfonyl: a mono- to trinuclear aryloxy group (as mentioned above) which is bonded to the structure via a sulfonyl group (-S0-); Arylthiosulfonyl: a mono- to trinuclear arylthio group (as mentioned above) which is bonded to the structure via a sulfonyl group (-S0-);

Arylaminosulfonyl: a mono- to trinuclear arylamino group (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-S0 ₂ -);

Hetaryl: - 5-σliedriσes hetaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-ring hetaryl groups, which in addition to carbon atoms contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom can contain as ring links, 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, l, 2,4-thiadiazol-3-yl, l, 2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, l, 3,4-oxadiazol- 2-yl, 1, 3, 4-thiadiazol-2-yl and 1, 3, 4-triazol-2-yl;

- Benzo-condensed 5-membered hetaryl, containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulfur atom: 5-ring hetaryl groups which, in addition to carbon atoms, can contain 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 a nitrogen and an adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group;

- 5-membered hetaryl bonded via nitrogen, containing one to four nitrogen atoms, or 5-membered hetaryl, which is bonded via nitrogen, contains one to three nitrogen atoms: 5-ring hetaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms May contain ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member by one

Buta-l, 3-dien-l, 4-diyl group can be bridged, these rings being bonded to the structure via one of the nitrogen ring members;

6-membered hetaryl containing one to three or one to four nitrogen atoms: 6-ring hetaryl groups which, in addition to carbon atoms, may contain one to three or one to four nitrogen atoms as ring members, for example 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;

organic rest: if necessary subst. Alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl or hetaryl.

The addition "possibly subst." In relation to alkyl, alkenyl and alkynyl groups is intended to express that these groups can be partially or completely halogenated [i.e. the hydrogen atoms of these groups can be partially or completely replaced by identical or different halogen atoms as mentioned above (preferably fluorine, chlorine or bromine) and / or can carry one to three (preferably one) of the following radicals:

- cyano, nitro, hydroxy, amino, formyl, carboxyl, aminocarbonyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, Alkylcarbonylarrd.no, alkoxycarbonylamino, alkylcarbonyl-N-alkylamino and Alkylcarbo nyl-N-alkylamino, the alkyl groups in these radicals preferably containing 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms;

- Unsubstituted or substituted by conventional groups cycloalkyl, cycloalkoxy, cycloalkylthio, cycloalkylamino, cycloalkyl-N-alkylamino, heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylamino or heterocyclyl-N-alkylamino, preferably 12 to 8, the cyclic systems 3 to 12, the cyclic systems, 3 to 12, the cyclic systems Contain ring members, in particular 3 to 6 ring members and the alkyl groups in these radicals preferably 1 to 6

Contain carbon atoms, in particular 1 to 4 carbon atoms;

aryl, aryloxy, arylthio, arylamino, aryl-N-alkylamino, arylalkoxy, arylalkylthio, arylalkylamino, arylalkyl-N-alkylamino, unsubstituted or substituted by conventional groups

Hetaryl, hetaryloxy, hetarylthio, hetarylamino, hetaryl-N-alkylamino, hetarylalkoxy, hetarylalkylthio, hetarylalkylamino and hetarylalkyl-N-alkylamino, the aryl radicals preferably containing 6 to 10 ring members, in particular 6 ring elements (phenyl), the hentaryl radicals (phenyl) Contain 5 or 6 ring members and the alkyl groups in these radicals preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms.

The addition "possibly subst" in relation to the cyclic (saturated, unsaturated or aromatic) groups is intended to express that these groups are partially or completely halogenated can [ie. the hydrogen atoms of these groups can be partially or completely replaced by identical or different halogen atoms as mentioned above (preferably fluorine, chlorine or bromine, in particular fluorine or chlorine)] and / or can carry one to four (in particular one to three) of the following radicals :

- Cyano, nitro, hydroxy, amino, carboxyl, aminocarbonyl, alkyl, haloalkyl, alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy, alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, alkylcarbonyl , Alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino, alkylcarbonyl-N-alkylamino and alkoxycarbonyl-N-alkylamino, the alkyl groups in these radicals preferably having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms contain and contain the alkenyl or alkynyl groups mentioned in these radicals 2 to 8, preferably 2 to 6, in particular 2 to 4 carbon atoms; and / or one to three (in particular one) of the following radicals:

- Unsubstituted or substituted by conventional groups cycloalkyl, cycloalkoxy, cycloalkylthio, cycloalkylamino, cycloalkyl-N-alkylamino, heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylamino or heterocyclyl-N-alkylamino, the cyclic systems preferably 3 to 12-membered rings, 3 to 12 ring members, contain in particular 3 to 6 ring members and the alkyl groups in these radicals preferably 1 to 6

Contain carbon atoms, in particular 1 to 4 carbon atoms;

aryl, aryloxy, arylthio, arylamino, aryl-N-alkylamino, arylalkoxy, arylalkylthio, arylalkylamino, arylalkyl-N-alkylamino, unsubstituted or substituted by conventional groups

Hetaryl, hetaryloxy, hetarylthio, hetarylamino, he aryl-N-alkylamino, hetarylalkoxy, hetarylalkylthio, hetarylalkylamino and hetarylalkyl-N-alkylamino, the aryl radicals preferably containing 6 to 10 ring members, in particular 6 ring members (phenyl), in particular the 5 radicals or contain 6 ring members and the alkyl groups in these radicals preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms and / or can carry one or two (in particular one) of the following radicals:

- formyl,

- CR ^{i: Li} = NOR ^iv [where R ^{111 is} hydrogen, alkyl, cycloalkyl and aryl and R ^{iv is} alkyl, alkenyl, haloalkenyl, alkynyl and arylalkyl (the alkyl groups mentioned preferably containing 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms , the cycloalkyl groups, alkenyl groups and alkynyl groups mentioned, preferably 3 to 8, in particular 3 to 6, carbon atoms. lenstoffatome included) and aryl in particular denotes phenyl, which is unsubstituted or may be substituted by customary groups] or - NR ^v -CO-DR ^vi [wherein R ^v is hydrogen, hydroxy, Cι-C ₆ alkyl, C ₂ -C ₆ -Alkenyl, C ₂ -C ₆ -alkynyl, Cι-C ₆ -alkoxy, C ₂ -C ₆ -alkenyloxy, C ₂ -C ₆ -alkynyloxy, Cι-C ₆ -alkoxy-Cι-C ₆ -alkyl, Cχ- C ₆ -alkoxy- Ci-Cβ-alkoxy and -CC ₆ alkoxycarbonyl, R ^{vi is} hydrogen, -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₃ - C6-Cycloalkyl, C ₃ -C ₆ -cycloalkenyl, aryl, aryl-Ci-Cβ-alkyl, hetaryl and hetaryl-Ci-C _δ -alkyl and D is a direct bond, oxygen or nitrogen, the nitrogen being one of the R ^vi mentioned groups can carry], and / or in which two adjacent C atoms of the cyclic systems a C ₃ -Cs alkylene, C ₃ -Cs alkenylene, oxy-C -C alkylene, oxy-Cι ~ C ₃ -alkyleneoxy, oxy-C ₂ -C ₄ -alkenylene, oxy-C -C ₄ -alkenyleneoxy or butadienediyl group can carry, these Bridges may in turn be partially or fully halogenated and / or may carry one to three, in particular one or two of the following radicals: - Cι-C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ -haloalkoxy and C ₁ -C ₄ -alkylthio.

Customary groups are in particular the following sub-substituents to be understood: halogen, cyano, nitro, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cx-Cj-alkoxy, _{Cι-C4-haloalkoxy,} Cι-C ₄ -Alkyl- amino, Di-Cι-C ₄ alkylamino and Cι ~ C -alkylthio.

Under possibly subst. Phenyl is in particular to be understood as a phenyl ring which is substituted by halogen, cyano, nitro, hydroxy, amino, carboxyl, aminocarbonyl, C ₁ -C ₄ -alkyl or halogen-C ₁ -C ₄ -alkyl.

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

Compounds IA are particularly preferred.

In addition, compounds of the formula IB in which A 'S0 ₂ means are particularly preferred.

Likewise, particular preference is given to compounds of the formula IB in which A 'is C = S.

In addition, compounds I are particularly preferred in which R ^{1 is} C ¹ -C 4 -haloalkyl. Compounds I in which R ^{1 is} C ₃ F ₇ or C ₂ F ₅ are also particularly preferred.

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

Likewise, particular preference is given to compounds I in which B is phenyl which has a substituent in the 2-position.

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

Also particularly preferred are compounds I in which B is phenyl which has substituents in the 3, 4 position.

In addition, compounds I are particularly preferred in which B represents hetaryl.

Furthermore, compounds I are particularly preferred in which R ² and R ^{3 are} hydrogen.

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

Likewise, particular preference is given to compounds I in which R ^{4 represents} trifluoromethyl.

In addition, compounds I are particularly preferred in which the substituents R ¹ and R ^{4 are} different.

In particular, in view of their use, the compounds I compiled in the tables below are preferred. The groups mentioned for a substituent in the tables also represent a particularly preferred embodiment of the substituent in question, regardless of the combination in which they are mentioned.

Table 1 Compounds of the general formula IA ', in which R ¹ for CFs _, R ⁴ for methyl and B for a compound each correspond to one row of Table A.

Table 2

Compounds of the general formula IA 'in which R ¹ for C ₂ F _{5 #} R ⁴ for ethyl and B for a compound corresponds in each case to one line of Table A.

Table 3

Compounds of the general formula IA 'in which R ¹ for C ₃ F _7, R ⁴ for methyl and B for a compound corresponds in each case to one line of Table A.

Table 4

Compounds of the general formula IA 'in which R ¹ for C ₃ F ₇ R ⁴ for ethyl and B for a compound corresponds in each case to one line of Table A.

Table 5

Compounds of the general formula IB.1 ', in which R ¹ for CFs _# R ⁴ for methyl and B for a compound corresponds in each case to one line of Table A.

Table 6

Compounds of the general formula IB.1 ', in which R ¹ for CF _5, R ⁴ for ethyl and B for a compound corresponds in each case to one line of Table A.

Table 7

Compounds of the general formula IB.1 ', in which R ¹ for C ₃ F _{7 /} R ⁴ for methyl and B for a compound corresponds in each case to one line of Table A.

Table 8

Compounds of the general formula IB.1 ', in which R ¹ for C ₃ F ₇ R ⁴ for ethyl and B for a compound corresponds in each case to one line of Table A.

Table 9

Compounds of the general formula IB.2 ', in which R ¹ for CF _{5 /} R ⁴ for methyl and B for a compound corresponds in each case to one line of Table A. IB.2 '

Table 10

Compounds of the general formula IB.2 ', in which R ¹ for CFs, R ⁴ for ethyl and B for a compound corresponds in each case to one line of Table A.

Table 11

Compounds of the general formula IB.2 ', in which R ¹ for C ₃ F _{7 #} R ⁴ for methyl and B for a compound corresponds in each case to one line of Table A.

Table 12

Compounds of the general formula IB.2 ', in which R ¹ for C ₃ F _{7 /} R ⁴ for ethyl and B for a compound corresponds in each case to one line of Table A.

Table A

The compounds I are suitable as fungicides. They are characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.

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

They are particularly suitable for combating the following plant diseases:

Alternaria species on vegetables and fruits,

Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, • Cercospora arachidicola on peanuts,

Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,

Erysiphe graminis (powdery mildew) on cereals, Fusarium and Verticillium species on various plants, • Helminthosporium species on cereals,

Mycosphaerella species on bananas and peanuts, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Podosphaera leucotricha on apples, • Pseudocercosporella herpotrichoides on wheat and barley, Pseudoperonospora species on hops and cucumbers, Puccinia species or cereals Rice, Rhizoctonia species on cotton, rice and lawn, • Septoria nodorum on wheat, Uncinula necator on vines,

Ustilago species on cereals and sugar cane, and Venturia species (scab) on apples and pears.

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 active amount of the active compound. Fabrics treated. The application can take place 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% by weight of active ingredient.

Depending on the type of effect desired, the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per hectare.

In the case of seed treatment, amounts of active ingredient of 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.

When used in material or storage protection, the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of treated material.

The compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; in any case, it should 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 carriers, if desired using emulsifiers and dispersants, and in the case of water as a diluent, other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. B. ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose. Suitable surfactants are alkali metal, Ammoni ^¬ come salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic sulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids such as so-their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, alkutyl phenol alcohol, ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, fatty alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, fatty alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, fatty alcohol, alkyl alcohol ethoxylated ethoxylated alcohol, fatty alcohol, alkyl alcohol ethoxylated alcohol, fatty alcohol, alkyl alcohol ethoxylated alcohol, fatty alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, fatty alcohol alkylene alcohol, alkyl alcohol ethoxylated alcohol, alkyl alcohol ethoxylated alcohol, fatty alcohol, alkyl alcohol ethoxylated alcohol, fatty alcohol and alcohols, and Castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin sulfite waste liquors and methyl cellulose.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions from medium to high boiling points, such as kerosene or diesel oil, furthermore coal tarols as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and herbal 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 the NMR spectrum).

Examples of formulations are:

I. 5 parts by weight of a compound according to the invention are intimately mixed with 95 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 5% by weight of the active ingredient.

II. 30 parts by weight of a compound according to the invention are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A preparation of the active ingredient with good adhesiveness (active ingredient content 23% by weight) is obtained in this way.

III. 10 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid-N-monoethanolamide, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil (active ingredient content 9% by weight).

IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 5 parts by weight. -Share the adduct of 40 moles of ethylene oxide with 1 mole of castor oil (active ingredient content 16% by weight).

V. 80 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel well mixed and ground in a hammer mill (active ingredient content 80% by weight).

VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution is obtained which is suitable for use in the form of tiny drops (active substance content 90% by weight). VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone,

3OGew. Parts of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide with 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

VIII.20 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel well mixed and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.

The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes; 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. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, wetting, adhesive,

Dispersants or emulsifiers and possibly solvents or oil existing concentrates are prepared which are suitable for dilution with water.

The active substance concentrations in the ready-to-use preparations can be varied over a wide range. 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 process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.

Oils of various types, herbicides, fungicides, other pesticides, bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.

The agents according to the invention can also be present in the use form as fungicides together with other active ingredients, which e.g. with herbicides, insecticides, growth regulators, fungicides or even with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases.

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:

• Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylenediamine bis dithiocarbamate, tetramethylthiurondarbamethyne damidulfide, , Ammonia complex of zinc (N, N '-propylene-bis-dithiocarbamate), zinc (N, N' -propylene-bis-dithiocarbamate), N, N '-polypropylene-bis- (thiocarbamoyl) disulfide;

Nitroderivate, such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-isopropyl carbonate, 5- Nitro-isophthalic acid-di-isopropyl ester, - • heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0- Diethyl phthalimidophosphonothioate, 5-amino-l- [bis- (dimethylamino-no) -phosphinyl] -3-phenyl-l, 2, 4-triazole, 2, 3-dicyano-l, 4-di-thioanthraquinone, 2- Thio-1,3-dithiolo [4,5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benz - imidazole, 2- (Thiazolyl- (4)) -benzimidazole, N- (1, 1, 2, 2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide, • N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-l, 2,3-thiadiazole, 2-rhodanomethyl thiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-di-hydro-5-carboxanilido-6-methyl- l, 4-oxathiin, 2, 3-dihydro-5-car-boxanilido-6-methyl-l, 4-oxathiin-4, 4-dioxide, 2-methyl-5, 6-di-hydro-4H-pyran 3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl furan-3-carboxylic acid anilide, 2, 5- Dimethyl-furan-3-carbon-acid cyclohexylamide, N-cyclohexyl-N-methoxy-2, 5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2,2-trichloroethyl-talc, piperazin-1,4-diylbis-l- (2,2,2-trichloroethyl) formamide, 1- (3,4-dichloroanilino) - 1-formylamino-2, 2, 2-trichloroethane, 2, 6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3 - (p-tert-Butylphenyl) -2-methylpropyl] cis-2, 6-dimethyl-morpholine, N- [3- (p-tert-butylphenyl ) -2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-l, 3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, 1 - [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-tri-chlorophenoxyethyl) -N'-imidazol-ylurea, 1- (4-chlorophenoxy) -3, 3-dimethyl-l- (1H-1, 2, 4 -triazol-l-yl) -2-butanone, 1- (4-chlorophenoxy) -3, 3-dimethyl-l- (1H-1,2,4-triazol-l-yl) -2-butanol, (2RS, 3RS) -1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxyran-2-ylmethyl] -1H-1, 2, 4-triazole, α- (2-chlorophenyl ) -α- (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene,

Strobilurins such as methyl-E-methoxyimino- [α- (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yl- oxy] -phenyl} -3-methoxyacrylate, methyl-E-methoxyimino- [α- (2-phenoxyphenyl)] acetamide, methyl-E-methoxyimino- [α- (2, 5-dimethylphenoxy) -o-tolyl ] acetamide,

Anilinopyrimidines such as N- (4, 6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- [4-Me- thyl-6-cyclopropyl-pyrimidin-2-yl] aniline,

Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile,

Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3, 4-dimethoxyphenyl) acrylic morpholide,

As well as various fungicides, such as dodecylguanidine acetate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide,

Hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) - alaninate, DL-N- (2,6-dimethyl-phenyl) -N- (2'-methoxyacetyl) - alamin-methyl-ester, N- (2, 6-dimethylphenyl) -N-chloroacetyl-D, L-2-ami-nobutyrolactone, DL-N- (2, 6-dimethylphenyl) -N- (phenylacetyl) - alanine methyl ester, 5-methyl-5-vinyl-3- (3, 5-dichlorophenyl) -2, 4- dioxo-1,3-oxazolidine, 3- (3,5-dichlorophenyl) -5-methyl-5-methoxy-methyl-1,3-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) - 1-isopropylcarbamoylhydantoin, N- (3, 5-dichlorophenyl) -1, 2-dimethylcyclopropan-1, 2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] - acetamide, 1- [2- (2,4-di-chlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H-1,2,4-triazolyl -l-methyl) -benzhydryl alcohol, N- (3-chloro-2, 6-dinitro-4-trif luormethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1- ((bis- ( 4-fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

Synthesis examples

The instructions given in the synthesis examples below were used with the appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the tables below with physical details.

A) Production of the preliminary products

Example 1 Preparation of 2-methyl-pyridine-3-carboxylic acid hydrazide

A solution of 1 g of 2-methyl-pyridine-3-carboxylic acid methyl ester in 5 ml of methanol was stirred for 14 hours at 20 to 25 ° C. after adding 3 g of hydrazine hydrate. After dilution with water, the mixture was extracted with methylene chloride. After the solvent had been distilled off, the combined organic phases became 0.45 g of the title compound as colorless crystals of mp 60 ° C.

Example 2 Preparation of 4-chlorophenylsulfonylhydrazide

24 g (0.48 mol) of hydrazine hydrate, dissolved in 25 ml of water, were added dropwise to a solution of 50 g (0.24 mol) of 4-chlorophenylsulfonyl chloride in 300 ml of THF at 10 to 20 ° C. while stirring. After stirring for 15 min at about 15 ° C, the reaction mixture was poured onto ice. After the solution had been concentrated, the precipitate was filtered off. 40 g of the title compound were isolated as colorless crystals of mp 79 ° C. Example 3 Preparation of

5,5,6,6,7,7, 7-heptafluoro-2,4-heptanedione

H ₃ CX "TH ₃ C ₃ F ₇ ' ^/ Υ)' _ '^' TH ₃ _ü_

4.1 g (170 mmol) sodium hydride (97%) in 45 ml anhydrous. Cyclohexane were mixed with a mixture of 68.4 g (300 mmol) perfluorobutyric acid methyl ester and 8.7 g (150 mmol) anhydrous. Acetone added at 30 ° C. After stirring for 14 hours at 20 to 25 ° C with dist. Diluted water, then acidified with dil. Hydrochloric acid. After phase separation, the aqueous phase was extracted with diethl ether. The combined organic phases were fractionated after washing with water through a 40 cm Vigreux column. 22 g of the title compound were obtained as a colorless liquid with a melting point of 135 ° C.

iH-MR (CDC1 ₃ ): δ (ppm) = 2.1 (s, 3H); 5.95 (S, 1H).

Example 4 Preparation of 5, 5, 6, 6, 6-pentafluoro-2, 4-hexanedione

Under the conditions mentioned in Example 3, 19.4 g of the title compound was obtained as a colorless liquid by reacting 2.7 g of sodium hydride in 27 ml of cyclohexane with 5.8 g (100 mmol) of acetone and 38.4 g (200 mmol) of ethyl perfluoropropionate obtained with bp of 119 ° C.

iH-NMR (CDCI ₃ ): δ (ppm) = 2.1 (s, 3H); 5.95 (s, 1H).

B) Preparation of the active ingredient

Example 4 Preparation of

5-hydroxy-5-trifluoromethyl-3-methyl-4,5-dihydro-pyrazol-l-yl- (4-hydroxyphenyl) methanone [1-73]

A solution of 5 g (33 mmol) of 4-hydroxybenzoic acid hydrazide and 5 g (33 mmol) of trifluoroacetylacetone in 100 ml of ethanol was heated at 70 ° C. for 6 hours. After the solvent was distilled off, 9.0 g of the title compound were obtained as colorless crystals. Example 5 Preparation of

5-hydroxy-5- (1, 1, 1,2, 2-pentafluoroethyl) -3-methyl-

4,5-dihydro-pyrazol-l-yl- (4-bromophenyl) -methanone [1-13]

Under the conditions mentioned in Example 4, by reaction of 1 g (5 mmol) of 4-bromobenzoic acid hydrazide with 1 g (5 mmol) of 5, 5,6,6,6-pentafluoro-2, 4-hexanedione in 100 ml of ethanol, 1.9 Obtain g of the title compound as colorless crystals.

Example 6 Preparation of

5-hydroxy-5- (1, 1, 1, 2, 2, 3, 3-heptafluoropropyl) -3-methyl-4, 5-dihydro-pyrazol-l-yl-phenyl-methanone [1-35]

Under the conditions mentioned in Example 4, 0.8 g (6 mmol) of benzoic acid hydrazide was reacted with 1.5 g (6 mmol) of 5,5,6,6,7,7,7-heptafluoro-2,4 -heptanedione in 100 ml of ethanol 9.0 g of the title compound as colorless crystals.

Example 7 Preparation of 2-benzenesulfonyi-3-trifluoromethyl-5-methyl-3,4-dihydro-2H-pyrazol-3-ol [II-1]

sy ^{s m>}

A solution of 1 g (6 mmol) of benzenesulfonic acid hydrazide and 0.9 g (6 mmol) of trifluoroacetylacetone in ethanol was heated to 70 ° C. for 6 hours. After the solvent was distilled off, 1.6 g of the title compound were obtained as colorless crystals. Table I

IA '

Table II

Examples of the action against harmful fungi

The fungicidal activity of the compounds of the general formula I was demonstrated by the following tests:

The active ingredients were separated or together as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight .-% Wettol® EM (non-ionic emulsifier based on ethoxylated castor oil) prepared and diluted with water according to the desired concentration.

Use Example 1 - Activity against Phytophthora infestans on tomatoes

Leaves of potted plants of the "large meat tomato" variety were sprayed to runoff point with an aqueous suspension which was prepared from a stock solution of 10 3 active ingredient, 63% cyclohexanone and 27% emulsifier. The following day, the leaves were infected with an aqueous suspension of zoospores from Phytophthora infestans. The plants were then placed in a steam-saturated chamber at temperatures between 16 and 18oC. After 6 days, the blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.

In this test, those with 250 ppm of the active ingredients showed 1-1 to 1-4, 1-6, 1-7, 1-9 to 1-11, 1-13 to 1-16, 1-26 to 1-35, 1-53, 1-59, 1-60, 1-63, 1-68, 1-72, 1-74, 1-94, 1-95, 1-97, 1-112, 1-113, 1- 117, 1-124, 1-127, 1-134, 1-164 and 11-13 treated plants up to 20% infestation, while untreated plants were 100% infested. Example of use 2 - effectiveness against Plasmopara viticola

Leaves of pot vines of the "Müller-Thurgau" variety were sprayed to the drip tray with aqueous active ingredient preparation which was prepared with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. In order to be able to assess the long-term effect of the substances, the plants were placed in the greenhouse for 7 days after the spray coating had dried on. Only then were the leaves inoculated with an aqueous suspension of zoospores from Plasmopara viticola. The vines were then placed for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a moist chamber for 16 hours in order to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.

In this test, those with 250 ppm of active ingredients 1-3, 1-4, 1-10, I-ll, 1-27, 1-34, 1-35, 1-46, 1-47, 1-53, 1-54, 1-73, 1-112, 1-113, 1-114, 1-116, 1-117, 1-124 and 1-127 treated plants did not infest more than 30%, while untreated plants infested 90% were.

Example of use 3 - effectiveness against Botrytis cinerea on paprika leaves

Pepper seedlings of the "Neusiedler Ideal Elite" variety, after 4-5 leaves had developed well, were sprayed to runoff point with an aqueous active compound preparation which was prepared from a stock solution of 10% active compound, 63% cyclohexanone and 27% emulsifier. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea, which contained 1.7 x 10 ⁶ spores / ml in a 2% aqueous biomalt solution. The test plants were then placed in a climatic chamber at 22 to 24 ° C and high air humidity. After 5 days, the extent of the fungal attack on the leaves could be determined visually in%.

In this test, those with 250 ppm of active ingredients I-II, 1-13, 1-24, 1-26, 1-29, 1-30, 1-45, 1-47, 1-57 to 1-61, 1-63, 1-64, 1-68, 1-70, 1-71, 1-74, 1-80, 1-94, 1-112, 1-114, 1-127 and 11-13 treated plants maximum 20% infection, while untreated plants were 100% infected.

Claims

claims

1. Use of 5-hydroxypyrazolines of the formula I.

in which the substituents have the following meaning:

B if necessary subst. Aryl or optionally subst. Hetaryl;

AC = 0, C = S or S0 ₂ ;

R ¹ C ₂ -Cιo alkyl, Cι -Cιo haloalkyl, C ₃ -Cι ₀ alkenyl,

C ₃ -Cιo haloalkenyl, C ₃ -Cι ₀ alkynyl or C ₃ -Cι ₀ haloalkynyl,

if necessary subst. C ₃ -Cι ₀ cycloalkyl, optionally subst. C ₃ -Cιo-cycloalkenyl, optionally subst. C ₃ -Cιo-cycloalkynyl, or

if necessary subst. Aryl, if necessary subst. Heterocyclyl or subst. Hetaryl;

R ^{2 is} hydrogen;

R ³ is hydrogen, nitro, cyano, N (R ') _2, Cι-C ₄ -alkyl, C -Ha- logenalkyl, C ₁ -C ₄ -alkoxy, C ₄ haloalkoxy, C ₂ -C - Alkenyl, C ₂ -C ₄ haloalkenyl, C ₂ -C ₄ alkynyl or C -C ₄ haloalkynyl, where

R 'independently of one another is hydrogen or C 1 -C ₄ -alkyl;

or R ² and R ³ together form a group

= 0, = S or = N-0-R ⁵ , where

R ⁵ are hydrogen, C ₄ -alkyl, C ₄ haloalkyl,

C ₃ -C ₆ alkenyl, C ₃ -C ₆ haloalkenyl, C ₃ -C ₆ alkynyl or C ₃ -C ₆ haloalkynyl;

R ^{4 is} hydrogen, halogen, nitro, cyano, N (R ') ₂ , -CC ₄ alkyl, -C-C haloalkyl, COOR', hetaryl or heterocyclyl;

to combat harmful fungi.

2. 5-hydroxypyrazolines of the formula IA according to claim 1, in the case of a:

R ^{3 is} nitro, cyano, N (R ') _2, Cι-C -alkyl, C haloalkyl, Cι-C ₄ -alkoxy, C ₄ haloalkoxy, C ₂ -C alkenyl, C ₂ -C _4- haloalkenyl, C ₂ -C alkynyl or C -C ₄ haloalkynyl;

or R ² and R ³ together form a group

= 0, = S or = N-0-R ⁵ , means

R ^{4 is} hydrogen, halogen, nitro, cyano, N (R ') ₂ , Cχ-C ₄ alkyl, Cι-C ₄ haloalkyl or heterocyclyl;

and B, R ¹ and R ^{2 have} the meaning given in claim 1, or

in case b:

B if necessary subst. Naphthyl, optionally subst. Heterocyclyl, optionally subst. Hetaryl or substituted phenyl, and

R ^{3 is} hydrogen,

R ^{4 is} hydrogen, halogen, nitro, cyano, N (R ') ₂ , -CC alkyl, -C ~ C ₄ haloalkyl or heterocyclyl;

where R ^{4 is} not methyl if R ^{1 is} methyl, tert. Butyl or phenyl and the group B is phenyl which is substituted by 3-bromo, 4-halogen, 4-methyl, 4-methoxy, 4-nitro, 4-dimethylamino or 4-fluoro-3-methyl, and

wherein R ^{4 is} not ethyl when both the group B and R ^{1 is} 4-fluorophenyl, or

in case c:

B unsubstituted phenyl,

R ^1, if necessary, subst. Aryl, if necessary subst. Heterocyclyl or subst. Hetaryl, if necessary subst. C ₃ -Cι ₀ cycloalkyl, optionally subst. C ₃ -Cι ₀ cycloalkenyl, optionally subst. C ₃ -Cι ₀ cycloalkynyl,

if necessary subst. n- propyl, if necessary subst. C -C ₀ alkyl, CHCI2, CH ₂ C1, CC1 ₃ , CHF ₂ , CF ₂ H, CF ₂ C1, CFC1 ₂ , C -C ₀ haloalkyl, optionally subst. C ₃ -Cιo-alkenyl, C ₃ -Cι ₀ -haloalkenyl, optionally subst. C ₃ alkynyl or C ₃ -Cι _{0 0} -Cι haloalkynyl;

R ^{2 is} hydrogen;

R ^{3 is} hydrogen, nitro, cyano, amino, methylamine, dimethylamino, Cχ-C ₄ alkyl, Cι-C ₄ haloalkyl, Cι-C ₄ alkoxy, Cι-C ₄ haloalkoxy, C ₂ -C ₄ alkenyl , C ₂ -C ₄ haloalkenyl, C ₂ ^_ C ₄ alkynyl or C ₂ -C ₄ haloalkynyl,

or R ² and R ³ together form a group

= 0, = S or = N-0-R ⁵ , and

R ^{4 is} hydrogen, halogen, nitro, cyano, N (R ') ₂ , C 1 -C ₄ alkyl, C 1 -C ₄ haloalkyl or heterocyclyl;

where R ^{1 is} not for tert. Butyl is when R ^{4 is} CF ₂ H and R ^{4 is} not methyl when R ^{1 is} phenyl.

3. 5-hydroxypyrazolines of the formula IB according to claim 1,

in the

A 'C = S or S0 ₂ mean.

4. A process for the preparation of compounds of the formula IA according to claim 2, characterized in that a hydrazine of the formula II,

O

, "_.NH, ^1X

B """ ² in which B has the meaning given in claim 2,

with a diketone of formula III, in which the substituents have the meanings given in claim 2.

5. A process for the preparation of compounds of the formula IB according to claim 3, in which A 'is C = S, characterized in that compounds of the formula I according to claim 1, in which AC = 0, are reacted with Lawesson's reagent .

6. A process for the preparation of compounds of the formula IB according to claim 3, in which A 'denotes SO ₂ , characterized in that sulfonylhydrazines of the formula IV are

%, ß

B ^ H ² in which B has the meaning given in claim 1, with diketones of the formula III,

in which the substituents have the meaning given in claim 1.

7. Use of compounds of formula I according to claim 1, in which A is C = 0, as intermediates for the preparation of

Compounds of formula IB according to claim 3, in which A 'is C = S.

8. Suitable for controlling harmful fungi, comprising a solid or liquid carrier and a compound of general formula I according to claim 1.

9. Use of the compounds I according to claim 1 for the preparation of an agent suitable for combating harmful fungi.

10. A method of combating harmful fungi, characterized in that the fungi or the materials, plants, soil or seeds to be protected against fungal attack are treated with an effective amount of a compound of the general formula I according to claim 1.