EP2046780A1

EP2046780A1 - Azolylmethyloxiranes, use thereof for controlling plant pathogenic fungi, and agents containing the same

Info

Publication number: EP2046780A1
Application number: EP07787668A
Authority: EP
Inventors: Jochen Dietz; Thomas Grote; Bernd Müller; Jan Klaas Lohmann; Jens Renner; Sarah Ulmschneider; Alice GLÄTTLI
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-07-24
Filing date: 2007-07-18
Publication date: 2009-04-15
Also published as: CN101495473A; CL2007002151A1; PE20080949A1; UY30502A1; JP2009544655A; BRPI0714365A2; TW200817381A; US8236788B2; US20090270256A1; AR062027A1; WO2008012246A1; JP5148610B2

Abstract

The invention relates to azolylmethyloxiranes of general formula (I) wherein A or B is phenyl which is substituted with a CN and optionally by between one and three of the following substituents, halogen, NO2, amino, C1-C4alkyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4alkylamino, C1-C4 dialkylamino, thio or C1-C4 alkylthio, and the respective other substituent A or B is phenyl or a 5-membered or 6-membered heteroaryl, said substituents being optionally substituted by between one and three of the following substituents, halogen, CN, NO2, amino, C1-C4alkyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4 alkylamino, C1-C4 dialkylamino, thio or C1-C4 alkylthio. The invention also relates to the plant-tolerant acid addition salts or metal salts of said compounds, to the use of compounds of formula (I) for controlling plant pathogenic fungi, and to agents containing the same.

Description

Azolylmethyloxirane, their use for controlling phytopathogenic fungi and agents containing them

description

The present invention relates to Azolylmethyloxirane of the general formula I.

wherein

A or B is phenyl which with a CN and optionally substituted by one to three of the following substituents: halogen, NO2, amino, Ci-C ₄ -alkyl, -C ₄ -alkoxy, Ci-C ₄ - haloalkyl, _Ci-C4- haloalkoxy, Ci-C ₄ alkylamino, Ci-C ₄ dialkylamino, thio, or Ci -C ₄ -alkyl alkylthio, substituted,

and the other substituent

A or B is phenyl or 5-membered or 6-membered heteroaryl, where these substituents are optionally substituted by one to three of the following substituents: halogen, CN, NO ₂ , amino, C 1 -C ₄ -alkyl, C 1 -C ₄ - Alkoxy, C 1 -C ₄ -haloalkyl, C 1 -C ₄ -

Haloalkoxy, Ci-C ₄ alkylamino, Ci-C ₄ dialkylamino, thio, or -C ₄ - substituted alkylthio,

as well as their plant tolerated acid addition or metal salts.

Furthermore, the invention relates to the use of the compounds of formula I for the control of phytopathogenic fungi and agents containing them.

Azolylmethyloxirane, their preparation and their use in crop protection are known for example from EP-A 0 094 564 and EP-A 0 196 038.

From EP-A 0 421 125 azolylmethyloxiranes are known which carry a hetaryl substituent on the oxirane ring.

Although the described Azolylmethyloxirane already have a good to very good fungicidal activity against a number of pathogens, the present invention an object of the invention to provide new Azolylmethyloxirane with an improved fungicidal effect available. This object has been achieved with the compounds of formula I described above.

The compound I is able to form salts or adducts with inorganic or organic acids or with metal ions because of the basic character of the nitrogen atoms contained in them.

Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, carbonic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms ), Arylsulfonic acids or disulfonic acids (aromatic radicals such as phenyl and naphthyl bearing one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or diphosphonic acids (aromatic radicals such as phenyl and Naphthyl which one or two

Carry phosphoric acid residues), wherein the alkyl or aryl radicals may carry further substituents, e.g. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

The metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main groups, in particular aluminum, tin and lead, and the first to eighth transition groups, in particular chromium, manganese, iron, cobalt, nickel, copper, Zinc and others into consideration. Particularly preferred are the metal ions of the elements of the subgroups of the fourth period. The metals can be present in the various valences that belong to them.

The preparation of the compounds of the formula I is known and described in detail in EP-A 0 094 564, EP-A 0 196 038 and EP-A 0 421 125.

Here, the corresponding CN-substituted phenyl is prepared from an aryl halide.

The conversion of an aryl halide into the corresponding cyanide is a known reaction (see Chem. Rev. 1994, 94, 1047). As aryl halides, the fluorine,

Chloro, bromine and iodine compounds in question. The reaction can be carried out thermally with cyanides such as Cu (I) CN, in high boiling solvents such as NMP or DMF or DMSO or nitrobenzene. An example of this is, for example, Bioorganic & Medical Cursive Letters, 16 (22), 5763-5766; 2006 or Journal of Medicinal Chemistry, 49 (2), 727-739; Of 2006.

Alternatively, the reaction can also be carried out under metal catalysis. Suitable catalysts are various transition metal complexes in question, such as. As nickel or palladium. The cyanide source can i.a. an alkali metal cyanide such as sodium cyanide and potassium cyanide, or a transition metal cyanide such as nickel cyanide or zinc cyanide. An example of a palladium-catalyzed cyanation can be found in Bioorganic & Medicinal Chemistry Letters, 16 (21), 5488-5492; 2006, Chem. Eur. J. 2003, 9, 1828, or in WO2006021886.

A palladium-free reaction under microwave conditions starting from aryl chlorides and bromides with nickel cyanide is described in J. Org. Chem. 2003, 68, 9122-9125. Suitable solvents are DMF or NMP.

In the definitions of the symbols given in the above formulas, collective terms have been used that are generally representative of the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl and the alkyl moieties of compound groups such as alkylamino: saturated, straight-chain or branched hydrocarbon radicals having preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl and 1 , 1-dimethylethyl.

Haloalkyl: Alkyl as mentioned above, wherein in these groups partially or completely the hydrogen atoms are replaced by halogen atoms as mentioned above. In one embodiment, the alkyl groups are substituted at least once or completely by a particular halogen atom, preferably fluoro, chloro or bromo. In a further embodiment, the alkyl groups are partially or completely halogenated by various halogen atoms; for mixed halogen substitutions, the combination of chlorine and fluorine is preferred. Particular preference is given to (C 1 -C 4) -haloalkyl, more preferably (C 1 -C 2) -haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl; Alkoxy: for an oxygen-bonded alkyl group as defined above, preferably having 1 to 4 carbon atoms. Examples of preferred alkoxy groups are: methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy.

Haloalkoxy: alkoxy, as defined above, wherein in these groups the hydrogen atoms are partially or completely replaced by halogen atoms, as described above under haloalkyl, in particular fluorine, chlorine or bromine. Examples of preferred haloalkoxy radicals are OCH ₂ F, OCHF ₂ , OCF ₃ , OCH ₂ Cl, OCHCl ₂ , OCCl ₃ , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2 , 2-Difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC ₂ F ₅ , 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3, 3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH ₂ -C ₂ F ₅ , OCF ₂ -C ₂ F ₅ , 1- (CH ₂ F) -2-fluoroethoxy, 1- (CH ₂ Cl) -2- chloroethoxy, 1- (CH ₂ Br) -2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.

Alkylthio: Alkyl as defined above attached via an S atom.

5-membered heteroaryl containing one, two, three or four nitrogen atoms or one, two or three nitrogen atoms and / or a sulfur or oxygen atom, which heteroaryl may be attached via C or N, if present: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and / or one sulfur or oxygen atom as ring members, eg Furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (1, 2,3-; 1,2,4-triazolyl), tetrazolyl, oxazolyl, isoxazolyl, 1, 3,4-oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl, in particular 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-oxadiazole-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-triazol-2-yl;

6-membered heteroaryl containing one, two, three or four, preferably one, two or three nitrogen atoms, wherein the heteroaryl can be attached via C or N, if present: 6-membered ring heteroaryl groups which contain, in addition to carbon atoms, one to four or may contain one to three nitrogen atoms as ring members, eg Pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1, 2,3-triazinyl, 1, 2,4-tirazinyl, 1, 3,5-triazinyl, in particular 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-tirazin-3-yl. The novel compounds of formula I contain chiral centers and are generally obtained in the form of racemates or as mixtures of diastereomers of erythro and threo forms. The erythro and threo diastereomers can be separated in the compounds of the invention, for example, due to their different solubility or by column chromatography and isolated in pure form. From such uniform pairs of diastereomers can be obtained by known methods uniform enantiomers. As antimicrobial agents it is possible to use both the uniform diastereomers or enantiomers and also their mixtures obtained in the synthesis. The same applies to the fungicides.

The compounds according to the invention can be present in various crystal modifications which may differ in their biological activity. They are also the subject of the present invention.

In the compounds of the formula I used according to the invention or according to the invention, the following meanings of the substituents, in each case alone or in combination, are particularly preferred. If appropriate, the preferred substituents or preferred combinations of substituents apply correspondingly to the precursors of the compounds according to the invention.

The substituent A or B is phenyl, d- with a CN and possibly additionally from one to three of the following substituents: halogen, NO2, amino, Ci-C ₄ -alkyl, -C ₄ -alkoxy C ₄ haloalkyl, Ci- C ₄ haloalkoxy, Ci-C ₄ alkylamino, Ci-C ₄ -dialkylamino, thio or Ci-C ₄ alkylthio, are substituted.

In one embodiment, the CN substituent is in the 4-position of the phenyl ring.

In another embodiment, the phenyl ring is substituted in the 2,4 position.

According to a further embodiment, A or B is phenyl which, with one CN and one to three further substituents, is selected from one to three of the following substituents: halogen, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, C 1 -C ₄ - Haloalkyl or CrC ₄ - haloalkoxy substituted.

In another embodiment, the substituent A or B is phenyl which is substituted with one CN and one to three further substituents selected from halogen, C 1 -C ₄ -alkyl or C 1 -C ₄ -alkoxy.

In another embodiment, the substituent A or B is phenyl substituted with one CN and one to three halogens. In another embodiment, the substituent A or B is phenyl which is substituted with a CN and one of the abovementioned substituents.

In a preferred embodiment, the substituent A or B is phenyl substituted with a CN and another substituent selected from halogen.

In a further preferred embodiment, the substituent A or B is phenyl which is substituted by one CN only.

In another preferred embodiment, the substituent A or B is phenyl substituted with one CN only for the case of the substituent A in the 4-position and for the case of the substituent B in the 2-position.

The following substituents A, in which X is F or Cl, are particularly preferred:

A1, B1

A10, B10

A15, B15 A16, B16 A17, B17 A18, B18

A19, B19 A20, B20 A21. B21 A22, B22 A23, B23 In one embodiment, A is A1.

In another embodiment, A is A2 with X = F.

In another embodiment, A is A2 with X = Cl.

According to a preferred embodiment, A stands for A3 with X = F. According to a preferred embodiment, A stands for A3 with X = Cl. According to another embodiment, A stands for A4 with X = F.

According to another embodiment, A stands for A4 with X = CL.

In another embodiment, A is A5 with X = F.

In another embodiment, A is A5 with X = Cl. In another embodiment, A is A6. In another embodiment, A is A7.

In another embodiment, A is A8.

In another embodiment, A is A9.

In another embodiment, A is A10. According to another embodiment, A stands for A1 1 with X = F. According to a further embodiment, A stands for A1 1 with X = Cl.

In another embodiment, A is A12 with X = F.

In another embodiment, A is A12 with X = Cl.

According to another embodiment, A stands for A13 with X = F. According to another embodiment, A stands for A13 with X = Cl. In another embodiment, A is A14 with X = F. In another embodiment, A is A14 with X = Cl.

In a preferred embodiment, A is A15.

According to a particularly preferred embodiment, A is A16.

In another embodiment, A is A17. In another embodiment, A is A18.

In another embodiment, A is A19.

In another embodiment, A is A20 with X = F.

In another embodiment, A is A20 with X = Cl.

According to a particularly preferred embodiment, A stands for A21 with X = F. According to another embodiment, A stands for A21 with X = Cl. In another embodiment, A is A22.

In another embodiment, A is A23.

In one embodiment, B is B1.

In another embodiment, B is B2 with X = F. In another embodiment, B is B2 with X = Cl. In a preferred embodiment, B is B3 with X = F.

In a preferred embodiment, B is B3 with X = Cl.

In another embodiment, B is B4 with X = F.

According to another embodiment, B stands for B4 with X = CL. In another embodiment, B is B5 with X = F. In another embodiment, B is B5 with X = Cl. In another embodiment, B is B6.

In another embodiment, B is B7.

In another embodiment, B is B8.

In another embodiment, B stands for B9. In another embodiment, B is B10.

According to another embodiment, B stands for B1 1 with X = F.

According to another embodiment, B stands for B1 1 with X = Cl.

In another embodiment, B is B12 with X = F.

In another embodiment, B is B12 with X = Cl. According to another embodiment, B stands for B13 with X = F. According to another embodiment, B stands for B13 with X = Cl.

In another embodiment, B is B14 with X = F.

In another embodiment, B is B14 with X = Cl.

In a preferred embodiment, B is B15. In a particularly preferred embodiment, B is B16. In another embodiment, B is B17.

In another embodiment, B stands for B18.

In another embodiment, B is B19.

In another embodiment, B is B20 with X = F. In another embodiment, B is B20 with X = Cl.

According to a particularly preferred embodiment, B stands for B21 with X = F. In another embodiment, B is B21 with X = Cl.

In another embodiment, B is B22.

In another embodiment, B is B23.

In a further embodiment of the present invention, the respective other substituent A or B is phenyl substituted by one to three of the following substituents: halogen, CN, NO _2, amino _Ci-C4 -alkyl, Ci-C ₄ alkoxy, Ci is -C ₄ -haloalkyl, Ci-C ₄ -

Haloalkoxy, Ci-C ₄ -alkylamino, Ci-C ₄ -dialkylamino, thio or Ci-C ₄ -alkylthio is substituted.

In another embodiment, the respective other substituent A or B is phenyl substituted by one to three of the following substituents: halogen, _Ci-C4-alkyl, d- _C4-alkoxy, _{Ci-C4-haloalkyl} or Ci-C ₄ is Haloalkoxy is substituted.

In a preferred embodiment, the other substituent A or B is phenyl which is substituted by one to three halogen.

In a further embodiment, the substituent A or B is a 5-membered heteroaryl which is optionally substituted by one to three of the following substituents: halogen, CN, NO ₂ , amino, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, ₄ -haloalkoxy, CrC ₄ _{Ci-C4-haloalkyl,} Ci-C - alkylamino, Ci-C ₄ dialkylamino substituted, thio, or Ci-C ₄ alkylthio.

In a further embodiment, the substituent A or B is a 5-membered heteroaryl selected from furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1, 3,4-oxadiazolyl, thiazolyl, isothiazolyl and thiadia - zolyl.

In a further embodiment, the substituent A or B is a 5-membered heteroaryl selected from furyl, thienyl, pyrrolyl, pyrazolyl, triazolyl and thiazolyl.

In a further embodiment, the substituent A or B is a 5-membered heteroaryl selected from thienyl, triazolyl and pyrazolyl.

In a further embodiment, the substituent A or B is a 5-membered heteroaryl which is substituted by one to three of the following substituents: halogen, CN, NO 2, amino, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, C i -C ₄ haloalkyl, _{Ci-C4-haloalkoxy,} -C ₄ - substituted ₄ dialkylamino, thio, or Ci-C ₄ alkylthio, alkylamino, Ci-C. In a further embodiment, the substituent A or B is a 5-membered heteroaryl which is substituted by one to three of the following substituents: halogen, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, C 1 -C ₄ -haloalkyl or C 1 -C ₄ -alkyl. Haloalkoxy is substituted.

In a further embodiment, the substituent A or B is a 5-membered heteroaryl which is substituted by one to three of the following substituents halogen, Ci-C4-alkyl or Ci-C4-alkoxy.

In a further embodiment, the substituent A or B is a 6-membered heteroaryl which is optionally substituted by one to three of the following substituents: halogen, CN, NO 2, amino, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -Haloalkyl, Ci-C4-haloalkoxy, C1-C4-alkylamino, Ci-C4-dialkylamino, thio or Ci-C4-alkylthio, is substituted.

In a further embodiment, the substituent A or B is a 6-membered heteroaryl selected from pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1, 2,3-triazinyl, 1, 2,4-triazinyl and 1, 3,5-triazinyl ,

In another embodiment, the substituent A or B is a 6-membered heteroaryl selected from pyridyl and pyrimidinyl.

In a further embodiment, the substituent A or B is a 6-membered heteroaryl which is substituted by one to three of the following substituents: halogen, CN, NO 2, amino, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -Haloalkyl, Ci-C4-haloalkoxy, C1-C4-alkylamino, Ci-C4-dialkylamino, thio or Ci-C4-alkylthio, is substituted.

In a further embodiment, the substituent A or B is a 6-membered heteroaryl which is substituted by one to three of the following substituents: halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl or C 1 -C 4 -haloalkoxy is substituted.

In a further embodiment, the substituent A or B is a 6-membered heteroaryl which is substituted by one to three of the following substituents: halogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.

In particular, with regard to their use, the compounds I according to the invention which are compiled in the following Tables 2 to 13 are preferred. The groups mentioned in the tables for a substituent are also considered individually, regardless of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.

Table 1

Table 3

Compounds of the formula I in which A is A1 and B in each case corresponds to a substituent of a row of Table 1.

Table 4

Compounds of the formula I in which A is A2 with X = F and B is in each case one

Substituents corresponds to a row of Table 1.

Table 5

Compounds of the formula I in which A is A2 with X = Cl and B in each case corresponds to a substituent of a line of Table 1.

Table 6 Compounds of the formula I, in which A stands for A3 with X = F and B in each case one

Substituents corresponds to a row of Table 1.

Table 7

Compounds of the formula I in which A is A3 with X = Cl and B in each case corresponds to a substituent of a line of Table 1.

Table 8

Compounds of the formula I, in which A is A4 with X = F and B in each case one

Substituents corresponds to a row of Table 1.

Table 9

Compounds of the formula I, in which A is A4 with X = Cl and B in each case one

Substituents corresponds to a row of Table 1. Table 10

Compounds of the formula I in which A is A5 with X = F and B in each case corresponds to a substituent of a line of Table 1.

Table 1 1

Compounds of the formula I in which A is A5 with X = Cl and B in each case corresponds to a substituent of a line of Table 1.

Table 12 Compounds of the formula I, in which A is A6 and B in each case corresponds to a substituent of a line of Table 1.

Table 13

Compounds of the formula I in which A is A7 and B in each case corresponds to a substituent of a row of Table 1.

Table 14

Compounds of the formula I in which A is A8 and B in each case corresponds to a substituent of a line of Table 1.

Table 15

Compounds of the formula I in which A is A9 and B in each case corresponds to a substituent of a line of Table 1.

Table 16

Compounds of the formula I in which A is A10 and B in each case corresponds to a substituent of a line of Table 1.

Table 17 Compounds of the formula I, in which A is A1 1 with X = F and B in each case one

Substituents corresponds to a row of Table 1.

Table 18

Compounds of the formula I in which A is A11 with X = Cl and B in each case corresponds to a substituent of a line of Table 1.

Table 19

Compounds of the formula I in which A is A12 with X = F and B in each case corresponds to a substituent of a line of Table 1. Table 20

Compounds of the formula I in which A is A12 where X = Cl and B in each case corresponds to one substituent of a line of Table 1.

Table 21

Compounds of the formula I in which A is A13 with X = F and B in each case corresponds to a substituent of a line of Table 1.

Table 22 Compounds of the formula I in which A is A13 where X = Cl and B are each one

Substituents corresponds to a row of Table 1.

Table 23

Compounds of the formula I in which A is A14 with X = F and B in each case corresponds to a substituent of a line of Table 1.

Table 24

Compounds of the formula I in which A is A14 with X = Cl and B in each case corresponds to a substituent of a line of Table 1.

Table 25

Compounds of the formula I in which A is A15 and B in each case corresponds to a substituent of a line of Table 1.

Table 26

Compounds of the formula I in which A is A16 and B in each case corresponds to a substituent of a line of Table 1.

Table 27 Compounds of the formula I, in which A is A17 and B corresponds in each case to one substituent of a row of Table 1.

Table 28

Compounds of the formula I in which A is A18 and B corresponds in each case to one substituent of one row of Table 1.

Table 29

Compounds of the formula I in which A is A19 and B in each case corresponds to a substituent of a line of Table 1. Table 30

Compounds of the formula I in which A is A20 with X = F and B in each case corresponds to a substituent of a line of Table 1.

Table 31

Compounds of the formula I in which A is A20 with X = Cl and B in each case corresponds to a substituent of a line of Table 1.

Table 32 Compounds of the formula I in which A is A21 where X = F and B are each one

Substituents corresponds to a row of Table 1.

Table 33

Compounds of the formula I in which A is A21 where X = Cl and B in each case corresponds to one substituent of a row of Table 1.

Table 34

Compounds of the formula I in which A is A22 and B in each case corresponds to a substituent of a line of Table 1.

Table 35

Compounds of the formula I in which A is A23 and B in each case corresponds to a substituent of a line of Table 1.

Table 36

Compounds of the formula I in which B is B1 and A in each case corresponds to one substituent of a row of Table 2.

Table 37 Compounds of the formula I in which B is B2 with X = F and A is in each case one

Substituents corresponds to one line of Table 2.

Table 38

Compounds of the formula I in which B is B2 with X = Cl and A in each case corresponds to one substituent of a row of Table 2.

Table 39

Compounds of the formula I in which B is B3 with X = F and A in each case corresponds to one substituent of a row of Table 2. Table 40

Compounds of the formula I in which B is B3 with X = Cl and A in each case corresponds to one substituent of a row of Table 2.

Table 41

Compounds of the formula I in which B is B4 with X = F and A in each case corresponds to a substituent of a line of Table 2.

Table 42 Compounds of the formula I in which B is B4 with X = Cl and A is each one

Substituents corresponds to one line of Table 2.

Table 43

Compounds of the formula I in which B is B5 with X = F and A in each case corresponds to one substituent of a row of Table 2.

Table 44

Compounds of the formula I in which B is B5 with X = Cl and A in each case corresponds to one substituent of a row of Table 2.

Table 45

Compounds of the formula I in which B is B6 and A in each case corresponds to a substituent of a line of Table 2.

Table 46

Compounds of the formula I in which B is B7 and A in each case corresponds to a substituent of a line of Table 2.

Table 47 Compounds of the formula I in which B is B8 and A in each case corresponds to one substituent of a row of Table 2.

Table 48

Compounds of the formula I in which B is B9 and A in each case corresponds to a substituent of a row of Table 2.

Table 49

Compounds of the formula I in which B is B10 and A in each case corresponds to a substituent of a line of Table 2. Table 50

Compounds of the formula I in which B is B1 1 with X = F and A in each case corresponds to one substituent of a row of Table 2.

Table 51

Compounds of the formula I in which B is B11 with X = Cl and A in each case corresponds to a substituent of a line of Table 2.

Table 52 Compounds of the formula I, in which B stands for B12 with X = F and A in each case one

Substituents corresponds to one line of Table 2.

Table 53

Compounds of the formula I in which B is B12 with X = Cl and A in each case corresponds to one substituent of a row of Table 2.

Table 54

Compounds of the formula I, in which B is B13 with X = F and A is in each case one

Substituents corresponds to one line of Table 2.

Table 55

Compounds of the formula I in which B is B13 with X = Cl and A is each one

Substituents corresponds to one line of Table 2.

Table 56

Compounds of the formula I in which B is B14 with X = F and A in each case corresponds to a substituent of a line of Table 2.

Table 57 Compounds of the formula I in which B is B14 with X = Cl and A is each one

Substituents corresponds to one line of Table 2.

Table 58

Compounds of the formula I in which B is B15 and A in each case corresponds to a substituent of one row of Table 2.

Table 59

Compounds of the formula I in which B is B16 and A in each case corresponds to a substituent of a line of Table 2. Table 60

Compounds of the formula I in which B is B17 and A in each case corresponds to a substituent of a row of Table 2.

Table 61

Compounds of the formula I in which B is B18 and B corresponds in each case to one substituent of one row of Table 1.

Table 62 Compounds of the formula I in which B is B19 and A corresponds in each case to one substituent of one row of Table 2.

Table 63

Compounds of the formula I in which B is B20 with X = F and A in each case corresponds to a substituent of a line of Table 2.

Table 64

Compounds of the formula I in which B is B20 with X = Cl and A is in each case one

Substituents corresponds to one line of Table 2.

Table 65

Compounds of the formula I, in which B is B21 with X = F and A is in each case one

Substituents corresponds to one line of Table 2.

Table 66

Compounds of the formula I in which B is B21 with X = Cl and A in each case corresponds to one substituent of a row of Table 2.

Table 67 Compounds of the formula I, in which B is B22 and A in each case corresponds to a substituent of a row of Table 2.

Table 68

Compounds of the formula I in which B is B23 and A in each case corresponds to a substituent of a line of Table 2.

The compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes, in particular from the class of the Oomycetes. They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides. They are particularly important for the control of a variety of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers. Beans, tomatoes, potatoes and pumpkins, as well as the seeds of these plants.

In particular, they are suitable for controlling the following plant diseases:

Alternaria species on vegetables, oilseed rape, sugar beets and fruits and rice, such as A.solani or A. alternata on potatoes and tomatoes, • Aphanomyces species on sugar beet and vegetables,

• Ascochyta species on cereals and vegetables,

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

• Blumeria graminis (powdery mildew) on cereals, • Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines,

• Bremia lactucae on salad,

Cercospora species on corn, soybeans, rice and sugar beet,

Cochliobolus species on corn, cereals, rice, e.g. Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice,

• Colletotricum species on soybeans and cotton,

• Drechslera species, Pyrenophora species on maize, cereals, rice and turf, e.g. D.teres to barley or D. tritici-repentis to wheat,

Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum, and Formitipora punctata (syn. Phellinus punctatus),

Exserohilum species on corn,

Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Fusarium and Verticillium species on various plants, e.g.

F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of plants, e.g. Tomatoes,

Gaeumanomyces graminis on cereals,

Gibberella species on cereals and rice (e.g., Gibberella fujikuroi on rice),

• Grainstaining complex on rice,

• Helminthosporium species on maize and rice, • Michrodochium nivale on cereals,

Mycosphaerella species on cereals, bananas and peanuts, e.g. M. graminicola on wheat or M.fijiensis on bananas,

Peronospora species on cabbage and bulbous plants, such as P. brassicae on cabbage or P. destructor on onion, • Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,

• Phomopsis species on soybeans and sunflowers,

• Phytophthora infestans on potatoes and tomatoes, Phytophthora species on various plants such as P. capsici on peppers,

Plasmopara viticola on grapevines,

• Podosphaera leucotricha on apple,

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

Puccinia species on various plants, e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals, or P. asparagi on asparagus,

Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum, Entenoma oryzae, on rice,

• Pyricularia grisea on grass and cereals,

• Pythium spp. on turf, rice, corn, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants such as e.g. P.ultiumum on various plants, P. aphanidermatum on lawns, • Rhizoctonia species on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various plants such as e.g. R.solani on turnips and various plants,

• Rhynchosporium secalis on barley, rye and triticale,

• Sclerotinia species on rape and sunflowers, • Septoria tritici and Stagonospora nodorum on wheat,

• Erysiphe (syn. Uncinula) necator on grapevine,

• Setospaeria species on corn and turf,

• Sphacelotheca reilinia on corn,

• Thievaliopsis species on soybeans and cotton, • Tilletia species on cereals,

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

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

In particular, they are suitable for controlling harmful fungi from the class of Peronosporomycetes (syn.Oomyceten), such as Peronospora species, Phytophthora species, Plasmopara viticola, Pseudoperonospora species and Pythium species.

The compounds I are also suitable for controlling harmful fungi in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In wood preservation, particular attention is paid to the following harmful fungi: ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sciophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleu- rotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae. The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.

The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.

In the seed treatment, in general, amounts of active ingredient of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of seed are needed.

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

The compounds of the formula I can be present in various crystal modifications, which may differ in their biological activity. They are also the subject of the present invention.

The compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

Water, aromatic solvents (e.g., Solvesso products, xylene), paraffins (e.g., petroleum fractions), alcohols (e.g., methanol, butanol, pentanol, benzyl alcohol),

Ketones (e.g., cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids, and fatty acid esters. In principle, solvent mixtures can also be used

Carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates);

Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene) Fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin liquors and methylcellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

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

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum). Examples of formulations are: 1. Products for dilution in water

A Water-soluble concentrates (SL, LS)

10 parts by weight of the active ingredients are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content.

B Dispersible Concentrates (DC) 20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight

C. Emulsifiable Concentrates (EC) 15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content.

D emulsions (EW, EO, ES)

25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E suspensions (SC, OD, FS)

20 parts by weight of the active ingredients are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active compounds are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and water-soluble powders (WP, SP, SS, WS)

75 parts by weight of the active ingredients are added with the addition of 25 parts by weight of dispersing and Wetting agents and silica gel in a rotor-Strator mill. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H gel formulations (GF)

In a ball mill, 20 parts by weight of the active ingredients, 10 parts by weight of dispersant, 1 part by weight of swelling agent ("gelling agent") and 70 parts by weight of water or an organic solvent are ground to a fine suspension With water results in a stable suspension with 20 wt .-% active ingredient content.

2. Products for direct application

I dusts (DP, DS)

5 parts by weight of the active ingredients are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content.

J Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

K ULV Solutions (UL) 10 parts by weight of the active ingredients are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with 10 wt .-% active ingredient content.

For seed treatment, water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are usually used. These formulations can be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or Pouring be applied. The forms of application depend entirely on the purposes of use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, possibly also just immediately before use (tank mix), are added. These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

As an adjuvant in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ^® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluro- nic RPE 2035 ^® and Genapol B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ^®.

The agents according to the invention, in the form of application as fungicides, may also be present together with other active substances, e.g. with herbicides, insecticides, growth regulators, fungicides or with fertilizers. When mixing the compounds I or the agents containing them with one or more further active compounds, in particular fungicides, for example, in many cases the spectrum of action can be broadened or resistance developments can be prevented. In many cases, synergistic effects are obtained.

A further subject matter of the present invention is a combination of at least one azolylmethyloxirane of the formula I, in particular an azolylmethyloxirane disclosed as preferred in the present description and / or an agriculturally acceptable salt thereof and at least one further fungicidal, insecticidal, herbicidal and / or growth-regulating active ingredient, wherein a synergistic effect may occur.

Another object of the present invention is a pesticidal composition comprising at least one compound of the formula I, in particular a compound of the formula I described as being preferred in the present specification and / or an agriculturally acceptable acid addition or metal salt thereof and at least one solid or liquid carrier , Such a pesticidal composition may contain at least one other fungicidal, insecticidal and / or herbicidal active ingredient, whereby a synergistic effect may also occur.

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

strobilurins

Azoxystrobin, Dimoxystrobin, Enestroburin, Fluoxastrobin, Kresoxim-methyl, Methyminostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Pyribencarb, Trifloxystrobin, 2- (2- (6- (3-chloro-2-methyl-phenoxy) -5-fluoro) pyrimidin-4-yloxy) -phenyl) -2-methoxyimino-N-methyl-acetamide, 2- (ortho - ((2,5-dimethylphenyl-oxymethylene) -phenyl) -3-methoxy-acrylic acid methyl ester, 3-methoxy- 2- (2- (N- (4-methoxyphenyl) -cyclopropanecarboximidoylsulfanylmethyl) -phenyl) -acrylic acid methyl ester;

carboxamides

- Carboxylic acid anilides: Benalaxyl, Benalaxyl M, Benodanil, Bixafen, Boscalid, Carboxin, Fenfuram, Fenhexamid, Flutolanil, Furametpyr, Isotianil, Kiralaxyl, Mepronil, Metalaxyl, Ofurace, Oxadixyl, Oxycarboxin, Penthiopyrad, Tecloftalam, Thifluzami- de, Tiadinil , 2-amino-4-methyl-thiazole-5-carboxylic acid anilide, 2-chloro-N- (1, 1, 3-trimethyl-indan-4-yl) -nicotinamide, N- (3 ', 4'- dichloro-5-fluoro-biphenyl-2-yl) -3-difluoromethyl-

1-methyl-1H-pyrazole-4-carboxylic acid amide, 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid [2- (1, 3-dimethyl-butyl) -phenyl] -amide , N- (4'-Chloro-3 ', 5-difluoro-biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (4'-chloro-3' , 5-difluorobiphenyl-2-yl) -3-trifluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (3 ', 4'-dichloro-5-fluorobiphenyl-2-yl) 3-trifluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (3 ', 5-difluoro-4'-methyl-biphenyl-2-yl) -3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxylic acid amide, N- (3 ', 5-difluoro-4'-methyl-biphenyl-2-yl) -3-trifluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (2-Bicyclopropyl-2-yl-phenyl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (cis-2-bicyclopropyl-2-yl-phenyl) -3-di-fluoromethyl 1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (trans-2-bicyclopropyl-2-yl-phenyl) -3-d-isluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide,

- Carboxylic acid morpholides: Dimethomorph, Flumorph; Benzoic acid amides: flumetover, fluopicolide, fluopyram, zoxamide, N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3-formylamino-2-hydroxybenzamide;

Other carboxamides: carpropamide, diclocymet, mandipropamide, oxytetracycline, silthiofam, N- (6-methoxypyridin-3-yl) cyclopropanecarboxamide;

azoles

- Triazoles: azaconazole, bitertanol, bromuconazoles, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothiocona - zole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1- (4-chloro-phenyl) -2 - ([1, 2,4] triazol-1-yl) -cycloheptanol;

- imidazoles: cyazofamide, imazalil, imazalil sulfate, pefurazoate, prochloraz, triflumizole; Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;

- Other: Ethaboxam, Etridiazole, Hymexazole, 1- (4-Chloro-phenyl) -1- (propyn-2-yloxy) -3- (4- (3,4-dimethoxyphenyl) -isoxazol-5-yl) -propan-2-one;

Nitrogen-containing heterocyclyl compounds - pyridines: fluazinam, pyrifenox, 3- [5- (4-chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine, 2,3,5,6-tetrachloro-4-methanesulfonyl -pyridine, 3,4,5-trichloro-pyridine-2,6-dicarbonitrile, N- (1 - (δ-bromo-S-chloro-pyridine-y-O-ethoxy) -dichloro-nicotinamide, N- ((5-bromo-3-chloro-pyridin-2-yl) -methyl) -2,4-dichloro-nicotinamide;

- pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, panipyrim, nitrapyrin, nuarimol, pyrimethanil;

- Pyrroles: fludioxonil, fenpiclonil;

- morpholines: aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph;

Dicarboximides: fluoroimide, iprodione, procymidone, vinclozolin; - Other: Acibenzolar-S-methyl, Amisulbrom, Anilazine, Blasticidin-S, Captafol, Captan, Chinomethionat, Dazomet, Debacarb, Diclomethine, Difenzoquat, Difenzoquat-methylsulphate, Famoxadone, Fenamidone, Fenoxanil, Fenpropidin, Folpet, Octhilinone, Oxolinic acid, Piperalin , Sample azoles, proquinazide, pyroquilon, quinoxyfen, triazoxide, tricyclazole, triforine, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyimidine, 2-butoxy-6-iodo-3-propyl-chromen-4-one; Carbamates and dithiocarbamates

Thio and dithiocarbamates: Ferbam, Mancozeb, Maneb, Metam, Methasulphocarb, Metiram, Propineb, Thiram, Zineb, Ziram; Carbamates: Diethofencarb, Benthiavalicarb, Iprovalicarb, Propamocarb,

Propamocarb hydrochloride, valiphenal, N- (1- (1- (4-cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid (4-fluorophenyl) ester; Other fungicides

Guanidines: dodine, dodine free base, guazatine, guazatine acetate, iminoctadine, iminoctadine triacetate, iminoctadine tris (albesilat); - antibiotics: kasugamycin, kasugamycin hydrochloride hydrate, polyoxins, streptomycin, validamycin A;

Nitrophenyl derivatives:

Binapacryl, dicloran, dinobutone, dinocap, nitrothal-isopropyl, tecnazene;

Organometallic compounds: Fentin salts such as, for example, fentin acetate, fentin chloride, fentin hydroxide;

Sulfur-containing heterocyclyl compounds: isoprothiolanes, dithianone;

Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl;

Organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophen, flusulfamides, hexachlorobenzene, pencycuron, pentachlorophenol and its salts, phthalocyanine

Nd, quintozene, thiophanate-methyl, tolylfluanid, N- (4-chloro-2-nitro-phenyl) -N-ethyl-4-methyl-benzenesulfonamide;

- Inorganic active substances: Phosphorous acid and its salts, sulfur, Bordeaux broth, copper salts such as copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate;

- Other: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamine, metrafenone, mildiomycin, oxine-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N- (cyclopropylmethoxyimino- (6-difluoromethoxy-2,3-difluorophenyl) - methyl) -2-phenylacetamide, N '- (4- (4-chloro-3-trifluoromethyl-phenoxy) -2,5-dimethylphenyl) -N-ethyl-N-methylformamidine, N' - 4-fluoro-3-trifluoromethyl-phenoxy) -2,5-dimethyl-phenyl) -N-ethyl-N-methylformamidine, N '- (2-methyl-5-trifluoromethyl-4- (3-trimethylsilanyl-propoxy) ) -phenyl) -N-ethyl-N-methylformamidine, N '- (5-difluoromethyl-2-methyl-4- (3-trimethylsilanyl-propoxy) -phenyl) -N-ethyl-N-methylformamidine.

Accordingly, the present invention further relates to the compositions listed in Table B, wherein in each case one row of Table B corresponds to a fungicidal composition comprising a compound of the formula I (component 1), which is preferably one of the compounds described herein as preferred, and the each additional active ingredient (component 2) indicated in the respective line. According to one embodiment of the invention, component 1 in each row of table B is in each case one of the compounds of the formula I which are specifically individualized in tables 1 to 68. Table B

The active compounds II mentioned above as component 2, their preparation and their action against harmful fungi are generally known (cf.: http://www.hclrss.demon.co.uk/index.html); they are commercially available. The compounds named after IUPAC, their preparation and their fungicidal action are also known [cf. EP-A 226 917; EP-A 10 28 125; EP-A 10 35 122; EP-A 12 01 648; WO 98/46608; WO 99/24413; WO 03/14103; WO 03/053145; WO 03/066609; WO 04/049804].

synthesis Examples

1) Synthesis of 4- {anti-2 - [(1H-1, 2,4-triazol-1-yl) methyl] -3- [2-fluorophenyl] oxiran-2-yl} -3-fluorobenzonitrile

A solution of anti-2- (4-chloro-2-fluorophenyl) -3- (2-fluorophenyl) oxiran-2-yl) methyl-1 H-1, 2,4-triazole (300 mg, 0.86 mmol), Zinc (II) cyanide (105 mg, 0.86 mmol), tris (dibenzylideneacetone) dipalladium (0) (78 mg, 0.086 mmol) and 2,2'-bis (diphenylphosphino) -1, 1'-binaphthyl (11 1 mg, 0.173 mmol) in NMP (17 ml) was stirred in a microwave oven for two hours at 200 ⁰ C. After cooling to room temperature, the reaction mixture was added to ice-water (100 ml). The resulting precipitate was filtered off, washed with water (50 ml) and the water removed azeotropically with acetone tril. The residue was purified by column chromatography (silica gel, diethyl ether / dichloromethane gradient). The target compound 4- {anti-2- [(1H-1, 2,4-triazol-1-yl) methyl] -3- [2-fluorophenyl] oxiran-2-yl} -3-fluorobenzonitrile (62 mg, 21 %) was obtained as a yellow solid after combining the appropriate fractions and removing the solvent.

H NMR (300 MHz, CDCl ₃ ): δ 7.92 (s, 1H), 7.78 (s, 1H), 7.58-7.52 (m, 1H), 7.48-7.29 (m, 5H), 7.23-7.17 (m, 1H), 4.81 (d, J = 15.0Hz, 1H), 4.33 (s, 1H), 4.09 (d, J = 15.0Hz, 1H).

Analogously to this procedure, the compounds of Table 69 were prepared.

Table 69

Biological part of greenhouse drug preparation

The active compounds were prepared separately or together as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or DMSO and the emulsifier Wettol EM 31 (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent- Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.

Use Example 1 - Curative Efficacy Against Soybean Rust Caused by Phakopsora pachyrhizi (Phakpa K3)

Leaves of potted soybean seedlings were inoculated with a spore suspension of soybean rust (Phakpsora pachyrhizi). Thereafter, the pots were placed in a high humidity chamber (90-95%) and 23-27 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The infected plants were kept in a chamber for a further 2 days with temperatures between 23 and 27 ° C and 60-80% relative humidity. After that were spray the plants with the above-described active substance solution in the concentration of active compound specified below to dripping wetness. After the spray coating had dried on, the test plants were cultivated in the greenhouse at temperatures between 23 and 27 ° C. and 60 to 80% relative atmospheric humidity for 14 days. Then the extent of rust fungus development on the leaves was determined.

The treated with the active ingredients 69.1 and 69.2 with 63 ppm aqueous active ingredient preparation plants showed an infestation of 0%, while the untreated plants were 90% infected.

Use Example 2 Protective Activity Against Puccinia recondita on Wheat (Wheat Brown Rust) (Puccrt P1)

Leaves of potted wheat seedlings were sprayed to drip point with an aqueous suspension at the drug concentration below. The next day, the treated plants were treated with a

Spore suspension of wheat brown rust (Puccinia recondita) inoculated. Subsequently, the plants were placed in a high humidity chamber (90 to 95%) at 20 to 22 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. On the following day, the test plants were returned to the greenhouse and cultured at temperatures between 20 and 22 ° C and 65 to 70% relative humidity for a further 7 days. Then the extent of rust fungus development on the leaves was visually determined.

The plants treated with the active compounds 69.1 and 69.3 with 63 ppm aqueous aqueous preparation showed an infection of 0%, while the untreated plants were 90% infected.

Use Example 3 Efficacy Against Powdery Mildew on Cucumber Leaves Caused by Sphaerotheca fuliginea in Protective Application (Sphrfu P1) Leaves of cucumber seedlings grown in pots were sprayed to drip point in the cotyledon stage with aqueous suspension in the concentration of active compound stated below. 20 hours after the spray coating had dried, the plants were inoculated with an aqueous spore suspension of cucumber mildew (Sphaerotheca fuliginea). Subsequently, the plants were cultivated in the greenhouse at temperatures between 20 and 24 ° C and 60 to 80% relative humidity for 7 days. Then, the extent of mildew development was determined visually in% of the cotyledon area.

The plants treated with the active ingredient 69.3 with 63 ppm aqueous aqueous preparation showed an attack of 1%, while the untreated plants were 90% infected.

Claims

claims

1. Azolylmethyloxirane of the general formula I.

wherein

A or B is phenyl which is substituted by one CN and optionally by one to three of the following substituents: halogen, NO 2, amino, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy , C 1 -C 4 -alkylamino,

Ci-C4-dialkylamino, thio or Ci-C4-alkylthio, is substituted,

and the other substituent

A or B is phenyl or 5-membered or 6-membered heteroaryl, where these substituents are optionally substituted by one to three of the following substituents: halogen, CN, NO ₂ , amino, C 1 -C ₄ -alkyl, C 1 -C ₄ - Alkoxy, C 1 -C ₄ -haloalkyl, C 1 -C ₄ -haloalkoxy, C 1 -C ₄ -alkylamino, C 1 -C ₄ -dialkylamino, thio or C 1 -C ₄ -alkylthio,

as well as their plant tolerated acid addition or metal salts.

2. Compounds according to claim 1, in which the CN-substituted phenyl is substituted by one to three of the following substituents: halogen, NO 2, amino, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy , C 1 -C 4 -alkylamino, d-

C4-dialkylamino, thio or Ci-C4-alkylthio substituted.

3. Compounds according to claim 2, in which the CN-substituted phenyl is substituted by one to three of the following substituents: halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl or C 1 -C 4 -haloalkoxy.

4. Compounds according to claim 3, in which the CN-substituted phenyl is additionally substituted by one to three of the following substituents: halogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.

5. Compounds according to claim 4, in which the CN-substituted phenyl is additionally substituted by one to three halogen.

6. Compounds according to any one of claims 2 to 5, wherein the CN-substituted phenyl is additionally substituted by one of said substituents.

7. Compounds according to one of claims 1 to 6, in which the respective other phenyl is substituted by one to three of the following substituents: halogen, CN, NO 2, amino, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, C 1 -C ₄ haloalkyl, _{Ci-C4-haloalkoxy,} -C ₄ - alkylamino, Ci-C ₄ dialkylamino substituted, thio, or Ci-C ₄ alkylthio.

8. Compounds according to any one of claims 1 to 6, in which the respective other phenyl substituted by one to three of the following substituents: halogen, _Ci-C4 alkyl, Cr C ₄ alkoxy, _{Ci-C4-haloalkyl} or Ci-C ₄ Haloalkoxy is substituted.

9. Compounds according to any one of claims 1 to 6, wherein the respective other phenyl by one to three of the following substituents halogen, Ci-C ₄ alkyl or

Ci-C ₄ alkoxy is substituted.

10. Compounds according to any one of claims 1 to 6, in which the 5-membered heteroaryl is selected from furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3,4-oxadiazolyl , Thiazolyl, isothiazolyl and

Thiadiazolyl.

1 1. Compounds according to claim 10, wherein the 5-membered heteroaryl is selected from furyl, thienyl, pyrrolyl, pyrazolyl, triazolyl and thiazolyl.

12. Compounds according to claim 1 1, wherein the 5-membered heteroaryl is selected from thienyl, triazolyl and pyrazolyl.

13. Compounds according to any one of claims 1 to 6, wherein the 6-membered heteroaryl is selected from pyridinyl, pyrimidinyl, pyrazinyl; Pyridazinyl, 1, 2,3-

Triazinyl, 1, 2,4-triazinyl and 1, 3,5-triazinyl.

14. Compounds according to claim 13, in which the 6-membered heteroaryl is selected from pyridyl and pyrimidinyl.

15. Use of compounds of the formula I according to any one of claims 1 to 14 and their acid addition or metal salts for controlling plant-pathogenic fungi.

16. An agent for crop protection, comprising a solid or liquid carrier and a compound of the formula I according to any one of claims 1 to 14 and / or a Acid addition or metal salt thereof.

17. Seed containing at least one compound of formula I according to any one of claims 1 to 14 and / or an acid addition or metal salt thereof.

18. A method for controlling phytopathogenic fungi, characterized in that the fungi, or to be protected against fungal attack materials, plants, the soil or seeds with an effective amount of a compound of formula I according to any one of claims 1 to 14 or an acid addition - treated ons or metal salt thereof.