WO2010115758A2 - Fungicidal compounds - Google Patents

Abstract

Compounds of the formula (I) in which the substituents have the meaning given in the description, processes for preparing these compounds, compositions comprising them and their use for controlling harmful fungi.

Description

Fungicidal compounds

Description

The present invention relates to compounds of the formula I

in which the substituents have the following meaning:

R¹ is d-Cs-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₃-C₈-cycloalkyl, C3-C₈-cycloalkenyl, phenyl or a three- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; R² is NR^AR^B, Ci-Ci2-alkylthio, phenyl or a 3- to 10-membered saturated, partially unsaturated or aromatic heterocyclyl, wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the phenyl and heterocyclyl groups R² are attached via an oxygen or sulfur atom, or -[0-(ZH₂)_n]m-H, wherein Z are independently of each other carbon or silicium; n is an integer between 1 and 5, m is an integer between 3 and 10; R³,R⁴ independently of one another are hydrogen, Ci-Cβ-alkyl, Ci-Cs-haloalkyl, Ci-C₈- alkylcarbonyl or d-Cβ-alkoxycarbonyl; R⁵,R⁶ independently of one another are Ci-Cβ-alkyl, Ci-Cβ-haloalkyI, Ci-C4-alkoxy or

C3-Cβ-cycloalkyl;

R⁷ is hydrogen, C-i-Cβ-alkyl, Ci-C₈-haloalkyl, Ci-C4-alkoxy or Ci-Cβ-haloalkoxy; and aliphatic and cyclic groups R¹ to R⁶ may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R^a which independently of one another are selected from:

R^a is amino, halogen, hydroxyl, oxo, nitro, cyano, carboxyl, Ci-C₄-alkyl, C₂-C₄- alkenyl, C₂-C₄-alkynyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy, Ci-C₄-haloalkoxy, C3-C6-cycloalkyl, C3-C₈-cycloalkenyl, C₂-C6-alkenyloxy, C3-C6-alkynyloxy, Ci-C4-alkoxyimino, C₂-C8-alkylidene, Cs-Cβ-cycloalkylidene, Ci-Ci₂- alkylamino, Ci-d-alkoxycarbonyl, d-d-alkylcarbonyloxy, NR^AR^B, C₂-C₈- alkylene, C₂-C₈-oxyalkylene, Ci-Cβ-oxyalkyleneoxy, phenyl, naphthyl or a three- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^a may be attached directly or via a nitrogen or oxygen atom; where the aliphatic or cyclic groups R^a for their part may be partially or fully halogenated and/or may carry one, two, three or up to the maximum possible number of identical or different groups R^b:

R^b is halogen, hydroxyl, nitro, cyano, carboxyl, Ci-C₄-alkyl, C₂-C₄-alken- yl, C2-Cβ-alkynyl, Ci-C₄-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-Cβ-alkylcarbonylamino, phenyl, phenoxy, pyridyl, pyridyloxy or C3-C8-cycloalkylcarbonylamino; where the cyclic groups R^b for their part may be partially or fully halogenated and/or may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^c:

R^c is halogen, hydroxyl, nitro, cyano, carboxyl, CrC₄-alkyl, C2-C4- alkenyl, C₂-Ce-alkynyl, CrC₄-haloalkyl, Ci-C₄-alkoxy or C1-C4- haloalkoxy;

R^A,R^B independently of one another are cyano, carboxyl, Ci-C4-alkyl, C₂- C₄-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C₄-alkoxy, Ci-C₄-halo- alkoxy, Cs-Ce-cycloalkyl, C₃-C8-cycloalkenyl, C∑-Cβ-alkenyloxy, C3-C6-alkynyloxy, CrC4-alkoxyimino, C∑-Cs-alkylidene, C3-Cβ-cyclo- alkylidene, Ci-Ci2-alkylamino, Ci-C₄-alkoxycarbonyl, Ci-C₄-alkylcar- bonyloxy, C2-C8-alkylene, C2-C8-oxyalkylene, Ci-Cβ-oxyalkyleneoxy, NR^CR^D, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains 1 to 4 heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^A and/or R^B may for their part be attached directly or via a nitrogen or oxygen atom; where the aliphatic or cyclic groups R^A and/or R^B for their part may be partially or fully halogenated and/or may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^b,

R^B may additionally be hydrogen;

R^C,R^D independently of one another are hydrogen, cyano, carboxyl, Ci-C₄-alkyl, C₂-C₄-alkenyl, C₂-C4-alkynyl, Ci-C₄-haloalkyl, Ci-C4-alkoxy, Ci-C₄-haloalkoxy, C₃-C6-cycloalkyl, C₃-C₈-Cy- cloalkenyl, C∑-Cβ-alkenyloxy, Ca-Cβ-alkynyloxy, Ci-C₄-alkoxy- imino, C∑-Cβ-alkylidene, Ca-Cβ-cycloalkylidene, Ci-Ci₂-alkyl- amino, Ci-C4-alkoxycarbonyl, CrC4-alkylcarbonyloxy, C₂-Ce- alkylene, C₂-Cβ-oxyalkylene, Ci-C₈-oxyalkyleneoxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsat- urated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains 1 to 4 heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^c and/or R^D may for their part be attached directly or via a nitrogen or oxygen atom; L¹,L²,L³,L⁴ independently of one another are hydrogen, halogen, d-C^alkyl,

Ci-C4-haloalkyl, CrC4-alkoxy or Ci-C4-haloalkoxy; where R⁵ and R⁶ in each case together with the atoms linking them may form a five- to ten-membered saturated or partially unsaturated cyclic group which, in addition to the carbon atoms, may contain 1 to 3 heteroatoms from the group consisting of N, O and S and/or may be partially or fully halogenated and/or may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^a; X is oxygen or sulfur; and the N-oxides and agriculturally acceptable salts of the compounds of the formula I.

Moreover, the invention relates to processes for preparing these compounds, to compositions comprising them and to their use for controlling harmful fungi.

Phenylamidines are known in a general manner from WO 2000/046184. Further phenylamidines are disclosed in WO 2003/093224, WO 2007/031508, WO 2007/031512, WO 2007/031513, WO 2007/031523, WO 2007/031524, WO 2007/031526. These compounds are known to be suitable for controlling harmful fungi.

In many cases, in particular at low application rates, the fungicidal activity of the known compounds is unsatisfactory. Based on this fact, it is an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum.

This object has been achieved by the compounds defined at the outset. Furthermore, we have found processes for their preparation, compositions comprising them and methods for controlling harmful fungi using the compounds I. The compounds I according to the invention can be obtained by different routes.

Advantageously, they are prepared by reacting compounds of the formula Il in which Y represents a nucleophilically replaceable group such as halogen, alkylsulfonyloxy and arylsulfonyloxy, preferably chlorine, bromine or iodine, particularly preferably chlorine, with appro

This reaction is usually carried out at from -20⁰C to 150⁰C, preferably at from 0⁰C to

120⁰C, in an inert organic solvent. With particular preference, the reaction is carried out in a neutral or slightly acidic medium which, if appropriate, may be prepared by addition of an acid or, if the salt of the hydroxylamine is used, by addition of a base. Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide. Particular preference is given to methanol, ethanol, propanol, tetrahydrofuran and dioxane. It is also possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, alkali metal and alkaline earth metal alkoxides, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, and also bicyclic amines. Particular preference is given to sodium carbonate, potassium carbonate, sodium bicarbonate, and also to tertiary amines. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

Suitable for use as acids and acidic catalysts are inorganic acids, such as hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, and also organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfionic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid. The acids are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use the hydroxylamine III in excess, based on the ketone M. This reaction may also be carried out in two steps by initially reacting hydroxylamine (formula III where R¹ = hydrogen) or a salt thereof under the conditions described above. The product can then be alkylated to the compound IV using a known process.

Under basic conditions, the compounds of the formula IV are condensed with N-4- mercapto- or N-4-hydroxyphenylamidines of the formula V.

This reaction is usually carried out at from ~40°C to 150°C, preferably from -20⁰C to 120°C, in an inert organic solvent in the presence of a base.

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether (MTBE), dioxane, anisole and tetrahydrofuran (THF), nitriles, such as acetonitrile and propionitrile, ketones, and also dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and dimethylacetamide. Particular preference is given to DMSO, DMF and dimethylacetamide, toluene, MTBE, dioxane, acetonitrile, propionitrile and THF. It is also possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, organometallic compounds, alkylmagnesium halides, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, and also to tertiary amines. The bases are generally employed in equimolar amounts; however, they can also be used in excess or, if appropriate, as solvent.

The starting materials are generally reacted with one another in equimolar amounts.

The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion. The starting materials required for preparing the compounds I are known from the literature or can be prepared in accordance with the literature cited. If individual compounds of the formula I can not be obtained by the routes described above, they can be prepared by derivatization of other compounds I.

If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during preparation for application or during application (for example under the action of light, acid or bases). Such conversions may also take place after application, for example in the case of the treatment of plants in the treated plants or in the harmful fungus to be controlled. In the definitions of the symbols given in the above formulae, collective terms were used which are generally representative for the following substituents: halogen: fluorine, chlorine, bromine and iodine; alkyl: saturated straight-chain or branched hydrocarbon groups having 1 to 4, 6 or 8 carbon atoms, for example C-i-Ce-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl- pentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1 ,2-trimethylpropyl, 1,2,2- trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above: in particular Ci-C2-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difIuoroethyl, 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 -trifluoro- prop-2-yl; alkenyl: unsaturated straight-chain or branched hydrocarbon groups having 2 to 4, 6 or 8 carbon atoms and one or two double bonds in any position, for example C∑-Cβ- alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl- 1-propenyl, 2-methyl- 1-propenyl, 1-methyl-2-propenyl, 2-methyl-2- propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl- 1-butenyl, 3-methyl- 1-butenyl, i-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2- butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2- propenyl, 1,2-dimethyl-1-propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl- 1-propenyl, 1-ethyl- 2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1- pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2- pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3- pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4- pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl- 2-butenyl, 1 ,1-dimethyl-3-butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1,2- dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3- butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3- dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3- butenyl, 1 ,1,2-trimethyl-2-propenyl, 1 -ethyl- 1-methyl-2-propenyl, 1-ethyl-2-methyl-1- propenyl and 1-ethyl-2-methyl-2-propenyl; alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4, 6 or 8 carbon atoms and one or two triple bonds in any position, for example C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3- pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1- pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1 ,1-dimethyl- 2-butynyl, 1,1-dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3- dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1- methyl-2-propynyl; cycloalkyl: mono- or bicyclic saturated hydrocarbon groups having 3 to 6 or 8 carbon ring members, for example C3-Cβ-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; cycloalkenyl: mono- or bicyclic unsaturated hydrocarbon groups having 3 to 6 or 8 carbon ring members and one or two double bonds in any position, for example C3-C8- cycloalkenyl, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctenyl; aryl or aromatic ring: a ring comprising mono-, bi- or tricyclic aromatic hydrocarbon groups and having 6, 8, 10, 12 or 14 ring members, such as phenyl, naphthyl or anthracenyl, preferably phenyl or naphthyl, in particular phenyl; heterocyclyl: three- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which contains one, two, three or four heteroatoms from the group consisting of O, N and S: in particular having five or six ring members non-aromatic saturated or partially unsaturated 5- or 6-membered heterocyclyl which contains one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-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, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1 ,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydro- pyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl; - 5-membered heteroaryl which contains one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1 ,3,4-triazol-2-yl;

6-membered heteroaryl which contains one to three or one to four nitrogen atoms: 6-membered heteroaryl groups which, in addition to carbon atoms, may contain one to three or one to four nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl; cyclic groups: cycloalkyl, cycloalkenyl, aryl or heterocyclyl groups as mentioned above; alkoxy: alkyl groups as mentioned above which are attached to the skeleton via oxygen, for example d-Cβ-alkoxy, such as OCH₃, OCH2CH3, O(CH₂)2CH3, O(CH₂)₃CH₃, O(CH₂)4CH₃, O(CH₂)₅CH₃, O(CH₂)6CH₃ and 0(CH₂J₇CH₃; alkenoxy: alkenyl groups as mentioned above which are attached to the skeleton via oxygen, for example C∑-Cβ-alkenoxy, such as OCH=CH₂, OCH₂CH=CH₂, OCH₂CH=CHCH₃; O(CH₂)₂CH=CHCH₃ and O(CH₂)₃CH=CHCH₃; alkynoxy: alkynyl groups as mentioned above which are attached to the skeleton via oxygen, for example C₃-C₈-alkynoxy, such as 0CH₂C≡CH, O(CH₂)2CH≡CH, O(CH₂)₃CH≡CH and O(CH₂)₄CH≡CH; alkylcarbonyl: alkyl groups as mentioned above which are attached to the skeleton via a carbonyl group, for example Ci-Cβ-alkylcarbonyl, such as COCH₃, COCH₂CH₃, CO(CH₂)₂CH₃, CO(CH₂)₃CH₃, CO(CH₂J₄CH₃, CO(CH₂)₅CH₃, CO(CH₂J₆CH₃ and CO(CH₂J₇CH₃; alkoxycarbonyl: alkoxy groups as mentioned above which are attached to the skeleton via a carbonyl group, for example Ci-C4-alkoxycarbonyl, such as COOCH₃, COOCH₂CH₃, COO(CH₂J₂CH₃, COO(CH₂J₃CH₃, COO(CH₂J₄CH₃, COO(CH₂J₅CH₃, COO(CH₂J₆CH₃ and COO(CH₂J₇CH₃; alkylcarbonyloxy or alkylcarboxyl: alkylcarbonyl groups as mentioned above which are attached to the skeleton via oxo, for example CrC₄-alkylcarbonyloxy, such as OCOCH₃, OCOCH₂CH₃, OCO(CH₂J₂CH₃ and OCO(CH₂J₃CH₃; alkylcarbonylamino: alkylcarbonyl groups as mentioned above which are attached to the skeleton via amino, for example Ci-Cβ-alkylcarbonylamino, such as NHCOCH₃, NHCOCH₂CH₃, NHCO(CH₂J₂CH₃, NHCO(CH₂J₃CH₃, NHCO(CH₂J₄CH₃, NHCO(CH₂J₅CH₃, NHCO(CH₂J₆CH₃ and NHCO(CH₂J₇CH₃; cycloalkylcarbonyl: cycloalkyl groups as mentioned above which are attached to the skeleton via a carbonyl group, for example C₃-C8-cycloalkylcarbonyl, such as cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl and cyclooctylcarbonyl; cycloalkylcarbonylamino: cycloalkylcarbonyl groups as mentioned above which are attached to the skeleton via amino, for example C₃-C8-cycloalkylcarbonylamino, such as cyclopropylcarbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, cycloheptylcarbonylamino and cyclooctylcarbonylamino; alkylene: divalent unbranched chains of 2 to 8 CH₂ groups, for example CH₂CH₂, CH₂CH₂CH₂, CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂CH₂CH₂ and CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂; oxyalkylene: divalent unbranched chains of 2 to 4 CH₂ groups where one valency is attached via an oxygen atom to the skeleton, for example OCH₂CH₂, OCH₂CH₂CH₂ and OCH₂CH₂CH₂CH₂; oxyalkyleneoxy: divalent unbranched chains of 1 to 3 CH₂ groups where both valencies are attached via an oxygen atom to the skeleton, for example OCH₂O, OCH₂CH₂O and OCH₂CH₂CH₂O. alkylidene: divalente straigh-chain or branched hydrocarbon groups which have 2 to 4, 6 or 8 carbon atoms and are attached to the skeleton via a double bond, for example Ci-Cβ-alkylidene, such as methylidene, ethylidene, propylidene, isopropylidene, butylidene, hexylidene and octylidene; cycloalkylidene: cycloalkyl groups as mentioned above which are attached to the skeleton via a double bond, for example C3-Cβ-cycloalkylidene, such as cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene; alkoxyimino: alkoxy groups as mentioned above which are attached to the skeleton via imino, for example Ci-C4-alkoxyimino, such as =NOCH3, =NOCH2CH3, =NO(CH₂)₂CH3, =NO(CH₂)3CH₃, =NO(CH₂)4CH₃, =NO(CH₂)5CH₃, =NO(CH₂)₆CH₃ and =NO(CH₂)₇CH₃; and divalent groups: oxo, alkylene, oxyalkylene, oxyalkyleneoxy, alkylidene and cycloalkylidene groups as mentioned above.

Agriculturally useful salts include in particular the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds of the formula I. Thus, suitable cations are in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry from one to four (Ci-C4)-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, and also phosphonium ions, sulfonium ions, preferably tri(Ci-C4)-alkylsulfonium, and sulfoxonium ions, preferably tri(Ci-C4)-alkylsulfoxonium.

Anions of useful acid addition salts are, primarily, chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and also the anions of (Ci-C4)-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of formula I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The scope of the present invention includes the (R)- and (S)-isomers and the racemates of compounds of the formula I having chiral centers.

As a result of hindered rotation of asymmetrically substituted groups, atrope isomers of compounds of the formula I may be present. They also form part of the subject matter of the invention.

The embodiments of the intermediates with respect to the variables correspond to those of the formula I.

With a view to the intended use of the compounds of the formula I and the compounds of all subformulae mentioned herein, such as formulae 1.1 to 1.10 and I.3A to I.3E, for example, particular preference is given to the following meanings of the substituents R¹, R², R³, R⁴, R⁵, R⁶, R⁷, L¹, L², L³, L⁴ and X, in each case on their own or in combination:

In the compounds according to the invention, R¹ is preferably d-Cβ-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C₃-C8-cycloalkyl, phenyl or a five- or six-membered saturated, partially unsaturated or aromatic heterocyclyl which, in addition to carbon atoms, contains one to three heteroatoms from the group consisting of O, N and S as ring members, where R¹ may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^a which are not heterocyclic groups.

One embodiment relates to compounds I in which R¹ is optionally R^a-substituted d-Cβ-alkyl, C∑-Cβ-alkenyl, C₃-C8-cycloalkyl, phenyl, pyridyl, pyrazolyl, imidazolyl or triazolyl.

A further embodiment relates to compounds I in which R¹ is optionally R^a-substituted C-i-Cβ-alkyl, C₂-C₈-alkenyl, C₃-C₈-cycloalkyl or phenyl.

A further embodiment relates to compounds I in which R¹ is optionally R^a-substituted Ci-Cβ-alkyl.

A further embodiment relates to compounds I in which R¹ is optionally R^a-substituted C₂-C₈-alkenyl. A further embodiment relates to compounds I in which R¹ is optionally R^a-substituted C3-C8-cycloalkyl.

A further embodiment relates to compounds I in which R¹ is optionally R^a-substituted phenyl.

A further embodiment relates to compounds I in which the α carbon atom in R¹ does not carry a cyclic group.

A further embodiment relates to compounds I in which R¹ is optionally R^a-substituted Ci-C₄-alkyl or C₂-C4-alkenyl.

A further embodiment relates to compounds I in which R¹ is optionally R^a-substituted methyl. A further embodiment relates to compounds I in which R¹ is unsubstituted.

Further embodiments relate to compounds I in which R¹ is in each case one of the following groups 1-1 to 1-19 in table I:

Table I:

In the compounds according to the invention, R² is preferably NR^AR^B. Even more preferably, R² is NR^AR^B' wherein R^A is phenyl or Ci-C4-alkyl. Even more preferably, R² is NR^AR^B' wherein R^A is phenyl or Ci-C₄-alkyl and R^B is H.

Another embodiment relates to compounds I in which R² is -[O-(ZH₂)n]m-H, wherein Z are independently of each other carbon or silicium; n is an integer between 1 and 5, m is an integer between 3 and 10.

Another embodiment relates to compounds I, wherein R² is phenoxy, heterocyclyloxy, phenylthio, heterocyclylthio or Ci-Ci₂-alkylthio, more preferably R² is phenoxy.

A further embodiment relates to compounds, R² is Ci-Cs-alkylthio. Further embodiments relate to compounds I in which R² is in each case one of the following groups 11-1 to 11-21 in table II: Table II:

One embodiment relates to compounds I in which X is oxygen. These compounds correspond to the formula 1.3:

A further embodiment relates to compounds I in which X is sulfur. One embodiment relates to compounds I in which R³ is Ci-C4-alkyl or d-Cβ- haloalkyl.

A further embodiment relates to compounds I in which R³ is Ci-C4-alkyl. A further embodiment relates to compounds I in which R³ is Ci-C₈-haloalkyl. A further embodiment relates to compounds I in which R³ is methyl. A further embodiment relates to compounds I in which R⁴ is hydrogen. These compounds correspond to the formula 1.4:

A further embodiment relates to compounds I in which R³ and R⁴ are hydrogen. These compounds correspond to the formula 1.5:

A further embodiment relates to compounds I in which R³ and R⁴ are not hydrogen. A further embodiment relates to compounds I in which X is oxygen and R³ and R⁴ are hydrogen. These compounds correspond to the formula I.3A:

A further embodiment relates to compounds I in which X is oxygen, R³ is methyl and

R⁴ is hydrogen. These compounds correspond to the formula I.3B:

A further embodiment relates to compounds I in which X is oxygen and R³ and R⁴ are methyl. These com

A further embodiment relates to compounds I in which X is oxygen, R³ is ethyl and R⁴ is hydrogen. These compounds correspond to the formula 1.3D:

A further embodiment relates to compounds I in which X is oxygen, R³ is ethyl and R⁴ is methyl. These compounds correspond to the formula I.3E:

One embodiment relates to compounds I in which R⁵ is methyl or ethyl. A further embodiment relates to compounds I in which R⁵ is methyl. One embodiment relates to compounds I in which R⁶ is ethyl. Further embodiments relate to compounds I in which R⁵ and R⁶ are one of the following combinations III-1 to III— 43 in table III: Table III:

One embodiment relates to compounds I in which L¹ and L² independently of one another are halogen, C-ι-C₄-alkyl, Ci-C4-haloalkyl or CrC4-haloalkoxy, even more preferably selected from the group of CH₃, CF₃, OCHF₂ and OCF₃.

Another embodiment relates to compounds I in which L¹ and L² independently of one another are halogen, such as chlorine or fluorine. A further embodiment relates to compounds I in which L¹ and L² independently of one another are methyl or halomethyl, such as CF₃, CCI3, CH₂CI, CH₂F, CHF₂ or CHCI₂.

A further embodiment relates to compounds in which L¹ and L² are methyl.

A futher embodiment relates to compounds I in which L¹ and L² independently of one another are Ci-C4-haloalkoxy, preferably OCHF₂ or OCF3.

One embodiment relates to compounds I in which L³ and L⁴ are hydrogen. These compounds correspond to the formula 1.6:

A more prefered embodiment relates to compounds I in which L³. L⁴, R³ and R⁴ are hydrogen. These compounds correspond to the formula I.6B:

A preferred embodiment relates to compounds I in which L¹ and L² independently of one another are halogen or Ci-C4-alkyl and L³ and L⁴ are hydrogen.

Preferably, R⁵ and R⁶ in the compounds I according to the invention are Ci-C₄-alkyl which may carry one, two, three, four or five identical or different groups R^a.

One embodiment relates to compounds I in which R⁵ and R⁶ are Ci-C₄-alkyl. One embodiment relates to compounds I in which R⁷ is unsubstituted. One embodiment relates to compounds I in which R⁷ is hydrogen. These compounds correspond to the formula I.7:

A further embodiment relates to compounds I in which R⁷ is methyl.

In the compounds according to the invention, R^a is preferably halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C₄-haloalkoxy, phenyl or a five- or six-membered saturated, partially unsaturated or aromatic heterocyclyl which, in addition to carbon atoms, contains one to three heteroatoms from the group consisting of O, N and S as ring members, where the cyclic groups R^a may be attached directly or via a nitrogen or oxygen atom; where the aliphatic and cyclic groups R^a for their part may be partially or fully halogenated and/or may carry one, two, three or up to the maximum possible number of identical or different groups R^b, where R^b is halogen, Ci-C₄-alkyl, C1-C₄- haloalkyl, Ci-C4-alkoxy or Ci-C₄-haloalkoxy.

In the compounds according to the invention, R^a is in particular halogen, Ci-C₄-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, phenyl, pyridyl, pyrimidinyl, pyridazinyl, triazinyl, pyrazolyl, imidazolyl or triazolyl, where the cyclic groups R^a may be attached directly or via an oxygen atom, where the aromatic and heterocyclic groups R^a for their part may be partially or fully halogenated and/or may carry one, two, three or up to the maximum possible number of identical or different groups R^b, where R^b is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy.

In a further preferred embodiment, R^a in the compounds according to the invention is halogen, Ci-C4-alkyl, CrC4-alkoxy, Ci-C4-haloalkoxy, phenyl or pyridyl, where the cyclic groups R^a may be attached directly or via an oxygen atom, where the aromatic and heterocyclic groups R^a for their part may be partially or fully halogenated and/or may carry one, two, three or up to the maximum possible number of identical or different groups R^b, where R^b is halogen, CrC4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C₄-haloalkoxy.

A further embodiment relates to compounds I in which R⁴, R⁷, L³ and L⁴ are hydrogen and X is oxygen. These compounds correspond to the formula 1.8:

A further embodiment relates to compounds I in which R⁴, R⁷ and L⁴ are hydrogen and X is oxygen. These compounds correspond to the formula 1.9:

According to a preferred embodiment of the compounds I:

R¹ is CrCβ-alkyl, C2-C8-alkenyl, Cs-Cβ-cycloalkyl, phenyl, pyridyl, pyrazoloyl, imidazolyl or triazolyl, where R¹ may carry one, two, three or up to the maximum possible number of identical or different groups R^a which are not heterocyclic groups; R² is NR^AR^B;

R^a is amino, halogen, hydroxyl, oxo, nitro, cyano, carboxyl, Ci-C4-alkyl, C2-C4- alkenyl, C2-C4-alkynyl, Ci-C₄-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C3-C6-cycloalkyl, Cs-Cβ-cycloalkenyl, C∑-Cβ-alkenyloxy, Cs-Cβ-alkynyloxy, Ci-C₄-alkoxyimino, C∑-Ca-alkylidene, C₃-C8-cycloalkylidene, C1-C12- alkylamino, Ci-C₄-alkoxycarbonyl, Ci-C₄-alkylcarbonyloxy, NR^AR^B, C₂-Ce- alkylene, C2-Cβ-oxyalkylene, d-Cβ-oxyalkyleneoxy, phenyl, naphthyl or a three- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^a may be attached directly or via a nitrogen or oxygen atom; where the aliphatic or cyclic groups R^a for their part may be partially or fully halogenated and/or may carry one, two, three or up to the maximum possible number of identical or different groups R^b: R^b is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C₄- haloalkoxy;

R^A,R^B independently of one another are cyano, carboxyl, Ci-C₄-alkyl, C2- C₄-alkenyl, C₂-C₄-alkynyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy, Ci-C4-halo- alkoxy, Cs-Cβ-cycloalkyl, C3-Cβ-cycloalkenyl, C2-C6-alkenyloxy, Cs-Cβ-alkynyloxy, Ci-C4-alkoxyimino, C∑-Cβ-alkylidene, C3-Cβ-cyclo- alkylidene, Ci-Ci2-alkylamino, Ci-C4-alkoxycarbonyl, Ci-C₄-alkylcar- bonyloxy, C2-Ce-alkylene, C∑-Cβ-oxyalkylene, d-Cβ-oxyalkyleneoxy, NR^CR^D, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains 1 to 4 heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^A and/or R^B may for their part be attached directly or via a nitrogen or oxygen atom; where the aliphatic or cyclic groups R^A and/or R^B for their part may be partially or fully halogenated and/or may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^b, R^B may additionally be hydrogen; R^C,R^D independently of one another are hydrogen, cyano, carboxyl,

Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy, Ci-C₄-haloalkoxy, C₃-C6-cycloalkyl, C₃-C₈-Cy- cloalkenyl, C₂-C6-alkenyloxy, C₃-C6-alkynyloxy, Ci-C4-alkoxy- imino, C₂-C8-alkylidene, Cs-Cβ-cycloalkylidene, CrCi2-alkyl- amino, Ci-C4-alkoxycarbonyl, Ci-C4-alkylcarbonyloxy, C∑-Cβ- alkylene, C2-C8-oxyalkylene, Ci-C₈-oxyalkyleneoxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains 1 to 4 heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^c and/or R^D may for their part be attached directly or via a nitrogen or oxygen atom;

R³, R⁴ independently of one another are hydrogen, Ci-C₄-alkyl or Ci-Cβ-haloalkyI; R⁵,R⁶is Ci-C₄-alkyl; R⁷ is hydrogen;

L¹, L² independently of one another are halogen, CrC₄-alkyl, Ci-C₄-haloalkyl or Ci-C₄-haloalkoxy;

L³, L⁴ are hydrogen; and X is oxygen. These compounds correspond to the formula 1.10:

According to a further preferred embodiment of the compounds I: R¹ Ci-Cβ-alkyl, C2-C8-alkenyl, C3-Cs-cycloalkyl or phenyl, where R¹ may carry one, two, three or up to the maximum possible number of identical or different groups

R^a which are not heterocyclic groups; is NR^AR^B;

R^a is amino, halogen, hydroxyl, oxo, nitro, cyano, carboxyl, Ci-C4-alkyl, C2-C4- alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C₄-haloalkoxy, C3-C6-cycloalkyl, Cs-Cs-cycloalkenyl, C∑-Cβ-alkenyloxy, Cs-Cβ-alkynyloxy,

Ci-C₄-alkoxyimino, C2-Cs-alkylidene, C₃-C8-cycloalkylidene, C1-C12- alkylamino, Ci-C4-alkoxycarbonyl, Ci-C₄-alkylcarbonyloxy, NR^AR^B, C₂-C₈- alkylene, C2-Cβ-oxyalkylene, d-Cβ-oxyalkyleneoxy, phenyl, naphthyl or a three- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^a may be attached directly or via a nitrogen or oxygen atom; where the aliphatic or cyclic groups R^a for their part may be partially or fully halogenated and/or may carry one, two, three or up to the maximum possible number of identical or different groups R^b: R^b is halogen, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy or Ci-C₄- haloalkoxy;

R^A,R^B independently of one another are CrC₄-alkyl or phenyl; where the aliphatic or cyclic groups R^A and/or R^B for their part may be partially or fully halogenated and/or may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^b, R^B may additionally be hydrogen;

R^C,R^D independently of one another are hydrogen, cyano, carboxyl, Ci-C₄-alkyl, C₂-C4-alkenyl, C₂-C₄-alkynyl, Ci-C4-haloalkyl,

Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ca-Cβ-cycloalkyl, C3-Cβ-cy- cloalkenyl, C∑-Cβ-alkenyloxy, C3-C6-alkynyloxy, Ci-C4-alkoxy- imino, C∑-Cβ-alkylidene, Cs-Cβ-cycloalkylidene, Ci-Ci2-alkyl- amino, Ci-C4-alkoxycarbonyl, Ci-C4-alkylcarbonyloxy, C₂-Ce- alkylene, C∑-Cs-oxyalkylene, Ci-Cβ-oxyalkyleneoxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains 1 to 4 heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^c and/or R^D may for their part be attached directly or via a nitrogen or oxygen atom;

R³, R⁴ independently of one another are hydrogen, Ci-C4-alkyl or Ci-Cβ-haloalkyl; R⁵, R⁶ are Ci-C₄-alkyl; R⁷ is hydrogen;

L¹, L² independently of one another are halogen, Ci-C4-alkyl, Ci-C4-haloalkyl or

Ci-C4-haloalkoxy; L³, L⁴ are hydrogen; and X is oxygen. These compounds correspond to the formula 1.10.

The compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.

The compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.

Preferably, compounds I and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

The term "plant propagation material" is to be understood to denote all the genera- tive parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germi- nation or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.

Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans. The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agrLproducts.asp). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.

The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sun- flowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape {A. brassicola or brassicae), sugar beets {A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. so/an/or A. alternata), tomatoes (e. g. A. so/an/ or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. //77/c/(anthracnose) on wheat and A. horde/on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolυs spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e.g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana. grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchil) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvunr. leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; CocMobo/υs (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodesr. black dot), beans (e. g. C. lindemυthianum) and soybeans (e. g. C. truncatumox C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendrf. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechs- lera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis. tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeha obtusa, E/s/noe spp. on pome fruits (E pyrή, soft fruits (E. veneta. anthracnose) and vines (E ampe/ina. anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pis/), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. so/an/ on soybeans and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi. Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grain- staining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; lsariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata. stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola. can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsicl), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans. late blight) and broad-leaved trees (e. g. P. ramorum. sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. ha/sted/i on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha or\ apples; Po/ymyxaspp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets {P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensisou cucurbits or P. hum/7/ on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; Pucc/niaspp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. horde/^' (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, and asparagus (e. g. P. asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricu/ariaspp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soy- beans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R. collo-cygni (Ramu\ar\a leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solan/ ^'(root and stem rot) on soybeans, R. so/ani {sheain blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus sto/onifer (b\ack mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotica spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. 5. rolfsiiox S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and 5. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tucker!) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. tυrcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. 5. re/liana, head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. 5. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. prυni(p\um pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritic/(syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Uro- cystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoll) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nυdaanό U. avaenae), corn (e. g. U. maydis. corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.

The compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials. The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, colling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humico/a spp., Petriella spp., Trichurus spp. ; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., A/ternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae. The compounds I and compositions thereof, resepectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively. The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.The above identified indicators for the health condition of a plant may be interdependent or may result from each other.

The compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention. The compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infec- tion of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.

Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting. The invention also relates to agrochemical compositions comprising a solvent or solid carrier and at least one compound I and to the use for controlling harmful fungi. An agrochemical composition comprises a fungicidally effective amount of a compound I. The term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.

The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.

Examples for composition types are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water- soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF).

Usually the composition types (e. g. SC, OD, FS, EC, WG, SG, WP, SP, SS, WS, GF) are employed diluted. Composition types such as DP, DS, GR, FG, GG and MG are usually used undiluted.

The compositions are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001).

The agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions. The auxiliaries used depend on the particular application form and active substance, respectively. Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti- foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations).

Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore 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, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e. g. amines such as N-methylpyrrolidone.

Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers. Suitable surfactants (adjuvants, wtters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse^® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet^® types, Akzo Nobel, U.S.A.), dibutylnaphthalene- sulfonic acid (Nekal^® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl- arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearyl- phenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol^® types, Clariant, Switzer- land), polycarboxylates (Sokolan^® types, BASF, Germany), polyalkoxylates, polyvinyl- amines (Lupasol^® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.

Examples for thickeners (i. e. compounds that impart a modified flowability to compositions, i. e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan^®, CP Kelco, U.S.A.), Rhodopol^® 23 (Rhodia, France), Veegum^® (RT. Vanderbilt, U.S.A.) or Attaclay^® (Engelhard Corp., NJ, USA).

Bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzyl- alcohol hemi formal (Proxel^® from ICI or Acticide^® RS from Thor Chemie and Kathon^® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide^® MBS from Thor Chemie). Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Examples for anti-foaming agents are silicone emulsions (such as e. g. Silikon^® SRE, Wacker, Germany or Rhodorsil^®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof. Suitable colorants are pigments of low water solubility and water-soluble dyes.

Examples to be mentioned und the designations rhodamin B, C. I. pigment red 112, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1 , pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

Examples for tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose^®, Shin-Etsu, Japan). Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the compounds I and, if appropriate, further active substances, with at least one solid carrier.

Granules, e. g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

Examples for composition types are: 1. Composition types for dilution with water i) Water-soluble concentrates (SL, LS) 10 parts by weight of a compound I according to the invention are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a composition having a content of 10% by weight of active substance is obtained. ii) Dispersible concentrates (DC)

20 parts by weight of a compound I according to the invention are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e. g. polyvinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight. iii)Emulsifiable concentrates (EC)

15 parts by weight of a compound I according to the invention 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 with water gives an emulsion. The composition has an active substance content of 15% by weight. iv)Emulsions (EW, EO, ES)

25 parts by weight of a compound I according to the invention 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 introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight. v) Suspensions (SC, OD₁ FS) In an agitated ball mill, 20 parts by weight of a compound I according to the invention are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight. vi)Water-dispersible granules and water-soluble granules (WG, SG)

50 parts by weight of a compound I according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. The composition has an active substance content of 50% by weight. vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)

75 parts by weight of a compound I according to the invention are ground in a rotor- stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance. The active substance content of the composition is 75% by weight. viii) Gel (GF)

In an agitated ball mill, 20 parts by weight of a compound I according to the invention are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained.

2. Composition types to be applied undiluted ix)Dustable powders (DP, DS)

5 parts by weight of a compound I according to the invention are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight. X) Granules (GR₁ FG, GG, MG)

0.5 parts by weight of a compound I according to the invention is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray- drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by weight. Xi)ULV solutions (UL)

10 parts by weight of a compound I according to the invention are dissolved in 90 parts by weight of an organic solvent, e. g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). Water-soluble concentrates (LS), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted. The compositions in question give, after two-to- tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting. In a preferred embodiment, a suspension-type (FS) composition is used for seed treatment. Typcially, a FS composition may comprise 1-800 g/l of active substance, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

The active substances can be used as such or in the form of their compositions, e. g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active substances according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water. The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1% by weight of active substance.

The active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.

When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha. In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required. When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, e. g., 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions com- prising them, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.

Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240^®; alcohol alkoxylates such as Atplus 245^®, Atplus MBA 1303^®, Plurafac LF 300^® and Lutensol ON 30^®; EO/PO block polymers, e. g. Pluronic RPE 2035^® and Genapol B^®; alcohol ethoxylates such as Lutensol XP 80^®; and dioctyl sulfosuccinate sodium such as Leophen RA^®.

The compositions according to the invention can, in the use form as fungicides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).

Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance develop- ment. Furthermore, in many cases, synergistic effects are obtained.

The following list of active substances, in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them: A) strobilurins

- azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, trifloxystrobin, 2-[2- (2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-

(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2- methoxyimino-N-methyl-acetamide;

B) carboxamides

- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fen- furam, fenhexamid, flutolanil, fluxapyroxad, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxanilide, N-(4¹-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide and N-(2-(1 ,3,3-trimethyl- butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide;

- carboxylic morpholides: dimethomorph, flumorph, pyrimorph;

- benzoic acid amides: flumetover, fluopicolide, fluopyram, zoxamide;

- other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthiofarm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide; C) azoles

- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothio- conazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole;

- imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol;

- benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;

- others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-di- methoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;

D) heterocyclic compounds

- pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine;

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

- piperazines: triforine;

- pyrroles: fenpiclonil, fludioxonil;

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

- dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;

- non-aromatic 5-membered heterocycles: famoxadone, fenamidone, flutianil, octhilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro- pyrazole-1-carbothioic acid S-allyl ester;

- others: acibenzolar-S-methyl, ametoctradin, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4- one, 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole and 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo- [1 ,5-a]pyrimidine; E) carbamates - thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram;

- carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamo- carb hydrochlorid, valifenalate and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2- yl) carbamic acid-(4-fluorophenyl) ester; F) other active substances

- guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);

- antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, validamycin A; - nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;

- sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane;

- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;

- organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quinto- zene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide; - inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

- antifungal biocontrol agents, plant bioactivators: Ampelomyces quisqualis (e.g. AQ 10^® from lntrachem Bio GmbH & Co. KG, Germany), Aspergillus flaws (e.g. AFLAGUARD^® from Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR^® from bio-ferm GmbH, Germany), Bacillus pυmilius (e.g. isolate NRRL-Nr. B-21661 in RHAPSODY^®, SERENADE^® MAX and SERENADE^® ASO from Fa. AgraQuest Inc., USA), Bacillus subti/isvar. amyloliquefaciens FZB24 (e.g. TAEGRO^® from Novozyme Biologicals, Inc., USA), Candida oleophila I-82 (e.g. ASPIRE^® from Ecogen Inc., USA), Candida saitoana (e.g. BIOCURE^® (in mixture with lysozyme) and BIOCOAT^® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g. ARMOUR- ZEN from BotriZen Ltd., NZ), Clonostachys rosea f. catenulata, also named Gliocladium catenulatum (e.g. isolate J1446: PRESTOP^® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS^® from Prophyta, Germany), Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g. YIELD PLUS^® from Anchor Bio-Technologies, South Africa), Fusarium oxysporum (e.g. BIOFOX^® from S.I.A.P.A., Italy, FUSACLEAN^® from Natural Plant Protection, France), Metschnikowia fructicola (e.g. SHEMER^® from Agrogreen, Israel), Microdochium dimerυm (e.g. ANTIBOT^® from Agrauxine, France), Phlebiopsis gigantea (e.g. ROTSOP^® from Verdera, Finland), Pseudozyma flocculosa (e.g. SPORODEX^® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVERSUM^® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis (e.g. REGALIA^® from Marrone Biolnnovations, USA), Talaromyces flavusVλ λlb (e.g. PROTUS^® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE^® from Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL^® from Agrimm Technologies Ltd, NZ), T. harzianum T-22 (e.g. PLANTSHIELD^® der Firma BioWorks Inc., USA), T. harzianum JH 35 (e.g. ROOT PRO^® from Mycontrol Ltd., Israel), T. harz/anυmT-39 (e.g. TRICHODEX^® and TRICHODERMA 2000^® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum ¹ ICCOI 2 and T. w/70te lCC080 (e.g. REMEDIER^® WP from lsagro Ricerca, Italy), T. polysporum and T. harzianum (e.g. BINAB^® from BINAB Bio-Innovation AB, Sweden), T. stromaticυm (e.g. TRICOVAB^® from C.E.P.LA.C, Brazil), T. virens GL- 21 (e.g. SOILGARD^® from Certis LLC, USA), T. viride (e.g. TRIECO^® from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE^® F from T. Stanes & Co. Ltd., Indien), T. virideTVλ (e.g. T. viride TV1 from Agribiotec srl, Italy), Ulocladium oudemansi/ΗR\J3 (e.g. BOTRY-ZEN^® from Botry-Zen Ltd, NZ);

- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metrafenone, pyriofenone, mildiomycin, oxin-copper, prohexadione-calcium, spiroxamine, tebufloquin, tolylfluanid, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3- difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3- trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2- methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine,

2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4- carboxylic acid methyl-(1,2,3₎4-tetrahydro-naphthalen-1-yl)-amide₎ 2-{1-[2-(5-meth- yl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide, methoxy-acetic acid 6-tert- butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester and ΛAMethyl-2-{1-[(5-methyl-3- trifluoromethyl-1 H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-ΛA[(1 R)-1,2,3,4-tetrahydro- naphthalen-1-yl]-4-thiazolecarboxamide. G) growth regulators abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dike- gulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, iπabeπfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tιϊ-iodobenzoic acid , trinexapac-ethyl and uniconazole; H) herbicides

- acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor; - amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;

- aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;

- Bipyridyls: diquat, paraquat;

- (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;

- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;

- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;

- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen;

- hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;

- imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;

- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;

- pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;

- pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;

- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6- dimethoxy-pyrimidin-2-yl)urea;

- triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;

- ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron.tebuthiuron;

- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;

- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone.benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon- ethlyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4- trifluoromethyl-S.δ-dihydro^H-pyrimidin-i-yO-phenoxyJ-pyridin^-yloxyJ-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3- chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic acid methyl ester, and 4- amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester. I) insecticides

- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;

- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;

- pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfen- valerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin;

- insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etox- azole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;

- nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro- thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3,5]triazinane; - GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl- 1 H-pyrazole-3-carbothioic acid amide;

- macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram; - mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;

- METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;

- Uncouplers: chlorfenapyr;

- oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite;

- moulting disruptor compounds: cryomazine;

- mixed function oxidase inhibitors: piperonyl butoxide;

- sodium channel blockers: indoxacarb, metaflumizone;

- others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon.

The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to I) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to F), as described above, and if desired one suitable solvent or solid carrier. Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Furthermore, combating harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to F), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to F). By applying compounds I together with at least one active substance from groups A) to I) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures).

According to this invention, applying the compounds I together with at least one further active substance is to be understood to denote, that at least one compound of formula I and at least one further active substance occur simultaneously at the site of action (i.e. the harmful fungi to be controlled or their habitats such as infected plants, plant propagation materials, particularly seeds, surfaces, materials or the soil as well as plants, plant propagation materials, particularly seeds, soil, surfaces, materials or rooms to be protected from fungal attack) in a fungicidally effective amount. This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or sperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.

In binary mixtures, i.e. compositions according to the invention comprising one compound I (component 1) and one further active substance (component 2), e. g. one active substance from groups A) to I), the weight ratio of component 1 and component 2 generally depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1, more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :3 to 3: 1.

In ternary mixtures, i.e. compositions according to the invention comprising one compound I (component 1) and a first further active substance (component 2) and a second further active substance (component 3), e. g. two active substances from groups A) to I), the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1 , and the weight ratio of component 1 and component 3 preferably is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 : 10 to 10: 1.

The active substances referred to as component 2, their preparation and their activity against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.

I. Synthesis examples

With appropriate modification of the starting materials, the procedures given in the synthesis examples below were used to obtain further compounds I. The compounds produced in this manner are listed in Table C below. The corresponding physical data can be found in Table D. Example 1 : Synthesis of N'-(4-{2-[ethoxyimino]-3-[2-trifluoromethylphenylhydrazinyl]- ethoxy}-2,5-dimethyl-phenyl)-N-ethyl-N-methyl-formamidine (example no. C-2) a) Synthesis of 1-Chloro-2-(ethoxyimino)-2-(2-trifluoromethylphenylhydrazinyl)-ethane A mixture of 1.0 g of o-trifluoromethylphenylhydrazine and 4.2g of chloroacetonitril and 773mg of anhydrous zinc chloride in 20 ml of anhydrous 4N solution of HCI in dioxane was stirred at about 20-25°C for 20 about hours. The solvent was evaporated at reduced pressure and the residue was dissolved in 20 ml of anhydrous ethanol, 630mg of O-ethylhydroxylamine were added and the mixture was stirred at about 20- 25⁰C for 20 hours. After evaporation of the solvent at reduced pressure the residue was dissolved in ethylacetate and washed twice with aqueous sodium hydrogencarbonate solution, dried over sodium sulfate and the solvent was evaporated at reduced pressure which yielded 2.5g of the title compound. b) Synthesis of N^l-(4-{2-[ethoxyimino]-3-[2-trifluoromethylphenylhydrazinyl]-ethoxy}-2,5- dimethyl-phenyl)-N-ethyl-N-methyl-formamidine

1.07g of N'-(4-hydroxy-2,5-dimethyl-phenyl)-N-Ethyl-N-methyl-formamidine were dissolved in 10 ml of anhydrous DMSO and 877mg of potassium tert.-butoxide were added at about 20-25⁰C and stirred for 5 minutes. This solution was added dropwise via syringe to a solution of 1.85 g of

1 -chloro-2-(ethoxyimino)-2-(2-trifluoromethylphenylhydrazinyl)-ethane dissolved (see preceding intermediate) in 27ml of anhydrous DMSO and 26mg of 18-crown-6 at about 20-25⁰C and stirred until the chloro compound was consumed. The reaction mixture was poured into 40ml of water and extracted tree times with ethyl acetate. The organic phases were dried over anhydrous sodium sulfate and the solvent was evaporated at reduced pressure. The residue was submitted to preparative HPLC with a gradient of water and acetonitril and 0.1% of trifluoroacetic acid that yielded 23 mg of the product.

Example 2: Synthesis of N-(3,4-dichloro-phenyl)-N'-methoxy-2-{4-[(ethyl-methyl- amino)-methyleneamino]-2,5-dimethyl-phenoxy}-acetamidine (example no. C-4) a) Synthesis of 2-chloro-N-(3,4-dichloro-phenyl)-N'-methoxy-acetamidine

A mixture of 1.1 g of 3,4-dichloroanilin and 678mg of chloroacetonitrile in 15 ml of anhydrous dioxane and 5 ml of anhydrous 4N solution of HCI in dioxane was stirred at about 20-25⁰C for 20 hours. Additional chloroacetonitrile and HCI solution were added to drive the reaction to completion. The solvent was evaporated at reduced pressure and 250 mg of the residue were dissolved in 10 ml of anhydrous ethanol, 76mg of O- ethylhydroxylamine and 0.13ml (0.91 mmol) of triethylamine were added and the mixture was stirred at about 20-25⁰C for 20 hours. After evaporation of the solvent at reduced pressure the residue was dissolved in ethylacetate and washed twice with aqueous sodium hydrogencarbonate solution, dried over sodium sulfate and the solvent was evaporated at reduced pressure. Column chromatography of the residue with a gradient of DCM and methanol as eluent yielded 85mg of the product. b) Synthesis of N-(3,4-dichloro-phenyl)-N'-methoxy-2-{4-[(ethyl-methyl-amino)- methyleneamino]-2,5-dimethyl-phenoxy}-acetamidine

52 mg of N'-(4-hydroxy-2,5-dimethyl-phenyl)-N-ethyl-N-methyl-formamidine were dissolved in 1.5 ml of anhydrous DMF and 32 mg of sodium hydride were added at about 0°C and stirred for 15 minutes at about 20-25⁰C. Then a solution of 85mg of 2- chloro-N-(3,4-dichloro-phenyl)-N'-methoxy-acetamidine dissolved in 1 ml of anhydrous DMF was added dropwise at about 20-25⁰C followed by the addition of 2mg of 15- crown-5. The reaction mixture was stirred at about 20-25⁰C for 16 hours. It was then poured into 40ml of water and extracted three times with ethyl acetate. The organic phases were dried over anhydrous sodium sulfate and the solvent was evaporated at reduced pressure. The residue was submitted to preparative HPLC with a gradient of water and acetonitril and 0.1 % of trifluoroacetic acid that yielded 40mg of the product.

Example 3: Synthesis of N'-(4-{2-[methoxyimino]-3-[N"-methylN"-phenylhydrazinyl]- propoxy}-2,5-dimethyl-phenyl)-N-ethyl-N-methyl-formamidine (example no. C-9) a) Synthesis of 1-chloro-2-(methoxyimino)-2-(N-methyl-N-phenylhydrazinyl)-ethane A mixture of 1.Og of 1-methyl-i-phenylhydrazine, 927mg of chloroacetonitrile and

558mg of anhydrous zinc chloride in 5 ml of anhydrous dioxane and 10 ml of anhydrous 4N solution of HCI in dioxane was stirred at about 20-25⁰C for 60 hours. Additional chloroacetonitrile and zinc chloride were added to drive the reaction to completion. The solvent was evaporated at reduced pressure and 950 mg of the residue was dissolved in 10 ml of anhydrous ethanol, 339 mg of O-ethylhydroxylamine and 0.56ml of triethylamine were added and the mixture was stirred at about 20-25⁰C for 20 hours. After evaporation of the solvent at reduced pressure the residue was dissolved in ethylacetate and washed twice with aqueous sodium hydrogencarbonate solution, dried over sodium sulfate and the solvent was evaporated at reduced pressure which yielded 540 mg of the title compound. b) Synthesis of N'-(4-{2-[methoxyimino]-3-[N"-methylN"-phenylhydrazinyl]-propoxy}-2,5- dimethyl-phenyl)-N-ethyl-N-methyl-formamidine 250mg of N'-(4-hydroxy-2,5-dimethyl-phenyl)-N-ethyl-N-methyl-formamidine were dissolved in 9.5 ml of anhydrous DMSO and 204mg of potassium tert-butoxide were added at about 20-25⁰C and stirred for 5 minutes. This solution was added dropwise via syringe to a solution of 352 mg of 1-chloro-2-(methoxyimino)-2-(N-methyl-N- phenylhydrazinyl)-ethane dissolved in 0.5 ml of anhydrous DMSO at about 20-25⁰C followed by the addition of 6 mg of 18-crown-6. The reaction mixture was stirred at about 8O⁰C for 16 hours. Then it was poured into 40 ml of water and extracted three times with ethyl acetate. The organic phases were dried over anhydrous sodium sulfate and the solvent was evaporated at reduced pressure. After column chromatography on silica gel with a gradient of DCM and methanol as eluent yielded 220mg of the product.

Example 3: Synthesis of N-ethoxy-2-{4-[(ethyl-methyl-amino)-methyleneamino]-2,5- dimethyl-phenoxy}-thioacetimidic acid ethyl ester (example no. C-11) 640mg (2.61 mmol) of N'-(4-cyanomethoxy-2,5-dimethyl-phenyl)-N-ethyl-N-methyl- formamidine were dissolved in 10 ml of an anhydrous 4N solution of HCI in dioxane, 178mg of ethane thiol were added. The reaction mixture was stirred at about 80⁰C for 5 hours in an microwave oven and after that the solvent was evaporated at reduced pressure. The crude mixture was dissolved in acetonitril, 219 mg of O- ethylhydroxylamine hydrochloride were added in one portion and the mixture was stirred at about 20-25⁰C for 20 hours and for further 6 hours at about 40⁰C. The solvent was evaporated at reduced pressure and column chromatography on silica gel with a gradient of DCM and methanol as eluent yielded 230mg of the product.

Example 4: Synthesis of N-cyclopropylmethyl-2-{4-[(ethyl-methyl-amino)-methylene- amino]-2,5-dimethyl-phenoxy}-N'-methoxy-acetamidine (example no. C-19) a) Synthesis of N'-(4-cyanomethoxy-2,5-dimethyl-phenyl)-N-ethyl-N-rnethyl- formamidine

To 50,0 g N-ethyl-N'-(4-hydroxy-2,5-dimethyl-phenyl)-N-methyl-formamidine (see WO 2007/031513) in 180 ml DMSO were added 32.6 g potassium tert.-butylate with stirring at about 20-25⁰C. After 10 min 641 mg 18-crown-6 and 21.96 g chloroacetonitrile were added slowly at about 2-25°C with stirring. After 20 h another 500 mg chloroacetonitrile were added and stirring was continued for 20 h at about 20- 25°C. The resulting mixture was poured into 2 I of water, adjusted to pH 9 with sodium carbonate and extracted 3 times with 700 ml of MTBE each. The combined organic layers were dried with sodium sulfate, filtrated and the solvent evaporated to yield 55.7 g of a crude oil which was purified by chromatography on silica with cyclohex- ane/MTBE as eluents. Yield was 31.7 g of pure title product. b) Syntesis of 2-{4-[(ethyl-methyl-amino)-methyleneamino]-2,5-dimethyl-phenoxy}- N-methoxy-acetamidine

To 15.8 g N'-(4-cyanomethoxy-2,5-dimethyl-phenyl)-N-ethyl-N-methyl-formamidine in 150 ml methanol were added 308 mg lithium hydroxide. After stirring for 2 h at about 20-25⁰C, 6.45 g methoxyamine hydrochloride were added and the mixture stirred over night at about 20-25⁰C. The solvent was removed in vacuo to yield 22.8 g of crude product to which 200 ml MTBE and 150 ml saturated aqueous sodium hydrogen- carbonate solution were added. The organic layer was collected, washed 3 times with 50 ml of water each, dried with sodium sulfate and the solvent removed in vacuo. Yield was 17.0 g of crude product which was used without further purification. c) Synthesis of N-cyclopropylmethyl-2-{4-[(ethyl-methyl-amino)-methyleneamino]- 2,5-dimethyl-phenoxy}-N'-methoxy-acetamidine

To 300 mg 2-{4-[(ethyl-methyl-amino)-methyleneamino]-2,5-dimethyl-phenoxy}- N-methoxy-acetamidine in 4 ml DMSO 135 mg potassium tert.-butylate were added and stirred for 15 min at about 20-25⁰C. Then 10 mg of 18-crown-6 were added followed by 165 mg cyclopropylmethylbromide in 2 ml DMSO. After stirring over night at about 20-25⁰C the mixture was poured into 40 ml MTBE and 60 ml water. The aqueous layer was extracted twice with 10 ml MTBE each. The combined organic layers were washed 3 times with 10 ml of water each, dried with sodium sulphate, filtrated and the solvent removed in vacuo to yield 240 mg of crude product. It was purified by mplc on a Merck Chromolith RP18e 100 x 25 mm column with a water plus 0.1 % acetic acid/acetonitrile gradient. The pure fractions were dissolved in acetic acetate, washed with aqueous sodium hydrogen carbonate and water, dried with sodium sulfate and the solvent removed in vacuo and yielded 140 mg of the title compound.

Table C - Compounds of the formula I.6B.

Table D. Physical data for compounds of the formula I.6B according to Table C

(s);

(s).

(d) 3.85. (s);

(s);

3.41

(q);

(s); 7.40

3.97

3.47

3.20 7.00-

No. in

Phys. data (¹H-NMR: δ [ppm]; HPLC/MS: R₄ [min]; m.p. [⁰C]) Table C

C-17 HPLC/MS: R, = 1.585.

C-18 m.p.: 135-155°C.

C-19 ¹H-NMR (CDCI₃): δ = 0.18 (m); 0.50 (m); 1.00 (m); 1.22 (t); 2.17 (s); 2.23 (s); 2.97 (S); 3.13 (m); 3.34 (broad); 3.82 (s); 4.47 (s); 5.12 (broad); 6.55 (s); 6.71 (s). 7.38 (s).

C-20 HPLC/MS: Rt = 4.150.

C-21 HPLC/MS: R, = 2.967.

C-22 ¹H-NMR (CDCI₃): δ = 1.20 (t); 2.25 (s); 2.29 (s); 2.98 (s); 3.36 (broad); 3.88 (s); 4.98 (s); 6.59 (s); 6.70 (s); 7.09-7.69 (m); 8.42 (d); major isomer.

C-23 ¹H-NMR (CDCI₃): δ = 1.18 (t); 1.67 (s); 2.04 (s); 2.27 (s); 3.01 (s); 3.46 (broad); 3.87 (s); 4.98 (s); 6.47 (s); 6.69 (s); 7.09-7.67 (m); 8.42 (d); major isomer.

C-23 ¹H-NMR (CDCI₃): δ = 1.11 (t); 1.90 (s); 2.08 (s); 2.18 (s); 2.20 (s); 2.92 (s); 3.28 (broad); 3.83 (s); 4.12 (s); 6.21 (s); 6.39 (s); 6.78 (s); 7.25 (s).

C-25 ¹H-NMR (CDCI₃): δ = 1.18 (t); 1.77 (s); 1.94 (s); 2.23 (s); 2.26 (s); 2.20 (s); 3.07 (broad); 3.48 (broad); 3.91 (s); 4.19 (s); 6.27 (s); 6.33 (s); 6.86 (s).

C-26 ¹H-NMR (CDCI₃): δ = 1.19 (t); 2.06 (s); 2.14 (s); 2.97 (s); 3.34 (broad); 4.07 (S); 4.42 (S); 6.35 (s); 6.46 (s); 7.18-7.40 (m); 7.31-7.42 (m); all isomers.

C-27 ¹H-NMR (CDCI₃): δ = 1.26 (t); 1.91 (s); 2.01 (s); 2.10 (s); 3.17 (s); 3.47 (broad); 3.62 (s); 4.00 (s); 4.42 (s); 6.35 (s); 6.74 (s); 7.30 (m); main isomer.

C-28 ¹H-NMR (CDCI₃): δ = 1.20 (t); 2.07 (s); 2.14 (s); 2.98 (s); 3.35 (broad); 4.05 (s); 4.38 (s);6.31 (s); 6.48 (s); 6.90 (dt); 7.21 (dd); 7.36 (s); 7.71 (dd).

C-29 ¹H-NMR (CDCI₃): δ = 1.32 (broad); 1.98 (s); 2.04 (s); 2.17 (s); 3.10-3.60 (broad); 3.69 (broad); 4.05 (s); 4.44 (s); 6.49 (s); 6.85 (s); 6.96 (dt); 7.21 (dd); 7.67 (dd); all isomers.

C-30 ¹H-NMR (CDCI₃): δ = 1.13-1.24 (m); 2.05 (s); 2.20 (s); 3.00 (s); 3.37 (broad); 3.48-3.70 (m); 3.93 (s); 4.31-4.57 (m); 6.53 (s); 6.67 (d); 6.83-6.92 (m); 7.22-7.29 (m); 7.38 (s); all isomers.

C-31 ¹H-NMR (CDCI₃): δ = 1.18 (t); 1.34 (t). 1.42 (t); 1.96 (s); 2.01 (s); 2.19 (s); 3.25 (S); 3.40-3.70 (m); 3.93 (s); 4.15 (m); 4.40-4.60 (m); 6.67 (s); 6.74 (d); 6.75-6.92 (m); 7.21-7.32 (m); all isomers.

C-32 ¹H-NMR (CDCI₃): δ = 1.16 (t); 1.34 (s); 2.01 (s); 2.32 (s); 2.34 (s); 3.20-3.70 (m); 3.93 (s); 4.30-4.60 (m); 6.60-6.80 (m); 7.15 (t); 7.39 (s); all isomers.

C-33 ¹H-NMR (CDCI₃): δ = 1.08 (t); 1.20-1.40 (m); 1.90 (s); 1.93 (s); 2.19 (s); 2.24 (s); 3.10-3.70 (m); 3.85 (s); 4.28-4.52 (m); 6.52-6.68 (m); 6.77 (s); 7.07 (t); all isomers.

C-34 ¹H-NMR (CDCI₃): δ = 0.88 (t); 1.10-1.40 (m); 1.40-1.62 (m); 1.88 (s); 2.29 (S); 3.10-3.70 (m); 3.85 (s); 4.28-4.49 (m); 6.60 (d); 6.65-6.82 (m); 7.12- 7.22 (m); 7.28 (s); all isomers.

C-35 ¹H-NMR (CDCI₃): δ = 0.95 (t); 1.27-1.50 (m); 1.52-1.80 (m); 1.96 (s); 2.02

HPLC column: RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany) Mobile phase: acetonitrile + 0.1% trifluoroacetic acid (TFA) / water + 0.1% TFA (gradient 5:95 to 95:5 over 5 min, 40⁰C.

MS: quadrupole electrospray ionization, 80 V (positive mode); m.p.: melting point.

II. Examples of the action against harmful fungi

The fungicidal action of the compounds of the formula I was demonstrated by the following tests: A. Greenhouse tests The active compounds were prepared separately as a stock solution comprising 19.6 mg of active compound which was made up to 10 ml using a mixture of acetone and/or DMSO, cyclohexanone and the emulsifier Wettol^® EM 31 (wetting agent having emulsifying and dispersing action based on ethoxylated castor oil) in a volume ratio of solvent/emulsifier of 99/1. The mixture was then made up to 32 ml with water. This stock solution was diluted with the solvent/emulsifier/water mixture described to the concentration of active compound stated below.

Use example 1 - Activity against brown rust of wheat caused by Puccinia recondita on wheat, protective application Leaves of potted wheat seedlings were sprayed with an aqueous suspension having the active compound concentration stated below. The next day, the treated plants were inoculated with a spore suspension of brown rust of wheat {Puccinia recondita). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%) at 20 to 22°C for 24 hours. During this time, the spores germinated and the germ tubes pe- netrated into the leaf tissue. The next day, the test plants were returned to the greenhouse and cultivated at temperatures between 20 and 22°C and 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust fungus development on the leaves was then determined visually in %.

In this test, the plants which had been treated with 600 ppm of the active compound from examples C-2, C-9, C-23, C-24, C-26, C-27, C-28, C-29 and C-34, respecttively, or with 300 ppm of the active compound from examples C-3, C-12, C-13 and C-21 , respectively, or with 150 ppm of the active compound from example C-6 showed an infection of at most 15%, whereas the untreated plants were 80 to 90% infected.

Use example 2: Activity against early blight on tomatoes caused by Phytophthora infestansw^'ftb protective application

Young seedlings of tomato plants were grown in pots. The plants were sprayed to runoff with an aqueous suspension containing the concentration of active ingredient stated below. The next day, the treated plants were inoculated with an aqueous suspension of sporangia of Phytophthora infestans. After inoculation, the trial plants were immediately transferred to a humid chamber. After 6 days at 18 to 20°C and a relative humidity close to 100%, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

In this test, the plants which had been treated with 600 ppm of the active compound from example C-25 showed an infection of less than or equal to 15 % whereas the untreated plants were 90% infected.

Use example 3: Protective action against Blumeria graminis tritici on wheat (mildew of wheat)

Leaves of potted wheat seedlings of the cultivar "Kanzler" were sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. The next day, the treated plants were dusted with a suspension of spores of mildew of wheat (Blumeria graminis tritici). The plants were then returned into the greenhouse and cultivated at temperatures between 20 and 24°C and at 60 to 90% relative atmospheric humidity for a further 7 days. The extent of the mildew development on the leaves was then determined visually.

In this test, the plants which had been treated with 600 ppm of the active compound from examples C-23, C-24, C-25, C-27 and C-34, respectively, showed an infection of less than or equal to 15 % whereas the untreated plants were 90% infected.

Use example 4: Protective action against Phakopsora pachyrhizi on soybean (rust of soybean) Leaves of potted soybean seedlings were sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. The next day, the treated plants were dusted with a suspension of spores of soybean rust (Phakop- sora pachyrhizi). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%), at 23 to 27°C, for 24 hours. During this time, the spores germinated and the germinal tubes penetrated into the leaf tissue. The plants were then returned into the greenhouse and cultivated at temperatures between 23 and 27⁰C and at 60 to 80% relative atmospheric humidity for a further 14 days. The extent of the rust development on the leaves was then determined visually.

In this test, the plants which had been treated with 600 ppm of the active compound from examples C-22, C-23, C-24, C-26, C-27, C-29 and C-34, respectively, showed an infection of less than or equal to 15 % whereas the untreated plants were 90% infected.

Use example 5: Protective action against Septoria tritici on wheat (Septoria leaf blotch of wheat) Leaves of potted wheat seedlings of the cultivar "Kanzler" were sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. Two days later, the treated plants were dusted with a suspension of spores of Septoria tritici. The plants were then placed in a greenhouse chamber with high atmos- pheric humidity (90 to 95%), at 20 to 24°C, for 4 days, afterwards at temperatures between 18 and 22°C aand at about 70% relative atmospheric humidity. The extent of the disease symptom development on the leaves was determined visually after 21 days. In this test, the plants which had been treated with 600 ppm of the active compound from examples C-23, C-26, and C-28, respectively, showed an infection of less than or equal to 15 % whereas the untreated plants were 90% infected.

B) Microtiter tests

The active compounds were formulated separately as a stock solution in DMSO at a concentration of 10 000 ppm.

The stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active compound concentration using nutrient medium as specified in the respective use example. An aqueous spore suspension as specified in the respective use example was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18°C.

Using an absorption photometer, the microtiter plates were measured at 405 nm on day 7 after the inoculation. The measured parameters were compared to the growth of the active compound-free control variant (= 100%) and the fungus- and active compound-free blank value to determine the relative growth in % of the pathogens in the individual active compounds.

Use example 6: Activity against the late blight pathogen Phytophthora infestans A pea juice-based aqueous nutrient medium for fungi and an aqueous zoospore suspension of Phytophthora infestans were used. In this test, the sample which had been treated with 31 ppm of the active compound from examples C-22 and C-26, respectively, showed up to at most 15 % growth of the pathogen.

Use example 7: Activity against the rice blast pathogen caused by Botrytis cinerea A malt-based aqueous nutrient medium for fungi and an aqueous spore suspension of

Botrytis cinerea were used.

In this test, the sample which had been treated with 31 ppm of the active compound from examples C-22, C-24, C-26 and C-28, respectively, showed up to at most 15% relative growth of the pathogen.

Use example 8: Activity against the Septoria blotch pathogen caused by Septoria tritici A malt-based aqueous nutrient medium for fungi and an aqueous spore suspension of Septoria tritici were used.

In this test, the sample which had been treated with 31 ppm of the active compound from examples C-26 and C-28, respectively, showed up to at most 15% relative growth of the pathogen.

Claims

Claims

1. Compounds of the formula I

in which the substituents have the following meaning:

R¹ is Ci-Cβ-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₃-C₈-cycloalkyl, C₃-C₈-cyclo- alkenyl, phenyl or a three- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members;

R² is NR^AR^B, Ci-Ci2-alkylthio, phenyl or a 3- to 10-membered saturated, partially unsaturated or aromatic heterocyclyl, wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the phenyl and heterocyclyl groups R² are attached via an oxygen or sulfur atom, or -[0-(ZH₂)Jm-H, wherein

Z are independently of each other carbon or silicium; n is an integer between 1 and 5, m is an integer between 3 and 10;

R³, R⁴ independently of one another are hydrogen, Ci-Cβ-alkyI, Ci-C₈-haloalkyl, d-Cβ-alkylcarbonyl or Ci-C₈-alkoxycarbonyl; R⁵, R⁶ independently of one another are Ci-C₈-alkyl, Ci-Cs-haloalkyl, Ci-C4-alkoxy or C3-Cβ-cycloalkyl; R⁷ is hydrogen, Ci-C₈-alkyl, Ci-C₈-haloalkyl, Ci-C₄-alkoxy or Ci-Cβ-haloalkoxy; and aliphatic and cyclic groups R¹ to R⁶ may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^a which independently of one another are selected from: R^a is amino, halogen, hydroxyl, oxo, nitro, cyano, carboxyl, Ci-C₄-alkyl,

C₂-C₄-alkenyl, C2-C₄-alkynyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy, CrC₄- haloalkoxy, C₃-C6-cycloalkyl, C3-C₈-cycloalkenyl, C2-C6-alkenyloxy, C3-C6-alkynyloxy, Ci-C₄-alkoxyimino, C∑-Cβ-alkylidene, C3-C₈-cyclo- alkylidene, Ci-Ci2-alkylamino, Ci-C₄-alkoxycarbonyl, CrC₄- alkylcarbonyloxy, NR^AR^B, C₂-C₈-alkylene, C₂-C₈-oxyalkylene, CrC₈- oxyalkyleneoxy, phenyl, naphthyl or a three- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^a may be attached directly or via a nitrogen or oxygen atom; where the aliphatic or cyclic groups R^a for their part may be partially or fully halogenated and/or may carry one, two, three or up to the maximum possible number of identical or different groups R^b: R^b is halogen, hydroxyl, nitro, cyano, carboxyl, Ci-C4-alkyl, C₂-C₄- alkenyl, C₂-C₈-alkynyl, Ci-C₄-haloalkyl, Ci-C4-alkoxy, Ci-C₄- haloalkoxy, Ci-Cs-alkylcarbonylamino, phenyl, phenoxy, pyridyl, pyridyloxy or

C3-C8-cycloalkylcarbonylamino; where the cyclic groups R^b for their part may be partially or fully halogenated and/or may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^c:

R^c is halogen, hydroxyl, nitro, cyano, carboxyl, Ci-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₈-alkynyl, Ci-C₄-haloalkyl, Ci-C₄- alkoxy or Ci-C₄-haloalkoxy;

R^A,R^B independently of one another are cyano, carboxyl, Ci-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy, d-

C₄-haloalkoxy, C3-C6-cycloalkyl, C3-Cs-cycloalkenyl, C₂-C6-alkenyloxy, Ca-Cβ-alkynyloxy, Ci-C₄-alkoxyimino, C₂-Cs- alkylidene, Ca-Cβ-cycloalkylidene, Ci-Ci₂-alkylamino, C1-C4- alkoxycarbonyl, Ci-C₄-alkylcarbonyloxy, C₂-C8-alkylene, C₂-Cs- oxyalkylene, d-Cs-oxyalkyleneoxy, NR^CR^D, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains 1 to 4 heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^A and/or R^B may for their part be attached directly or via a nitrogen or oxygen atom; where the aliphatic or cyclic groups R^A and/or R^B for their part may be partially or fully halogenated and/or may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^b,

R^B may additionally be hydrogen;

R^C,R^D independently of one another are hydrogen, cyano, carboxyl, Ci-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, Ci- C₄-haloalkyl, CrC₄-alkoxy, Ci-C₄-haloalkoxy, Cs-Cβ-cycloalkyl, C3-

Cβ-cycloalkenyl, C₂-C6-alkenyloxy, C3-Cβ-alkynyloxy, Ci-C₄-alkoxyimino, C₂-C8-alkylidene, C3-Cs-cyclo- alkylidene, Ci-Ci₂-alkylamino, CrC₄-alkoxycarbonyl,

C∑-Cβ-alkylene, C∑-Cβ- oxyalkylene, CrC₈-oxyalkyleneoxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains 1 to 4 heteroatoms from the group consisting of O₁ N and S as ring members; where the cyclic groups R^c and/or R^D may for their part be attached directly or via a nitrogen or oxygen atom; L¹,L²,L³,L⁴ independently of one another are hydrogen, halogen, Ci-C₄-alkyl,

Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C₄-haloalkoxy; where R⁵ and R⁶ in each case together with the atoms linking them may form a five- to ten-membered saturated or partially unsaturated cyclic group which, in addition to the carbon atoms, may contain 1 to 3 heteroatoms from the group consisting of N, O and S and/or may be partially or fully halogenated and/or may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^a;

X is oxygen or sulfur; and the N-oxides and agriculturally acceptable salts of the compounds of the formula I.

2. The compounds of the formula I according to claim 1 in which

R¹ is d-Cs-alkyl, C∑-Cβ-alkenyl, C3-C₈-cycloalkyl, phenyl, pyridyl, pyrazoloyl, imidazolyl or triazolyl, where R¹ may carry one, two, three or up to the maximum possible number of identical or different groups R^a which are not heterocyclic groups; R² is NR^AR^B;

R^a is amino, halogen, hydroxyl, oxo, nitro, cyano, carboxyl, Ci-C4-alkyl,

C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C₄-alkoxy, CrC₄- haloalkoxy, C3-C6-cycloalkyl, C3-C₈-cycloalkenyl, C∑-Cβ-alkenyloxy,

Ca-Cβ-alkynyloxy, Ci-C4-alkoxyimino, C∑-Cβ-alkylidene, C3-Cβ-cyclo- alkylidene, Ci-Ci2-alkylamino, Ci-C4-alkoxycarbonyl, C1-C4- alkylcarbonyloxy, NR^AR^B, C2-C₈-alkylene, C₂-C₈-oxyalkylene, CrC₈- oxyalkyleneoxy, phenyl, naphthyl or a three- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^a may be attached directly or via a nitrogen or oxygen atom; where the aliphatic or cyclic groups R^a for their part may be partially or fully halogenated and/or may carry one, two, three or up to the maximum possible number of identical or different groups R^b: R^b is halogen, CrC₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy or CrC₄- haloalkoxy;

R^A,R^B independently of one another are cyano, carboxyl, Ci-C₄-alkyl, C₂-C4-alkenyl, C₂-C₄-alkynyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy, Ci- C₄-haloalkoxy, Cs-Cβ-cycloalkyl, Cs-Cβ-cycloalkenyl, C2-C6- alkenyloxy,

C3-C6-alkynyloxy, Ci-C₄-alkoxyimino, C2-C8-alkylidene, C3-C8- cycloalkylidene, Ci-Ci2-alkylamino, Ci-C₄-alkoxycarbonyl, Ci- C4-alkylcarbonyloxy, C2-Cβ-alkylene, C2-C8-oxyalkylene, Ci-Cs- oxyalkyleneoxy, NR^CR^D, phenyl, naphthyl or a 3- to 10- membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains 1 to 4 heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^A and/or R^B may for their part be attached directly or via a nitrogen or oxygen atom; where the aliphatic or cyclic groups R^A and/or R^B for their part may be partially or fully halogenated and/or may carry 1 , 2, 3 or up to the maximum possible number of identical or different groups R^b,

R^B may additionally be hydrogen;

R^C,R^D independently of one another are hydrogen, cyano, carboxyl, Ci-C₄-alkyl, C₂-C₄-alkenyl, C2-C₄-alkynyl, Ci- C4-haloalkyl, Ci-C₄-alkoxy, Ci-C₄-haloalkoxy, C₃-C₆-cycloalkyl, C₃-

Cβ-cycloalkenyl, C2-C6-alkenyloxy, C3-C6-alkynyloxy, C-ι-C₄-alkoxyimino, C2-C8-alkylidene, C3-Cβ-cyclo- alkylidene, CrCi₂-alkylamino, Ci-C₄-alkoxycarbonyl, CrC₄-alkylcarbonyloxy, C₂-C₈-alkylene, C₂-C₈- oxyalkylene, Ci-C₈-oxyalkyleneoxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains 1 to 4 heteroatoms from the group consisting of O, N and S as ring members; where the cyclic groups R^c and/or R^D may for their part be attached directly or via a nitrogen or oxygen atom;

R³, R⁴ independently of one another are hydrogen, CrC₄-alkyl or d-Cβ-haloalkyl; R⁵,R⁶is Ci-C₄-alkyl; R⁷ is hydrogen;

L¹, L² independently of one another are halogen, Ci-C₄-alkyl, Ci-C₄-haloalkyl or

Ci-C₄-haloalkoxy; L³,L⁴ are hydrogen; and X is oxygen.

3. The compounds of formula I according to any of claims 1 to 2 wherein R³ is optionally R^a-substituted Ci-Cβ-alkyI or Ci-Cβ-haloalkyl.

4. The compounds of formula I according to any of claims 1 to 3 wherein the α carbon atom in R¹ does not carry a cyclic group.

5. The compounds of formula I according to any of claims 1 to 4 wherein R² is NR^AR^B.

6. The compounds of formula I according to claim 5 wherein R^A is optionally substituted phenyl or CrC₄-alkyl.

7. The compounds of formula I according to any of claims 1 to 4 wherein R² is optionally substituted phenoxy, heterocyclyloxy, phenylthio, heterocyclylthio or Ci-Ci2-alkylthio.

8. The compounds of formula I according to any of claims 1 to 4 wherein R² is optionally substituted -[O-(ZH₂)n]m-H, wherein

Z are independently of each other carbon or silicium; n is an integer between 1 and 5, m is an integer between 3 and 10.

9. The compounds of formula I according to any of claims 1 to 8 wherein R³ and R⁴ are both hydrogen.

10. A process for preparing a compound of the formula I according to any of claims 1 to 8 wherein a compound Il

in which Y is a nucleophlically replaceable group is condensed with a compound

/^NH2

R¹-0 and the resulting compound IV

is converted under basic conditions with a compound V

into a compound of formula I.

11. A composition comprising a solvent or solid carrier and a compound of the formula I according to any of claims 1 to 9.

12. The composition according to claim 10, comprising a further active compound.

13. Seed, comprising a compound of formula I according to any of claims 1 to 9 in an amount of from 1 to 1000 g per 100 kg.

14. A method for controlling phytopathogenic harmful fungi wherein the fungi or the materials, plants, the soil or seed to be protected from fungal attack are treated with an effective amount of a compound of the formula I according to any of claims 1 to 9.