JP2002526536A - Use of substituted 5-hydroxypyrazoles, novel 5-hydroxypyrazoles, processes for their preparation and compositions containing them - Google Patents

Abstract

(57) Abstract: The present invention relates to a compound of the formula I: Wherein, B is an aryl or hetaryl, A represents, C = O, a C = S or SO _2,, R ¹ is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, or at haloalkynyl Or cycloalkyl, C ₃ -C ₁₀ -cycloalkenyl, cycloalkynyl, or aryl, heterocycle, or hetaryl, R ² is hydrogen, R ³ is hydrogen, nitro, cyano, N (R ') or _2, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, or haloalkynyl (R' is independently of one another are hydrogen or alkyl), or, R ² and R ³ is = O group, = S group, or NNOR ⁵ group (R ⁵ is hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, or haloalkynyl) Wherein R ⁴ is hydrogen, halogen, nitro, cyano, N (R ′) ₂ , alkyl, haloalkyl, COOR ′, hetaryl, or a heterocyclic ring. And a composition containing them, and a novel 5-hydroxypyrazole, and a method for producing them.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a compound of formula I:

Embedded image Wherein, B is aryl which may or may not be substituted, or an optionally hetaryl may not be substituted, A is, C = O, a C = S or SO _2,, R ¹ is C ₂ -C ₁₀ -alkyl, C ₁ -C ₁₀ -haloalkyl, C ₃ -C ₁₀ -alkenyl, C ₃ -C _10-
Haloalkenyl, C ₃ -C ₁₀ - alkynyl, or C ₃ -C ₁₀ - or a haloalkynyl, may or may not be substituted C ₃ -C ₁₀ - cycloalkyl, or may not be substituted Good C ₃ -C ₁₀ -cycloalkenyl, optionally substituted C _3-
A C ₁₀ -cycloalkynyl or an optionally substituted aryl, an optionally substituted heterocycle or an optionally substituted hetaryl, R ² Is hydrogen, R ³ is hydrogen, nitro, cyano, N (R ′) ₂ , C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C _1- C ₄ -haloalkoxy, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -haloalkenyl, C ₂ -C ₄ -alkynyl, or C ₂ -C ₄ -haloalkynyl (R ′ is independently of each other Hydrogen or C ₁ -C ₄ -alkyl), or R ² and R ³ are both = O, SS, or NNOR ⁵ (R ⁵ is hydrogen, C _1-
C ₄ - alkyl, C ₁ -C ₄ - haloalkyl, C ₃ -C ₆ - alkenyl, C ₃ -C ₆ - haloalkenyl, C ₃ -C ₆ - alkynyl, or C ₃ -C ₆ - a haloalkynyl) Wherein R ⁴ is hydrogen, halogen, nitro, cyano, N (R ′) ₂ , C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, COOR ′, hetaryl, or heterocycle. The present invention relates to the use of 5-hydroxypyrazoline for inhibiting harmful fungi, and compositions containing them.

Furthermore, the present invention relates to novel 5-hydroxypyrazoles and a method for producing them.

[0003] Substituted pyrazolin-5-ones having herbicidal and fungicidal activity are described in DE-A 37 28 27
8-arylpyrazole, which is known from US Pat. No. 8 and has fungicidal activity, is described in WO-A 94/2
No. 9276.

However, their activity is often inadequate.

It is an object of the present invention to provide compounds with improved activity.

We have found that this object is achieved by the use of substituted 5-hydroxypyrazoles of the formula I as fungicides and compositions containing them.

The individual 1-benzoyl-5-hydroxypyrazolines are known from the following literature: Acta Chem. Scand., 24 (1970), 1744; Zh. Org. Khim., 15 (1979), 1100 ;
Id. 16 (1980), 415 and 2235; id. 17 (1981), 284; id. 18 (1982), 762;
Id. 20 (1984), 1371; id. 21 (1985), 2493; id. 22 (1986), 286 and 20
43; Ditto 23 (1987), 1433; Khim.Geterotski Soedin 9 (1987), 1210; Indian
J. Chem. Sect. B, 29B (1990), 887; Inorg. Chem. 331 (1992), 598; J. Fluo
rine Chem. 65 (1993), 21 and Tetrahedron 50 (1994), 11447. But,
The biological activity of these compounds is not known in the prior art.

The compounds of the formula I exist in tautomeric equilibrium with the ring-opened form Ia [see J. Org. Chem. USSR (1983), 2037; ibid. (1984), 1247].

The present invention therefore relates to both forms, even if for clarity only the cyclic form I is described in each case.

[0010]

Embedded image Compounds of formula I wherein A is C = O (formula IA) can be obtained, for example, by the following route.

[0011]

Embedded image This reaction is usually performed at 0 ° C. to 200 ° C., preferably 20 ° C. to 100 ° C., in an inert organic solvent [J. Org. Chem. USSR (English translation), 16 (1980), 371; 21 (1985)
, 2279; id. 22 (1986), 250; id. 23 (1987), 1291; Indian J. Chem. Sect.
B, 29 (1990), 887; Bull. Soc. Chem. Jp. 62 (1989), 3409].

[0012] Suitable solvents include aliphatic hydrocarbons, aromatic hydrocarbons (eg, toluene, 0-
, M-, and p-xylene), halogenated hydrocarbons (eg, methylene chloride, chloroform, and chlorobenzene), ethers (eg, diethyl ether, diisopropyl ether, t-butyl methyl ether, dioxane, and tetrahydrofuran), nitriles ( For example acetonitrile, and propionitrile),
There are alcohols (eg, methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol) and dimethyl sulfoxide, dimethylformamide, and dimethylacetamide, with methanol, ethanol, and tetrahydrofuran being particularly preferred. Mixtures of the above-mentioned solvents can also be used.

The starting materials are usually reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of III based on II.

[0014] The hydrazide of the formula II required for producing the compound I is described in the literature [Ref: J
Heterocycl. Chem. 16 (1976), 561; Helv. Chim. Acta, 27 (1944), 883; J.
Chem. Soc. (1943), 413] or may be prepared according to the cited references.

[0015] The hydrazide of formula II is usually prepared from the corresponding carboxylic acid ester of formula V by reaction with hydrazine hydrate. In formula V, R ′ is C ₁ −
C ₄ -alkyl.

[0016]

Embedded image The reaction is usually carried out at 0 ° C. to 150 ° C., preferably at 20 ° C. to 100 ° C., in an inert organic solvent [see J. Heterocycl. Chem. 16 (1976), 561; Helv. Chim. Acta, 27
(1944), 883; J. Chem. Soc. (1943), 413].

The diketones of the formula III required to prepare the compounds I are also described in the literature [Organiku
m, VEB Verlag der Wissenschaften, 15th edition, p.584ff., Berlin 1976] or may be prepared according to the cited references.

The compound of formula I wherein A is SO ₂ (formula IB.1) can preferably be obtained by the following route.

[0019]

Embedded image This reaction is advantageously carried out under the conditions set for producing compound IA.

The starting materials are usually reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of III based on IV.

The sulfohydrazide of the formula IV required to produce compound I is described in the literature [J
Chem. Soc. Chem. Commun. (1972), 1132; J. Chem. Soc. (1949), 1148; Hel.
v. Chim. Acta, 42. (1962), 996] or may be prepared according to the cited references.

Compounds of formula I wherein A is C = S (formula IB.2) can be obtained by reacting the corresponding compound of formula IA with a sulfurizing agent.

[0023]

Embedded image The sulfuration of IA is carried out under conditions known per se, usually from 0 ° C to 180 ° C, preferably from 20 ° C to
Performed in an inert organic solvent at 140 ° C. [Ref: Liebigs Ann. Chem., (1989), 177]
.

Suitable solvents include aliphatic hydrocarbons (eg, pentane, hexane, cyclohexane, and petroleum ether), aromatic hydrocarbons (eg, toluene, 0-, m-,
And p-xylene), halogenated hydrocarbons (eg, methylene chloride, chloroform, and chlorobenzene), ethers (eg, diethyl ether, diisopropyl ether, t-butyl methyl ether, dioxane, anisole and tetrahydrofuran), nitriles (eg, acetonitrile, And propionitrile), and dimethyl sulfoxide, with toluene and tetrahydrofuran being particularly preferred. Mixtures of the above-mentioned solvents can also be used.

Suitable sulphiding agents include, for example, phosphorus pentasulfide or Lawesson's reagent.

The reaction mixture is produced in a customary manner, for example by adding water, mixing, phase separation and, if necessary, chromatographic purification of the crude product. Some intermediates and end products, in the form of clear or slightly brownish viscous oils, can be obtained by purification or separation from volatile components under reduced pressure and at moderately high temperatures There is. If the intermediates and end products are obtained as solids, purification can also be performed by recrystallization or digestion.

In the definitions of the symbols shown in the above formulas, collective terms representing the following substituents were generally used.

Halogen: fluorine, chlorine, bromine and iodine.

Alkyl: Saturated linear or branched hydrocarbon radicals having _{1 to 4, 6} , 8 or 10 carbon atoms, for example C ₁ -C ₆ -alkyl include 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-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: a straight-chain or branched alkyl group having 1 to 10 carbon atoms (described above), wherein part or all of the hydrogen atoms of these groups are substituted by the halogen atom. Those such as C ₁ -C ₂ -haloalkyl include 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.

Alkoxy: A straight-chain or branched alkyl group having 1 to 10 carbon atoms, linked to the skeleton via an oxygen atom (-O-) (described above).

Haloalkoxy: a straight-chain or branched haloalkyl group having 1 to 10 carbon atoms, linked to the skeleton via an oxygen atom (-O-) (described above).

Alkylthio: 1 to 10 or linked to the skeleton via a sulfur atom (-S-)
Linear or branched alkyl groups having 1 to 4 carbon atoms (as described above).

Alkylamino: A linear or branched alkyl group having 1 to 10 carbon atoms, linked to the backbone via an amino group (-NH-) (described above).

Dialkylamino: two straight-chain or branched alkyl groups each having 1 to 10 carbon atoms, each independent of one another and both linked to the skeleton via a nitrogen atom, as described above. .

Alkylcarbonyl: 1-1 linked to the skeleton via a carbonyl group (—CO—)
A linear or branched alkyl group having 0 carbon atoms (as described above).

Alkoxycarbonyl: 1 linked to the skeleton through a carbonyl group (—CO—)
Alkoxy groups having up to 10 carbon atoms (as described above).

Alkylthiocarbonyl: linked to the backbone through a carbonyl group (—CO—),
Alkylthio groups having 1 to 10 carbon atoms (described above).

Alkylsulfonyl: 1 to 1 linked to the skeleton via a sulfonyl group (—SO ₂ —)
A straight or branched alkyl group having 10 carbon atoms (as described above).

Dialkylaminosulfonyl: A dialkylamino group linked to the skeleton via a sulfonyl group (—SO ₂ —) (described above).

Alkenyl: unsaturated linear or branched hydrocarbon radical having 2 to 4, 6, 8 or 10 carbon atoms and one double bond at any position, for example C ₂ -C _6- As alkenyl, ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl- 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1- Butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl
2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-
Pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2- Methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1- Butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-
Butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl
-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl 2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3 -Butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, and 1-ethyl-2-methyl-2- And propenyl.

Haloalkenyl: an unsaturated linear or branched hydrocarbon group having 2 to 10 carbon atoms and one double bond at any position (as described above), and a hydrogen atom of these groups Is partially or entirely substituted by the halogen atoms, particularly fluorine, chlorine, and bromine.

Alkenyloxy: having from 3 to 10 carbon atoms, linked to the skeleton via an oxygen atom (-O-), and having one double bond at any position not adjacent to a heteroatom;
Unsaturated linear or branched hydrocarbon groups (described above).

Alkenylcarbonyl: 2 linked to the skeleton through a carbonyl group (-CO-)
Unsaturated linear or branched hydrocarbon groups having 1010 carbon atoms and one double bond at any position (described above).

Alkynyl: a linear or branched hydrocarbon group having _{2 to 4, 6} , 8 or 10 carbon atoms and one triple bond at any position, for example C ₂ -C ₆ -alkynyl , 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: an unsaturated linear or branched hydrocarbon group having 2 to 10 carbon atoms and one triple bond at any position (described above), Some or all of which are substituted by the halogen atoms, particularly fluorine, chlorine, and bromine.

Cycloalkyl: a monocyclic saturated hydrocarbon group having _{3 to 6, 8} , 10, or 12 carbon ring atoms, for example, C ₃ -C ₈ -cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cycloheptyl, and cyclooctyl.

Cycloalkoxy: a monocyclic saturated hydrocarbon group having 3 to 12 carbon ring atoms linked to the skeleton via an oxygen atom (-O-) (described above).

Cycloalkylamino: 3 to 12 linked to the backbone via an amino group (—NH—)
A monocyclic saturated hydrocarbon group having three carbon ring atoms (described above).

Heterocycle: including 1 to 3 nitrogen atoms and / or 1 oxygen or sulfur atom, or 1 or 2 oxygen and / or sulfur atoms in addition to carbon ring atoms; Or 6-membered heterocycles, such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolyl Dinyl, 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-oxadiazolidine-3-yl, 1,2,4-oxadiazolidine-5-
Yl, 1,2,4-thiadiazolidine-3-yl, 1,2,4-thiadiazolidine-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-dihydrothien-2-yl, 2,3-dihydrothien- 3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrolin-2-yl, 2-pyrolin-3-yl, 3-pyrolin-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-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2
-Isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-
Yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazoline
-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-dihydropyra Sol-3-yl, 3,4
-Dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydro Pyrazol-4-yl, 4
, 5-Dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3 -Dihydrooxasol
-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-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexahydro-triazine-2- Il, and 1,2,
4-hexahydrotriazin-3-yl.

Aryl: includes mononuclear to trinuclear aromatic ring systems containing 6 to 14 carbon ring atoms, such as phenyl, naphthyl, and anthracenyl.

Aryloxy: a mononuclear aromatic ring system to a trinuclear aromatic ring system linked to the skeleton via an oxygen atom (—O—) (described above).

Arylthio: mononuclear aromatic ring system linked to the skeleton through a sulfur atom (—S—)
Trinuclear aromatic ring system (described above).

Arylamino: Mononuclear to trinuclear aromatic ring systems (described above) linked to the skeleton via an amino group (—NH—).

Arylcarbonyl: a mononuclear aromatic ring system to a trinuclear aromatic ring system linked to the skeleton via a carbonyl group (—CO—) (described above).

Aryloxycarbonyl: a mononuclear aryloxy group to a trinuclear aryloxy group linked to the skeleton via a carbonyl group (—CO—) (described above).

Arylthiocarbonyl: linked to the backbone via a carbonyl group (-CO-),
Mononuclear arylthio group to trinuclear arylthio group (described above).

Arylaminocarbonyl: a mononuclear arylamino group to a trinuclear arylamino group linked to the skeleton via a carbonyl group (—CO—) (described above).

Arylcarbonyloxy: a mononuclear aromatic ring system to a trinuclear aromatic ring system linked to the skeleton through a carbonyloxy group (—CO ₂ —) (described above).

Arylcarbonylthio: a mononuclear aromatic ring system to a trinuclear aromatic ring system linked to the skeleton via a carbonylthio group (—COS—) (described above).

Arylcarbonylamino: a mononuclear aromatic ring system to a trinuclear aromatic ring system linked to the skeleton through a carbonylamino group (—CONH—) (described above).

Arylsulfonyl: Mononuclear to trinuclear aromatic ring systems (described above) linked to the skeleton via a sulfonyl group (—SO ₂ —).

Aryloxysulfonyl: a mononuclear aryloxy group to a trinuclear aryloxy group (described above) linked to the skeleton through a sulfonyl group (—SO ₂ —).

Arylthiosulfonyl: a mononuclear arylthio group to a trinuclear arylthio group (described above) linked to the skeleton via a sulfonyl group (—SO ₂ —).

Arylaminosulfonyl: a mononuclear arylamino group to a trinuclear arylamino group (described above) linked to the skeleton via a sulfonyl group (—SO ₂ —).

Hetaryl: 5-membered hetaryl containing 1-4 nitrogen atoms, or 1-3 nitrogen atoms and one sulfur or oxygen atom: 1-4 nitrogen atoms in addition to carbon atoms A hetaryl group having 5 ring atoms, including atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom as ring atoms, 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 ,Four-
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-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, and 1,3,4-triazole -2-fused hetaryl containing 1 to 3 nitrogen atoms, or 1 nitrogen atom and 1 oxygen or sulfur atom: in addition to carbon atoms, 1 to 4 A hetaryl group having 5 ring atoms, including 1 nitrogen atom or 1 to 3 nitrogen atoms and 1 sulfur atom or oxygen atom as ring atoms, wherein two adjacent carbon ring atoms are Bridged by buta-1,3-diene-1,4-diyl groups; 5-membered hetaryl linked via nitrogen and containing 1 to 4 nitrogen atoms, or nitrogen A benzo-fused 5-membered hetaryl ring containing 1 to 3 nitrogen atoms and containing, in addition to carbon atoms, 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring atoms; A hetaryl group having two ring atoms, wherein two adjacent carbon ring atoms or one nitrogen and one adjacent carbon ring atom are buta-1,3-diene-1,4-diyl 6-membered hetaryl containing 1-3 or 1-4 nitrogen atoms, other than carbon atoms, bridged by a group, the rings of which are connected to the skeleton via one of the nitrogen ring atoms To
A hetaryl group having 6 ring atoms, including 1-3 or 1-4 nitrogen atoms as ring atoms, for example, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, Examples include 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl.

Organic radical: an alkyl, alkenyl, alkynyl, cycloalkyl, heterocycle, aryl, or hetaryl, which may be substituted or unsubstituted.

With respect to the alkyl, alkenyl, and alkynyl groups, the term “optionally substituted or unsubstituted” means that these groups may be partially or fully halogenated (ie, these groups Part or all of the hydrogen atoms may be substituted by the same or plural kinds of the halogen atoms, preferably fluorine, chlorine, or bromine), and / or 1 to 3 (preferably Means 1) may be retained:-cyano, nitro, hydroxyl, amino, formyl, carboxyl, aminocarbonyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,
Alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino, alkylcarbonyl-N-alkylamino, and alkoxycarbonyl-N-alkylamino. The radicals of these radicals preferably contain from 1 to 6, in particular from 1 to 4, carbon atoms; cycloalkyl, cycloalkoxy, cycloalkyl, which may or may not be substituted by customary radicals Alkylthio, cycloalkylamino, cycloalkyl-N-
Alkylamino, heterocycle, heterocycleoxy, heterocyclethio, heterocycleamino,
Or a heterocycle-N-alkylamino, wherein the ring system comprises 3 to 12 ring atoms, preferably 2 to 8 ring atoms, especially 3 to 6 ring atoms, and the alkyl of these radicals Those in which the group preferably contains from 1 to 6 carbon atoms, in particular from 1 to 4 carbon atoms; aryl, aryloxy, arylthio, arylamino, aryl-, which may or may not be substituted by customary groups N-alkylamino, arylalkoxy, arylalkylthio, arylalkylamino, arylalkyl
-N-alkylamino, hetaryl, hetaryloxy, hetarylthio, hetarylamino, hetaryl-N-alkylamino, hetarylalkoxy, hetarylalkylthio, hetarylalkylamino, and hetarylalkyl-N-alkylamino The aryl radicals preferably contain 6 to 10 ring atoms, in particular 6 ring atoms (phenyl), the hetaryl radicals contain in particular 5 or 6 ring atoms, and the alkyl radicals of these radicals are preferred. Is a group containing 1 to 6 carbon atoms, especially 1 to 4 carbon atoms.

With respect to cyclic groups (saturated, unsaturated, or aromatic), the term “optionally substituted
"May not be present" means that these groups are partially or completely halogenated.
(Ie, all or some of the hydrogen atoms in these groups may be the same or
Represents a plurality of the aforementioned halogen atoms, preferably fluorine, chlorine, or bromine, particularly fluorine.
May be replaced by nitrogen or chlorine), and / or
Radicals:-cyano, nitro, hydroxyl, amino, carboxyl, aminocarbonyl
, Alkyl, haloalkyl, alkenyl, haloalkenyl, alkenyloxy,
Haloalkenyloxy, alkynyl, haloalkynyl, alkynyloxy, halo
Alkynyloxy, alkoxy, haloalkoxy, alkylthio, halogenal
Kirthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxy
Cicarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dial
Killaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamido
, Alkylcarbonyl-N-alkylamino, and alkoxycarbonyl-N-
Alkylamino, wherein the alkyl group of these radicals is preferably 1 to 6,
In particular they contain from 1 to 4 carbon atoms and the alkenyl or
Those in which the quinyl group contains 2 to 8, preferably 2 to 6, especially 2 to 4 carbon atoms, may have 1 to 4 (especially 1 to 3), and / or Radicals of the formula: cycloalkyl, cycloalkyl, cycloalkyl, which may or may not be substituted by customary groups
Alkoxy, cycloalkylthio, cycloalkylamino, cycloalkyl-N-
Alkylamino, heterocycle, heterocycleoxy, heterocyclethio, heterocycleamino,
Or heterocycle-N-alkylamino, wherein the ring system has 3 to 12 ring atoms,
It preferably contains 2 to 8 ring atoms, in particular 3 to 6 ring atoms,
Those in which the kill group preferably contains 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms, aryl, aryloxy, which may or may not be substituted by customary groups
Si, arylthio, arylamino, aryl-N-alkylamino, aryla
Lucoxy, arylalkylthio, arylalkylamino, arylalkyl
-N-alkylamino, hetaryl, hetaryloxy, hetarylthio, hetari
Amino, hetaryl-N-alkylamino, hetarylalkoxy, hetary
Alkylthio, hetarylalkylamino, and hetarylalkyl-N-A
Alkylamino, wherein the aryl radical is preferably 6 to 10 ring atoms, in particular
It contains 6 ring atoms (phenyl), and the hetaryl radical is in particular 5 or 6
Ring atoms and the alkyl groups of these radicals are preferably 1-6 carbon atoms
1 to 3 (especially 1) atoms, especially those containing 1 to 4 carbon atoms, and / or the following radicals:-formyl;ⁱⁱⁱ= NOR^iv [Where RⁱⁱⁱIs hydrogen, alkyl, cycloalkyl, and ant
And R^ivIs alkyl, alkenyl, haloalkenyl, alkynyl, and
(The alkyl group is preferably 1 to 6 carbon atoms, especially
Having from 1 to 4 carbon atoms, wherein said cycloalkyl, alkenyl, and alky!
Quinyl groups preferably contain 3 to 8, especially 3 to 6, carbon atoms), further aryl
Is especially phenyl, which may or may not be substituted by conventional groups.
Or −NR^v-CO-D-R^vi [Where R^vIs hydrogen, hydroxyl, C₁-C₆-Alkyl, C_Two-C₆-A
Lucenyl, C_Two-C₆-Alkynyl, C₁-C₆-Alkoxy, C_Two-C₆-Alkenyloxy, C_Two -C₆-Alkynyloxy, C₁-C₆-Alkoxy-C₁-C₆-Alkyl, C₁-C₆-Alkoxy-
C₁-C₆-Alkoxy, and C₁-C₆-Alkoxycarbonyl, R^viIs hydrogen, C₁-
C₆-Alkyl, C_Two-C₆-Alkenyl, C_Two-C₆-Alkynyl, C_Three-C₆-Cycloalkyl, C _Three -C₆-Cycloalkenyl, aryl, aryl-C₁-C₆-Alkyl, hetaryl, and
And hetaryl-C₁-C₆-Alkyl, D is a direct bond of oxygen or nitrogen,
Nitrogen is R^viOne or two (especially one) may be retained, provided that two adjacent carbon atoms of the ring system are C_Three-C_Five-Alkylene, C_Three-C_Five-Arche
Nylene, oxy-C_Two-C_Four-Alkylene, oxy-C₁-C_Three-Alkyleneoxy, oxy-C _Two -C_Four-Alkenylene, oxy-C_Two-C_Four-Alkenyleneoxy or butadienedi
These crosslinks are partially or completely halogenated
And / or the following radical: -C₁-C_Four-Alkyl, C₁-C_Four-Haloalkyl, C₁-C_Four-Alkoxy, C₁-C_Four-Halo Alco
Xy, and C₁-C_Four-Means that one to three, especially one or two, alkylthio may be retained.

The customary radicals are in particular the following substituents: halogen, cyano, nitro, C₁-C_Four-A
Lucil, C₁-C_Four-Haloalkyl, C₁-C_Four-Alkoxy, C₁-C_Four-Haloalkoxy, C₁-C _Four -Alkylamino, di-C₁-C_Four-Alkylamino and C₁-C_Four-Alkylthio.

Unsubstituted or substituted phenyl groups are in particular halogen-, cyano-, nitro-, hydroxy-, amino-, carboxy-, aminocarbonyl-, C ₁ -C ₄ -alkyl-, Or halo-C ₁ -C ₄ -alkyl-substituted phenyl rings are understood to mean phenyl rings.

[0072] Formula regard to the intended use of the 5-hydroxy pyrazoline I, meaning enumerating substituents below in combination or their own in each case are particularly preferred: compounds IA are particularly preferred addition, A 'is SO ₂ wherein the compound is particularly preferred the same as IB is a compound of formula IB a 'is a C = S is also particularly preferable Moreover, R ¹ is C ₁ -C ₄ - haloalkyl, compound I is particularly preferred as well In particular, compound I in which R ¹ is C ₃ F ₇ or C ₂ F ₅ is particularly preferred.In addition, compound I in which R ¹ is a substituted or unsubstituted phenyl group is particularly preferred. Compound I, which is a phenyl group having a substituent at the 2-position, is particularly preferred.Compound I, wherein B is a phenyl group having a substituent at the 4-position, is particularly preferred. Having a group Particularly preferred other compounds I are Eniru group, B is hetaryl (hetaryl) Compound I is a group are particularly preferred addition, R ² and R ^3, compound I is particularly preferred further each hydrogen, R ⁴ Is particularly preferably compound I which is hydrogen or a methyl group.Similarly, compound I in which R ⁴ is a trifluoromethyl group is particularly preferred.In addition, compound I in which substituents R ¹ and R ⁴ are different Particularly preferred.

The compounds I summarized in the table below are particularly preferred for their use. Furthermore, the groups mentioned as substituents in the table are, themselves and in the individual combinations mentioned, particularly preferred embodiments of the substituent in question.

Table 1 R ¹ is C ₂ F ₅ , R ⁴ is methyl and B is a compound of formula IA ′ corresponding to the column in Table A for each compound.

[0075]

Embedded image Table 2 R ¹ is C ₂ F ₅ , R ⁴ is ethyl and B is the compound of formula IA ′ corresponding to the column in Table A for each compound.

Table 3 R ¹ is C ₃ F ₇ , R ⁴ is methyl and B is a compound of formula IA ′ corresponding to the column in Table A for each compound.

Table 4 R ¹ is C ₃ F ₇ , R ⁴ is ethyl and B is a compound of formula IA ′ corresponding to the column in Table A for each compound.

Table 5 R ¹ is C ₂ F ₅ , R ⁴ is methyl and B is a compound of formula IB.1 ′ corresponding to the column in Table A for each compound.

[0079]

Embedded image Table 6 R ¹ is C ₂ F ₅ , R ⁴ is ethyl and B is the compound of formula IB.1 ′ corresponding to the column in Table A for each compound.

Table 7 R ¹ is C ₃ F ₇ , R ⁴ is methyl and B is a compound of formula IB.1 ′ corresponding to the column in Table A for each compound.

Table 8 R ¹ is C ₃ F ₇ , R ⁴ is ethyl and B is a compound of formula IB.1 ′ corresponding to the column in Table A for each compound.

Table 9 R ¹ is C ₂ F ₅ , R ⁴ is methyl and B is a compound of formula IB.2 ′ corresponding to the column in Table A for each compound.

[0083]

Embedded image Table 10 R ¹ is C ₂ F ₅ , R ⁴ is ethyl and B is the compound of formula IB.2 ′ corresponding to the column in Table A for each compound.

Table 11 R ¹ is C ₃ F ₇ , R ⁴ is methyl and B is a compound of formula IB.2 ′ corresponding to the column in Table A for each compound.

Table 12 R ¹ is C ₃ F ₇ , R ⁴ is ethyl and B is a compound of formula IB.2 ′ corresponding to the column in Table A for each compound.

Table A Compound I is suitable for use as a fungicide. Compound I has outstanding activity against a broad spectrum of phytopathogenic fungi, especially those from the classes Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes.
Some of the compounds I act systemically and can be used for protection of cereals as foliar and soil active fungicides.

These include various cereal plants such as wheat, rye, barley, oats, rice, corn, grass, banana, cotton, soybean, coffee, sugarcane, vines,
Of particular importance for controlling a large number of fungi in fruit, ornamental and vegetable species (cucumber, legumes, tomatoes, potatoes and cucumber, etc.) and in the seeds of these plants.

In particular, they are suitable for controlling the following plant diseases: Alternaria species in vegetable and fruit species, strawberry, vegetables, ornamental plants and Botrytis cinerea (gray mold) in vines, rhizome plants Cercospora a in (groundnut)
Eysiphe cichoracearum and Sphaerotheca fulig in rachidicola, cucumber
inea, Erysiphe graminis (ground powdery mildew) in cereals, F in diverse plants
usarium and Verticillium species, Helminthosporium species in cereals, Mycosphaerella species in banana and rhizome plants, Phyt in potatoes and tomatoes
ophythora infestans, Plasmopara viticola in vines, Podosphaera leucotricha in apples, Pseudocercosporella her in wheat and barley
potrichoides, Pseudoperonospora species in hops and cucumbers, Puccinia species in cereals, Pyricularia oryzae in rice, in cotton, rice and turf
Rhizoctonia species, Septoria nodorum in wheat, Uncinula in vines
necator, Ustilago species in cereals and sugarcane, Venturia species in apples and pears (broom disease).

Compound I is used in an amount of active compound effective for killing fungi to treat fungi or plants, seeds, materials or soil to be protected against fungal attack. This application can take place before or after infection of the material, plant or seed with the fungus. The fungicidal composition generally comprises from 0.1 to 95% by weight, preferably 0.5% by weight.
It contains 9090% by weight of active compound.

For use in grain protection, the rate of application may vary depending on the type of effect desired.
It is in the range from 0.01 to 2.0 kg of active compound per ha.

For the treatment of seed, generally 0.001 to 0.1 g, preferably 0.01 to 0.05 g per kg of seed
Of the active compound are required.

For the protection of materials and stored products, the rate of application depends on the desired area of application and the type of effect. Customary application rates are, for example, in the protection of materials, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active compound per m ^{3 of} material to be treated.

Compound I can be used in conventional formulations (eg, solutions, emulsions, suspensions, dusts).
, Powders, pastes and granules). The dosage form employed depends on the particular use intended. In each case, a fine and homogeneous distribution of the compound according to the invention must be ensured.

The preparation can be prepared by a known method. The active compound is prepared by spreading, for example, with a solvent and / or carrier and, if desired, with emulsifiers and dispersants. If water is used as the diluent, other organic solvents may be used as auxiliary solvents. Suitable co-solvents for this purpose are essentially the following: aromatics (such as xylene), chlorinated aromatics (such as chlorobenzene), paraffins (such as mineral oil fractions), alcohols (methanol, butanol) Solvents such as ketones (cyclohexanone), amines (ethanolamine, dimethylformamide, etc.) and water; powdered natural minerals (kaolin, clay, mica, chalk, etc.) and powdered synthetic minerals (finely divided silica, silicate, etc.) ); Nonionic and anionic emulsifiers (such as polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates); and dispersants (such as lignin sulfite waste liquors and methylcellulose).

Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid and dibutylnaphthalenesulfonic acid, alkyl aryl sulfonates, alkyl sulfates,
Alkyl sulfonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, formaldehyde and sulfonated naphthalenes, condensation products of naphthalene derivatives, phenol and formaldehyde with naphthalene or Condensation products with naphthalenesulfonic acid, polyoxyethylene octyl phenol ether, ethoxylated isooctyl phenol, octyl phenol and nonyl phenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohol, isotridecyl alcohol, fatty alcohol ethylene oxide Condensate, ethoxylated castor oil, polyoxyethylene Down alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin sulfite waste liquors and methylcellulose.

Suitable for preparing directly sprayable solutions, emulsions, pastes or oil dispersions are petroleum fractions having a medium to high boiling point, such as kerosene or diesel fuel oils, and also coal tar oils, and Oils, aliphatic, cyclic and aromatic hydrocarbons of vegetable or animal origin, such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methanol, ethanol, propanol, butanol, chloroform, tetrachloride Carbon, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, highly polar solvents such as dimethylformamide, dimethylsulfoxide, N-
Methylpyrrolidone, and water.

Powders, dustable compositions and dusts can be prepared by mixing or joint grinding the active substance with a solid carrier.

Granules, for example coated granules, impregnated granules and homogenized granules, can be prepared by binding the active compounds to solid carriers. Solid carriers include, for example, mineral earths, such as silica gel, silica, silicates, talc, kaolin, and ataclay.
), Limestone, lime, chalk, balls, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, powdered synthetics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and products of plant origin For example, cereal flour, tree bark flour, wood flour, and nut shell flour, cellulose flour and other solid carriers.

The formulations generally comprise between 0.01 and 95% by weight of active compound, preferably between 0.1 and 90%. The active compounds are employed in a purity of from 90 to 100%, preferably 95 to 100% (as determined by NMR spectrum).

Examples of formulations are given below: I. 5 parts by weight of a compound of the invention give 95 parts by weight of a powdery composition II. 30 parts by weight of a compound of the invention and 92 parts by weight of a compound of the invention The mixture of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of the silica gel is thoroughly mixed. This gives an active compound preparation with good adhesive properties (active compound content of 23% by weight) III. 10 parts by weight of a compound of the invention, 90 parts by weight of xylene, 6 parts by weight (1-10 mol of oleic acid N-monoethanolamide, 8-10 mol of ethylene oxide), 2 parts by weight of dodecylbenzenesulfonic acid and 2 parts by weight of an addition product (
Dissolve in a mixture containing 40 mol of ethylene oxide (1 mol of castor oil). (9% by weight of active compound content) IV. 20 parts by weight of a compound of the invention, 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of an addition product (based on 1 mol of isooctylphenol Dissolved in a mixture containing 7 mol of ethylene oxide) and 5 parts by weight of an addition product (40 mol of ethylene oxide per mol of castor oil) (16% by weight of active compound) V. 80 parts by weight of a compound according to the invention And 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of sodium salt of lignosulfonic acid (derived from sulfurous acid waste liquid), and 7 parts by weight of powdered silica gel are sufficiently mixed and powdered in a hammer mill. I do. (
VI. 90 parts by weight of a compound of the invention and 10 parts by weight of N-methyl-α-pyrrolidone are thoroughly mixed. This gives a solution which is suitable for use in very small drop dosage forms (active compound content of 90% by weight). VII.20 parts by weight of a compound of the invention and 40 parts by weight of cyclohexanone, 30 parts by weight Dissolved in a mixture containing parts by weight of isobutanol, 20 parts by weight of an addition product (7 mol of ethylene oxide for 1 mol of isooctylphenol) and 10 parts by weight of an addition product (40 mol of ethylene oxide for 1 mol of castor oil) Let it. 100,000 of this solution
Pour into fine parts by weight of water and disperse finely to obtain an aqueous dispersion containing 0.02% by weight of active compound. VIII. 20 parts by weight of the compound of the invention and 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid, 17 Part by weight of the sodium salt of lignosulfonic acid (from the sulfite waste liquor) and 60 parts by weight of powdered silica gel are thoroughly mixed and powdered in a hammer mill.
This mixture is finely dispersed in 20,000 parts by weight of water to give a spray liquid containing 0.1% by weight of active compound.

The active compounds can be applied in the form of their formulations or application forms prepared therefrom, for example, directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, Dust, dusting composition or granules, spray,
It can be applied by atomization, dusting, spraying and watering. The application form depends entirely on the intended use. In each case, they must ensure a fine dispersion of the active compounds according to the invention.

The aqueous dosage forms can be prepared from emulsion concentrates, pastes, or wet powders (spray powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances can be homogenized in such waters or dissolved in oils or solvents by means of wetting agents, tackifiers, dispersants or emulsifiers. However, concentrates containing the active compound, wetting agents, tackifiers, dispersing or emulsifying agents, and optionally solvents or oils suitable for dilution with water, may also be prepared.

The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. Generally, it is 0.0001-10%, preferably 0.01-1%.

The active compounds can be used successfully by the micro-volume method (ULV), and formulations with more than 95% by weight of active compound or even active compounds without additives can be applied.

The various types of oils, herbicides, fungicides which can be added to the active compounds, other insecticides and bactericides, if desired, even immediately before application (tank mix). These agents can be added to the composition of the present invention in a weight ratio of 1:10 to 10: 1.

The compositions of the present invention in a fungicidally utilized form may comprise other active compounds, for example,
It may be present in combination with herbicides, insecticides, growth regulators, fungicides or fertilizers. In many cases, compositions combined with other fungicides in the form of mixtures of Compound I, or fungicides containing them, will result in a broader spectrum of fungicidal activity.

The following list of fungicides illustrates, without any limitation, the possible combinations that could be used in combination with the compounds of the present invention.

Sulfur, dithiocarbamate and derivatives thereof, for example, iron (III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, zinc manganese ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide , (N, N-
Ammonia complex of ethylenebisdithiocarbamate) zinc, ammonia complex of (N, N'-propylenebisdithiocarbamate) zinc, (N, N'-propylenebisdithiocarbamate) zinc, N, N'-polypropylenebis (thiocarbamoyl) Disulfide; nitro derivative, for example, dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6- Dinitrophenyl isopropyl carbonate, diisopropyl 5-nitroisophthalate.

Heterocycles, for example 2-heptadecyl-2-imidazoline acetate, 2,4-
Dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethylphthalimidophosphonothioate, 5-amino-1- [bis (dimethylamino) phosphinyl] -3-phenyl
-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-
Dithiolo [4,5-b] quinoxaline, methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate, 2-methoxycarbonylaminobenzimidazole, 2- (furyl- (2)) benzimidazole, 2- (thiazolyl- ( 4)) Benzimidazole, N- (1,
(1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide.

N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenylsulfuric diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole , 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-dihydro-5-carboxanilide-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilide-6-methyl-1, 4-oxathiin-4,4-dioxide, 2-methyl-5,6-dihydro-4H-
Pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide,
N-cyclohexyl-2,5-dimethylfuran-3-carboxamide, N-cyclohexyl-N
-Methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2
-Iodobenzanilide, N-formyl-N-morpholine 2,2,2-trichloroethylacetal, piperazine-1,4-diyl-bis-1- (2,2,2-trichloroethyl) formamide, 1- (3 , 4-Dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2,
6-dimethyl-N-tridecylmorpholine or a salt thereof, 2,6-dimethyl-N-cyclododecylmorpholine or a salt thereof, N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis- 2,6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methyl-propyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3- 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-trichlorophenoxyethyl) -N'- Imidazolyl urea, 1- (
4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, 1- (4-chlorophenoxy) -3,3-dimethyl-1 -(1H-1,2,4-triazol-1-yl) -2-butanol, (2RS, 3RS) -1
-[3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H-1,2,4-triazole, α- (2-chlorophenyl) -α- (4 -Chlorophenyl)
-5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl) -3-pyridinemethanol, 1,2-bis (3-ethoxycarbonyl-2-thioureido ) Benzene, 1,2-bis- (3-methoxycarbonyl-2
-Thioureido) benzene.

• Strobilurin, for example methyl E-methoxyimino- [α- (o-tolyloxy) -o-tolyl] acetate, methyl E-2- {2- [6- (2-cyanophenoxy)- Pyrimidin-4-yloxy] -phenyl} -3-methoxyacrylate, methyl E-methoxyimino- [α- (2-phenoxyphenyl)] acetamide, methyl-E-methoxyimino-
[α- (2,5-dimethoxyphenoxy) -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-Methyl-6-cyclopropylpyrimidin-2-yl) aniline.

A phenylpyrrole, for example 4- (2,2-difluoro-1,3-benzodioxole-4-
Ill) pyrrole-3-carbonitrile.

• Cinnamamide, such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl
) Acryloylmorpholine.

• and a variety of other fungicides, such as dodecylguanidine acetate, 3-
[3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, methyl N- (2,6-dimethylphenyl) -N- (2-furoyl
) -DL-alaninate, DL-N- (2,6-dimethylphenyl) -N- (2′-methoxyacetyl)-
Alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-
Aminobutyrolactone.

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-methoxymethyl-1 , 3-Oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-di Carboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoxyimino] -acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2 ,Four-
Difluoro-α- (1H-1,2,4-triazoyl-1-methyl) benzhydryl alcohol,
N- (3-chloro-2,6-dinitro-4-trifluoromethylphenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1-((bis- (4-fluorophenyl) -methylsilyl ) Methyl) -1H-1,2,4-triazole.

Synthetic Examples Further modifications of the starting materials gave further compounds I using the methods described in the synthetic examples below. The compounds obtained by this method are listed in the following table, together with their physical data.

A) Preparation of Precursor Example 1 Preparation of 2-methylpyridine-3-carbohydrazide

Embedded image To a solution of 1 g of methyl 2-methylpyridine-3-carboxylate in 5 ml of methanol was added 3 g of hydrazine hydrate and mixed, followed by stirring at 20-25 ° C. for 14 hours. The mixture was diluted with water and extracted with methylene chloride. The solvent was distilled off from the combined organic phases to give 0.45 g of the title compound as colorless crystals with a melting point of 60 ° C.

Example 2 Preparation of 4-chlorophenylsulfohydrazide

Embedded image At 10-20 ° C., 24 g (0.48 mol) of hydrazine hydrate dissolved in 25 ml of water are treated with 300 m
A solution of 50 g (0.24 mol) of 4-chlorophenylsulfonyl chloride in 1 of THF was added dropwise. The reaction mixture was mixed at about 15 ° C. for 15 minutes and subsequently poured on ice. The solution was concentrated and the precipitate was collected by filtration. 40 g of the title compound were isolated as colorless crystals, mp 79 ° C.

Example 3 Preparation of 5,5,6,6,7,7,7-heptafluoro-2,4-heptanedione

Embedded image At 30 ° C., 4.1 g (170 mmol) of sodium hydride (97%) in 45 ml of anhydrous cyclohexane were mixed with a solution of 68.4 g (300 mmol) of methyl perfluorobutyrate and 8.7 g (150 mmol) of anhydrous acetone. The mixture was stirred at 20-25 ° C. for 14 hours, diluted with distilled water and acidified with dilute hydrochloric acid. The phases were separated and the aqueous phase was extracted with diethyl ether. The organic phases were combined, washed with water and fractionated through a 40 cm Vigreux column. This gives 2
2 g of the title compound were obtained as colorless crystals, mp 135 ° C. ¹ H NMR (CDCl ₃ ): δ (p
pm) = 2.1 (s, 3H); 5.95 (s, 1H).

Example 4 Preparation of 5,5,6,6,6-pentafluoro-2,4-hexanedione Using the conditions described in Example 3, 2.7 g of sodium hydride and 27 ml of cyclohexane were prepared . Reaction with 5.8 g (100 mmol) of acetone and 38.4 g (200 mmol) of ethyl perfluoropropionate gave 19.4 g of the title compound as a colorless liquid, mp 119 ° C.

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

B) Preparation of Active Compound Example 4 of 5-Hydroxy-5-trifluoromethyl-3-methyl-4,5-dihydropyrazol-1-yl- (4-hydroxyphenyl) methanone [I-73] Preparation

Embedded image 5 g (33 mmol) of 4-hydroxybenzhydrazide and 5 g (100 g
(33 mmol) of trifluoroacetylacetone was heated at 70 ° C. for 6 hours. The solvent was distilled off to obtain 9.0 g of the title compound as colorless crystals.

[0124] Example 5 5-hydroxy-5- (1,1,1,2,2, - pentafluoroethyl) -3-methyl-4,5 Jihidoropi Razoru-1-yl - (4-bromophenyl) Preparation of Methanone [I-13] Using the conditions described in Example 4, 1 g (5 mmol) of 4-bromobenzhydrazide and 1 g (
Reaction of 5 mmol) of 5,5,6,6,6-pentafluoro-2,4-hexanedione in 100 ml of ethanol gave 1.9 g of the title compound as colorless crystals.

Example 6 5-hydroxy-5- (1,1,1,2,2,3,3-heptafluoropropyl) -3-methyl-4,5-dihydroxy
Preparation of Dropyrazol -1-yl-phenylmethanone [I-35] Using the conditions described in Example 4, 0.8 g (6 mmol) of benzhydrazide and 1.5 g (6 mmo)
Reaction of l) with 5,5,6,6,7,7,7-pentafluoro-2,4-heptanedione in 100 ml of ethanol gave 9.0 g of the title compound as colorless crystals. .

Example 7 2-benzenesulfonyl-3-trifluoromethyl-5-methyl-3,4-dihydro-2H-pyra
Preparation of Zol-3-ol [II-1]

Embedded image A solution of 1 g (6 mmol) of benzenesulfohydrazide and 0.9 g (6 mmol) of trifluoroacetylacetone in ethanol was heated at 70 ° C. for 6 hours. Evaporate the solvent,
1.6 g of the title compound were obtained as colorless crystals.

Table 1

[Table 1] Table 2

[Table 2] Examples of activity against harmful fungi The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments: The active compound was converted to 70% by weight of cyclohexanone, 20% by weight of Nekanil® L
N (Lutenosol® AP6, a wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Wettol® EM (nonionic emulsifier based on ethoxylated castor oil) Were separately or simultaneously formulated as 10% emulsions and diluted with water to the desired concentration.

Use Example 1 Against Phytophthora infestans in Tomatoes A stock solution of 10% of active compound, 63% of cyclohexanone and 27% of emulsifier on leaves of cultivated variety "Grosse Fleischtomate" grown in an active pot The aqueous suspension prepared using was sprayed and dried. The next day, the leaves were infected with an aqueous suspension of zoospores of Phytophthora infestans. The plants were subsequently placed in a steam saturated chamber at 16-18 ° C. Six days later, in control plants infected without treatment, tomato blight developed to such an extent that the percentage (%) of disease could be evaluated visually.

In this test, 250 ppm of active compounds I-1 to I-4, I-6, I-7, I-9 to I-11, I-1
3-I-16, I-26 to I-35, I-53, I-59, I-60, I-63, I-68, I-72, I-74, I-94, I-9
5, Plants treated with I-97, I-112, I-113, I-117, I-124, I-127, I-134, I-164 and II-13 show up to 20% infection However, on the other hand, 100 untreated plants
% Infected.

Use Example 2 Active leaves against "Pulsmopara viticola " were grown on leaves of cultivated varieties "Muller-Thurgau" grown in flowerpots using a stock solution of 10% active compound, 63% cyclohexanone and 27% emulsifier. The aqueous suspension was sprayed to dryness. To be able to evaluate the long-term effects of a substance,
After the spray coating had dried, the plants were stored in a greenhouse for 7 days. The leaves were then inoculated with an aqueous suspension of zoospores of Plasmopara viticola. Followed by vines 2
Placed in a steam saturated chamber at 4 ° C for 48 hours, followed by 5 days in a greenhouse at 20-30 ° C. After this, the plants were once again placed in a humid chamber for 16 hours to promote the development of sporangia. The degree of infection on the back of the leaves was measured visually.

In this test, 250 ppm of active compounds I-3, I-4, I-10, I-11, I-27, I-34,
I-35, I-46, I-47, I-53, I-54, I-73, I-97, I-112, I-113, I-114, I-116, I-
Plants treated with 117, I-124 and I-127 showed less than 30% infection, while untreated plants were 90% infected.

Use Example 3 Active cultivation of Botrytis cinerea on Acanthus leaves Leaves of a pepper variety of "Neusiedler Ideal Elite" with 4 to 5 fully grown leaves, 10% of active compound, 63% Aqueous suspension made using a stock solution of cyclohexanone and 27% emulsifier was spray dried. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 × 10 ⁶ spores / ml in a 2% strength aqueous solution of Biomalz. Test plants were placed in an environmental control cabinet at 22-24 ° C. with high atmospheric humidity. Five days later, the degree of fungal disease in the leaves was visually determined in%.

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

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Sauter Hubert, Germany Dee-68305 Mannheim, Corvanger 21 (72) Inventor Buyer, Herbert Dee-68159 Mannheim, Dee 3.4 (72) Inventor Kalman, Oliver Dee-68199 Mannheim Heinrich-Heine-Strasse 27 (72) Inventor Gever, Marx D-56288 Kastellern, Goethestrasse 21 (72) Inventor Gra Nos, Vasilios D-67063 Ludwigshafen, Borsigstrasse 5 (72) Inventor Müller, Bernd D-67227 Frankenthal, Jean-Gans-Strasse 21 (72) Inventor Putok, Arne Germany D-67065 Ludwigshafen, Bergstrasse 13th (72) Inventor Tormo i Brasco, Jordi Germany D-67117 Lin Burgerhof, Mühlweg 47 (72) Inventors Ammerman, Eberhard Germany D-64646 Heppenheim, von-Gagern-Strasse 2 (72) Inventor Grote, Thomas Germany D-67105 Schifferstadt, Breslauer Strasse 6 (72) Inventors Lorenz, Gizela Germany D-67434 Neustadt, Ahrenweg 13 (72) Inventors Strassmann, Siegfried D-67117 Lin Burgerhof, Donnersbergstrasse 9 F-term (reference) 4H011 AA01 AA03 BA01 BB09 BC05 BC19 DA15 DA16 DD03 DH03

Claims (10)

[Claims] 1. Formula I: ## STR1 ## Wherein, B is aryl which may or may not be substituted, or an optionally hetaryl may not be substituted, A is, C = O, a C = S or SO _2,, R ¹ is C ₂ -C ₁₀ -alkyl, C ₁ -C ₁₀ -haloalkyl, C ₃ -C ₁₀ -alkenyl, C ₃ -C _10-
Haloalkenyl, C ₃ -C ₁₀ - alkynyl, or C ₃ -C ₁₀ - or a haloalkynyl, may or may not be substituted C ₃ -C ₁₀ - cycloalkyl, or may not be substituted Good C ₃ -C ₁₀ -cycloalkenyl, optionally substituted C _3-
A C ₁₀ -cycloalkynyl or an optionally substituted aryl, an optionally substituted heterocycle or an optionally substituted hetaryl, R ² Is hydrogen, R ³ is hydrogen, nitro, cyano, N (R ′) ₂ , C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C _1- C ₄ -haloalkoxy, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -haloalkenyl, C ₂ -C ₄ -alkynyl, or C ₂ -C ₄ -haloalkynyl (R ′ is independently of each other Hydrogen or C ₁ -C ₄ -alkyl), or R ² and R ³ are both = O, SS, or NNOR ⁵ (R ⁵ is hydrogen, C _1-
C ₄ - alkyl, C ₁ -C ₄ - haloalkyl, C ₃ -C ₆ - alkenyl, C ₃ -C ₆ - haloalkenyl, C ₃ -C ₆ - alkynyl, or C ₃ -C ₆ - a haloalkynyl) Wherein R ⁴ is hydrogen, halogen, nitro, cyano, N (R ′) ₂ , C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, COOR ′, hetaryl, or heterocycle. Use of 5-hydroxypyrazolin represented by (1) for inhibiting harmful fungi. 2. A compound of formula IA:[Where, in case a: R^ThreeIs nitro, cyano, N (R ')_Two, C₁-C_Four-Alkyl, C₁-C_Four-Haloalkyl, C₁-C _Four -Alkoxy, C₁-C_Four-Haloalkoxy, C_Two-C_Four-Alkenyl, C_Two-C_Four-Haloalkenyl
, C_Two-C_Four-Alkynyl or C_Two-C_Four-Haloalkynyl, or R^TwoAnd R^ThreeAre both = O group, = S group, or = N-O-R^FiveGroup, R^FourIs hydrogen, halogen, nitro, cyano, N (R ')_Two, C₁-C_Four-Alkyl, C₁-C_Four-C
B, R¹, And R^TwoAre each as defined in claim 1, or in case b: B is naphthyl, optionally substituted or unsubstituted,
Heteroaryl, hetaryl which may be substituted or unsubstituted, or substituted
Nil and R^ThreeIs hydrogen and R^FourIs hydrogen, halogen, nitro, cyano, N (R ')_Two, C₁-C_Four-Alkyl, C₁-C_Four-C
A loalkyl or heterocycle, R¹R is methyl, t-butyl, or phenyl^FourIs not methyl,
B group is 3-bromo, 4-halo, 4-methyl, 4-methoxy, 4-nitro, 4-dimethyla
Phenyl substituted by mino or 4-fluoro-3-methyl,
, B group and R¹R if both groups are 4-fluorophenyl^FourIs not ethyl
Or in case c: B is unsubstituted phenyl and R¹Is aryl which may be substituted or unsubstituted,
Heteroaryl, or hetaryl, which may or may not be substituted
, C, which may or may not be substituted_Three-C_Ten-Cycloalkyl, even if substituted
C that doesn't have to be_Three-C_Ten-Cycloalkenyl, optionally substituted C_Three-
C_Ten-Cycloalkynyl, or n-phenyl which may or may not be substituted
Ropyl, optionally substituted C_Four-C_Ten-Cycloalkyl, CHCl_Two, CH_TwoC
l, CCl_Three, CHF_Two, CF_TwoH, CF_TwoCl, CFCl_Two, C_Two-C_Ten-Haloalkyl, even when substituted
C that doesn't have to be_Three-C_Ten-Alkenyl, C_Three-C_Ten-Haloalkenyl, even if substituted
C that doesn't have to be_Three-C_Ten-Alkynyl or C_Three-C_Ten-Haloalkynyl, R^TwoIs hydrogen and R^ThreeIs hydrogen, nitro, cyano, amino, methylamino, dimethylamino, C₁-C _Four -Alkyl, C₁-C_Four-Haloalkyl, C₁-C_Four-Alkoxy, C₁-C_Four-Haloalkoxy,
C_Two-C_Four-Alkenyl, C_Two-C_Four-Haloalkenyl, C_Two-C_Four-Alkynyl or C_Two-C_Four-
Is haloalkynyl, or R^TwoAnd R^ThreeAre both = O group, = S group, or = N-O-R^FiveGroup, R^FourIs hydrogen, halogen, nitro, cyano, N (R ')_Two, C₁-C_Four-Alkyl, C₁-C_Four-C
A loalkyl or heterocycle, R^FourIs CF_TwoR if H¹Is not t-butyl and R¹When is phenyl
R^FourIs not methyl.] The 5-hydroxypyrazoline according to claim 1, wherein (3) Formula IB: Wherein A ′ is C = S or SO _2. 5. The 5-hydroxypyrazoline according to claim 1, wherein 4. A process for the preparation of a compound of the formula IA according to claim 2, wherein the compound has the formula II: [Wherein B is as defined in claim 2] and a hydrazine represented by the formula III: Wherein the substituents are each as defined in claim 2. 5. A process for the preparation of a compound of formula IB wherein A ′ according to claim 3 is C = S, wherein the compound of formula I wherein A is C = O according to claim 1 and Lawesson The above method, comprising the step of reacting with a reagent. 6. A process for preparing a compound of formula IB according to claim 3, wherein A ′ is SO ₂ , wherein the compound of formula IV is Wherein B is as defined in claim 1; and a sulfohydrazine of the formula III: Wherein the substituents are each as defined in claim 1. 7. As an intermediate for the preparation of a compound of the formula I wherein A according to claim 1 is C = O, and a compound of the formula IB wherein A ′ according to claim 3 wherein C = S Use of. 8. A composition suitable for controlling harmful fungi, comprising a compound of formula I according to claim 1 and a solid or liquid carrier. 9. Use of a compound I according to claim 1 for preparing a composition suitable for controlling harmful fungi. 10. Protecting against fungal attack by treating fungi or materials, plants, soil or seeds with an effective amount of a compound of formula I according to claim 1. A method for controlling harmful fungi, comprising: