EP2451785A2

EP2451785A2 - Substituted phenyl(oxy/thio)alkanol derivatives

Info

Publication number: EP2451785A2
Application number: EP10735188A
Authority: EP
Inventors: Carl Friedrich Nising; Klaus Kunz; Jörg Nico GREUL; Hendrik Helmke; Gorka Peris; Jürgen BENTING; Peter Dahmen; Isolde HÄUSER-HAHN; Ines Heinemann; Christian Paulitz; Dirk Schmutzler; Ulrike Wachendorff-Neumann; Christoph Andreas Braun; Ruth Meissner; Hiroyuki Hadano
Original assignee: Bayer CropScience AG
Current assignee: Bayer Intellectual Property GmbH
Priority date: 2009-07-08
Filing date: 2010-06-25
Publication date: 2012-05-16
Also published as: EA023170B1; CO6480988A2; AU2010268838A8; CA2775312A1; CN102471285B; AU2010268838A1; AR077307A1; EA201391356A1; CN102471285A; BR112012000170A2; CL2012000006A1; AU2010268838B2; US9187431B2; WO2011003528A2; TW201107300A; US20150376147A1; US20110059990A1; WO2011003528A3; JP2012532157A; TWI519525B

Abstract

The present invention relates to novel substituted phenyl(oxy/thio)alkanol derivatives, to a method for producing said compounds, to agents comprising said compounds, and to the use thereof as biological active compounds, in particular for combating harmful microorganisms in crop protection and material protection and as plant growth regulators.

Description

Substituted phenyl (bxy / thio) alkanol derivatives

The present invention relates to novel substituted phenyl (oxy / thio) alkanol derivatives, processes for preparing these compounds, compositions containing these compounds, and their use as biologically active compounds, in particular for controlling harmful microorganisms in plant protection and in the protection of materials and as plant growth regulators.

It is already known that certain phenyl (oxy / thio) alkanol derivatives can be used in crop protection as fungicides and / or growth regulators (cf., DE-A 39 05 317, JP-A 58-124772, EP-A 0298 332, US Pat. EP-A 0028 755, EP-A 0061 835, EP-A 0040345, EP-A 0 001 399, EP-A 0 297 383, EP-A 0 793 657 and EP-A 0 594 963). Since the ecological and economic requirements of modern drugs, e.g. Fungicides, continuously increase, for example, in terms of spectrum of activity, toxicity, selectivity, application rate, residue formation and favorable manufacturability, and also, for. Problems with resistances may occur, there is a constant need to develop new fungicidal agents that have at least in some areas advantages over the known. There have now been new substituted phenyl (oxy / thio) alkanol derivatives of the formula (I)

found in which

X is 5-pyrimidinyl, 1H-1, 2,4-triazol-1-ylmethyl, 3-pyridinyl, 1H-1,3-imidazolylmethyl or

2,4-dihydro-3H-1, 2,4-triazole-3-thion-1-ylmethyl,

Y is O, S, SO, SO ₂ or CH ₂ ,

Z ^{1 is} bromine, iodine or trifluoromethyl,

Z ² and Z ³ are each independently halogen, C _r C ₄ alkyl, C _r C ₄ alkoxy, C _r C ₄ alkylthio, C _r C ₄ - haloalkyl, _{Ci-C4-haloalkoxy} or C _r C ₄ - Halogenoalkylthio,

n is 0 or 1,

R is tert-butyl, isopropyl, 1-halogenocyclopropyl, l- (Ci-C ₄ alkyl) cyclopropyl, 1- (C) -C ₄ alkoxy) - l- cyclopropyl, and (Ci-C ₄ alkylthio) cyclopropyl .

and their agrochemically active salts,

the connections

l- (3-bromo-2-chloφhenoxy) -3,3-dimethyl-2- (lH-l, 2,4-triazol-l-ylmethyl) butan-2-ol,

l- (4-bromo-2-chlθφhenoxy) -3,3-dimethyl-2- (lH-l, 2,4-triazol-l-ylmethyl) butan-2-ol,

4- (3-Bromo-4-fluorophenyl) -2- (1-chlorocyclopropyl) -1- (1H-1,2,4-triazol-1-yl) butan-2-ol,

1- [3,5-bis (trifluoromethyl) phenyl] -4,4-dimethyl-3- (1H-l ₎ 2,4-triazol-1-ylmethyl) -pentan-3-ol

with exception of. The salts thus obtainable also have fungicidal and / or plant growth-regulating properties.

The phenyl (oxy / thio) alkanol derivatives which can be used according to the invention are generally defined by the formula (I). Preferred radical definitions of the above and below formulas are given in the following. These definitions apply equally to the end products of formula (I) as well as to all intermediates (see also below under "Explanatory Notes on Processes and Intermediates").

X preferably represents 5-pyrimidinyl, 1H-1, 2,4-triazol-1-ylmethyl, 3-pyridinyl or 2,4-dihydroxyethyl

3H-1, 2,4-triazole-3-thion-1-ylmethyl.

X is more preferably 5-pyrimidinyl.

X is also particularly preferably 1 H-1, 2,4-triazol-1-ylmethyl.

X is also particularly preferably 2,4-dihydro-3H-1, 2,4-triazole-3-thion-1-ylmethyl.

X is most preferably 5-pyrimidinyl.

X is also most preferably LH-l, 2,4-triazol-1-ylmethyl.

Y is preferably O, S or CH ₂ .

Y is particularly preferably O or CH- ,.

Y is most preferably O.

Z ¹ is preferably bromine or iodine.

Z ¹ is particularly preferably bromine.

Z ¹ is also particularly preferably iodine.

Z ¹ is most preferably in the 4-position for bromine.

Z ¹ is most preferably in the 4-position for iodine.

Z ² is preferably fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, trichloromethyl, difluoromethyl, Dichloromethyl, trifluoromethoxy or trifluoromethylthio.

Z ² is particularly preferably in the 2- or 3-position for fluorine, chlorine, bromine, iodine, methyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

Z ² is very particularly preferably in the 2- or 3-position for fluorine, chlorine, methyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

Z ³ is preferably fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, trichloromethyl, difluoromethyl,

Dichloromethyl, trifluoromethoxy or trifluoromethylthio.

Z ³ particularly preferably represents fluorine, chlorine, bromine, iodine, methyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

Z ³ very particularly preferably represents fluorine, chlorine, methyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio. n is preferably 0.

n is also preferably 1.

n is particularly preferably 0.

R is preferably tert-butyl, isopropyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl, 1-methylcyclopropyl, 1-methoxycyclopropyl and 1-methylthiocyclopropyl.

R is particularly preferably tert-butyl, isopropyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl or

1-methylcyclopropyl.

Another embodiment of the present invention relates to compounds of the formula (I-a)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given above.

Another embodiment of the present invention relates to compounds of the formula (I-b)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given above.

In this formula (I-b), n in another embodiment is 0. Another embodiment of the present invention relates to compounds of the formula (I-c)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given above.

A further embodiment of the present invention relates to compounds of the formula (I-d)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given above.

In this formula (I-d), n is 0 in another embodiment.

Another embodiment of the present invention relates to compounds of the formula (Ie) in which Y, Z, Z, Z, n and R have the meanings given above.

Another embodiment of the present invention relates to compounds of the formula (I-f)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given above.

In this formula (I-f), n is 0 in another embodiment.

Another embodiment of the present invention are compounds of the formula (I) in which

Z ^{1 is} bromine and R is tert-butyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} bromine and R is isopropyl.

Z ^{1 is} bromine and R is 1-chlorocyclopropyl.

Z ^{1 is} bromine and R is 1-fluorocyclopropyl.

Z ^{1 is} bromine and R is 1-methylcyclopropyl.

Z ^{1 stands} for iodine and R stands for tert-butyol.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} iodine and R is isopropyl.

Z ^{1 is} iodine and R is 1-chlorocyclopropyl.

Z ^{1 is} iodine and R is 1-fluorocyclopropyl.

Z ^{1 is} iodine and R is 1-methylcyclopropyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} trifluoromethyl and R is tert-butyl. A further embodiment of the present invention are compounds of formula (I) in which Z ¹ is trifluoromethyl and R is isopropyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} trifluoromethyl and R is 1-chlorocyclopropyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} trifluoromethyl and R is 1-fluorocyclopropyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} trifluoromethyl and R is 1-methylcyclopropyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} bromine, R is tert-butyl and X is 5-pyrimidinyl.

Z ^{1 is} bromine, R is tert-butyl and X is 1H-l, 2,4-triazol-1-ylmethyl.

Z ^{1 is} bromine, R is tert-butyl and X is 3-pyridinyl.

Z ^{1 is} bromine, R is tert-butyl and X is 1H-1,3-imidazol-1-ylmethyl.

Z ^{1 is} bromine, R is tert-butyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thion-1-ylmethyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} bromine, R is isopropyl and X is 5-pyrimidinyl.

Z ^{1 is} bromine, R is isopropyl and X is 1H-l, 2,4-triazol-1-ylmethyl.

Z ^{1 is} bromine, R is isopropyl and X is 3-pyridinyl.

Z ^{1 is} bromine, R is isopropyl and X is 1H-1,3-imidazolylmethyl.

Z ^{1 is} bromine, R is isopropyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thion-1-ylmethyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} bromine, R is 1-chlorocyclopropyl and X is 5-pyrimidinyl.

Z ^{1 is} bromine, R is 1-chlorocyclopropyl and X is 1H-l, 2,4-triazol-1-ylmethyl.

Z ^{1 is} bromine, R is 1-chlorocyclopropyl and X is 3-pyridinyl.

Z ^{1 is} bromine, R is 1-chlorocyclopropyl and X is 1H-1,3-imidazolylmethyl. - -

A further embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} bromine, R is 1-chlorocyclopropyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thione-1 -ylmethyl stands.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} bromine, R is 1-fluorocyclopropyl and X is 5-pyrimidinyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} bromine, R is 1-fluorocyclopropyl and X is 1H-l, 2,4-triazol-1-ylmethyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} bromine, R is 1-fluorocyclopropyl and X is 3-pyridinyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} bromine, R is 1-fluorocyclopropyl and X is 1H-1,3-imidazolylmethyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} bromine, R is 1-fluorocyclopropyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thione-1 -ylmethyl stands.

Z ^{1 is} iodo, R is tert-butyl and X is 5-pyrimidinyl.

Z ^{1 is} iodo, R is tert -butyl and X is 1H-l, 2,4-triazol-1-ylmethyl.

Z ^{1 is} iodo, R is tert-butyl and X is 3-pyridinyl.

A further embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} iodine, R is tert-butyl and X is IH-1,3-imidazolylmethyl.

Z ^{1 is} iodo, R is tert-butyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thione-1-ybnethyl.

Z ^{1 is} iodo, R is isopropyl and X is 5-pyrimidinyl.

Z ^{1 is} iodine, R is isopropyl and X is 1H-l, 2,4-triazol-1-ylmethyl.

Z ^{1 is} iodo, R is isopropyl and X is 3-pyridinyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} iodo, R is isopropyl and X is 1H-1,3-imidazolylmethyl.

Z ^{1 is} iodine, R is isopropyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thion-1-ylmethyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} iodo, R is 1-chlorocyclopropyl and X is 5-pyrimidinyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} iodo, R is 1-chlorocyclopropyl and X is 1H-l, 2,4-triazol-1-ylmethyl. Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} iodo, R is 1-chlorocyclopropyl and X is 3-pyridinyl.

A further embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} iodine, R is 1-chlorocyclopropyl and X is 1H-1,3-imidazolylmethyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} iodo, R is 1-chlorocyclopropyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thione-1 -ylmethyl stands.

A further embodiment of the present invention are compounds of the formula (I) in which

Z ^{1 is} iodo, R is 1-fluorocyclopropyl and X is 5-pyrimidinyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} iodo, R is 1-fluorocyclopropyl and X is 1H-l, 2,4-triazol-1-ylmethyl.

Z ^{1 is} iodo, R is 1-fluorocyclopropyl and X is 3-pyridinyl.

Z ^{1 is} iodo, R is 1-fluorocyclopropyl and X is 1H-1,3-imidazolylmethyl.

Z ^{1 is} iodo, R is 1-fluorocyclopropyl and X is 2,4-dihydro-3H-1, 2,4-triazol-3-thion-1-ylmethyl.

Z ^{1 is} trifluoromethyl, R is tert-butyl and X is 5-pyrimidinyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} trifluoromethyl, R is tert-butyl and X is 1H-1,2,4-triazol-1-ylmethyl.

Z ^{1 is} trifluoromethyl, R is tert-butyl and X is 3-pyridinyl.

Z ^{1 is} trifluoromethyl, R is tert-butyl and X is 1H-1,3-imidazolylmethyl.

Z ^{1 is} trifluoromethyl, R is tert-butyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thion-1-ylmethyl.

Z ^{1 is} trifluoromethyl, R is isopropyl and X is 5-pyrimidinyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} trifluoromethyl, R is isopropyl and X is 1H-1,2,4-triazol-1-ylmethyl.

Z ^{1 is} trifluoromethyl, R is isopropyl and X is 3-pyridinyl.

Z ^{1 is} trifluoromethyl, R is isopropyl and X is 1H-1,3-imidazolylmethyl.

A further embodiment of the present invention are compounds of the formula (T) in which

Z ^{1 is} trifluoromethyl, R is isopropyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thion-1-ylmethyl. A further embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} trifluoromethyl, R is 1-chlorocyclopropyl and X is 5-pyrimidinyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} trifluoromethyl, R is 1-chlorocyclopropyl and X is 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} trifluoromethyl, R is 1-chlorocyclopropyl and X is 3-pyridinyl.

Another embodiment of the present invention are compounds of the formula (I) in which Z ^{1 is} trifluoromethyl, R is 1-chlorocyclopropyl and X is 1H-1,3-imidazolylmethyl.

Another embodiment of the present invention are compounds of formula (I) in which Z ^{1 is} trifluoromethyl, R is 1-chlorocyclopropyl and X is 2,4-dihydro-3H-1, 2,4-triazole-3-thione-1 - ylmethyl stands.

Z ^{1 is} trifluoromethyl, R is 1-fluorocyclopropyl and X is 5-pyrimidinyl.

Another embodiment of the present invention are compounds of formula (I) wherein Z ^{1 is} trifluoromethyl, R is 1-fluorocyclopropyl and X is 1H-l, 2,4-triazol-1-ylmethyl.

Z ^{1 is} trifluoromethyl, R is 1-fluorocyclopropyl and X is 3-pyridinyl.

Z ^{1 is} trifluoromethyl, R is 1-fluorocyclopropyl and X is 1H-1,3-iridazolylmethyl.

Z ^{1 is} trifluoromethyl, R is 1-fluorocyclopropyl and X is 2,4-dihydro-3H-1, 2,4-triazol-3-thion-1-ylmethyl.

However, the general or preferred radical definitions or explanations given above can also be combined as desired between one another and thus between the respective ranges and preferred ranges. They apply accordingly to the end products as well as to the precursors and intermediates. In addition, individual definitions can be omitted.

Preference is given to those compounds of the formula (I) in which all radicals each have the abovementioned preferred meanings.

Particular preference is given to those compounds of the formula (I) in which all radicals each have the abovementioned particularly preferred meanings.

Explanation of processes and intermediates

The phenyl (oxy / thio) alkanol derivatives of the formula (I) can be prepared in different ways. In the following, the possible methods are first shown schematically. Unless indicated otherwise, the radicals given have the meanings given above. - -

Scheme 1: Process A - Preparation of phenyl (oxy / thio) alkanol derivatives of the formula (I-g)

(X ¹ = 1H-l, 2,4-triazol-1-ylmethyl, 1H-l, 3-imidazol-1-ylmethyl)

stands for CH or N.

Scheme 2: Process B - Preparation of phenyl (oxy / thio) alkanol derivatives of the formula (Ih) (X ² = IH-1, 2,4-triazol-1-ylmethyl, 1H-1,3-imidazole-1 ylmethyl, 5-pyrimidinyl or 3-pyridinyl)

Scheme 3: Process C - Preparation of phenyl (oxy / thio) alkanol derivatives of the formula (I-i)

(X ³ = 5-pyrimidinyl or 3-pyridinyl)

HaI stands for halogen.

Scheme 4: Process D - Preparation of phenyl (oxy / thio) alkanol derivatives of the formula (I-k)

(X ⁴ = 5-pyrimidinyl or 3-pyridinyl)

M stands for metal.

Scheme 5: Process E - Preparation of phenyl (oxy / thio) alkanol derivatives of the formula (I-e)

Preferred radical definitions of the above and below formulas and schemes are already given above. These definitions apply equally not only to the end products of formula (I) but also to all intermediates. Method A

The oxirane derivatives of the formula (II) required as starting materials for carrying out the process A according to the invention are novel, where the compound 2- {2- [3,5-bis (trifluoromethyl) phenyl] ethyl} -2-tert-butyl- butyloxirane is excluded. They can be prepared by known processes from the phenyloxy (thio) ketones of the formula (VI) (cf., EP-A 0 040 345).

The 1,2,4-triazole and 1,3-imidazole of the formula (III) are known.

Process A according to the invention is carried out in the presence of a diluent and if appropriate in the presence of a base. Optionally, an acid or a metal salt is added to the resulting compound of formula (I-g) (see below). Suitable diluents for the reaction according to the invention are all inert organic solvents. These include, preferably, alcohols, e.g. Ethanol and methoxyethanol; Ketones, e.g. 2-butanone; Nitriles, e.g. acetonitrile; Esters, e.g. Essigester; Ethers, e.g. dioxane; aromatic hydrocarbons, e.g. Benzene and toluene; or amides, e.g. Dimethylformamide.

Suitable bases for the reaction according to the invention are all customary organic and inorganic bases. These include, preferably, alkali carbonates, e.g. Sodium or potassium carbonate; Alkali hydroxides, e.g. sodium hydroxide; Alkali alcoholates, e.g. Sodium and potassium methylate and ethylate; Alkali hydrides, e.g. sodium hydride; as well as lower tertiary alkylamines, cycloalkylamines and aralkylamines, in particular triethylamine.

The reaction temperatures can be varied within a relatively wide range when carrying out the process according to the invention. In general, one works at temperatures between 0 ⁰ C and 200 ⁰ C, preferably between 60 ⁰ C and 150 ⁰ C.

The erfϊndungsgemäße reaction may optionally be carried out under elevated pressure. In general, one works between 1 and 50 bar, preferably between 1 and 25 bar.

When carrying out process A according to the invention, 1 to 2 mol of 1,2,4-triazole of the formula (III) and, if appropriate, 1 to 2 mol of base are preferably employed per mole of oxirane of the general formula (II). The isolation of the end products takes place in a generally customary manner.

Method B

Some of the oxirane derivatives of the formula (IV) required as starting materials for carrying out the process B according to the invention are novel. They can be prepared by known processes from the corresponding triazolyl ketones (cf., DE-A 31 11 238, EP-A 0 157 712).

New are oxirane derivatives of the formula (FV-a) (IV-a) in which

R ^{a is} isopropyl, L-halogenocyclopropyl, C 1 -C ₄ -alkyl) cyclopropyl, C 1 -C ₄ -alkoxycyclopropyl and C 1 -C ₄ -alkylthio) cyclopropyl,

A is CH or N

R ^a is preferably isopropyl, 1-chlorocyclopropyl, 1-methylcyclopropyl, 1-methoxycyclopropyl and 1-methylthiocyclopropyl.

R ^a is particularly preferably isopropyl, 1-chlorocyclopropyl or 1-methylcyclopropyl.

R ^a is very particularly preferably isopropyl.

Also new are oxirane derivatives of the formula (IV-b)

in which

R has the meanings given above and

A is CH or N,

where R is not tert-butyl when A is CH. R is preferably, more preferably or very particularly preferably of the abovementioned meanings, R in each case not being tert-butyl, when A is CH.

The (thio) phenols of the formula (V) are known.

The inventive method B is carried out in the presence of a diluent and optionally in the presence of a base. Optionally, an acid or a metal salt is added to the resulting compound of formula (I-h) (see below).

Suitable diluents for the erfmdungsgemäße implementation of all inert organic solvents. These include, preferably, alcohols, e.g. Ethanol and methoxyethanol; Ketones, e.g. 2-butanone; Nitriles, e.g. acetonitrile; Esters, e.g. Essigester; Ethers, e.g. dioxane; aromatic hydrocarbons, e.g. benzene and toluene; or amides, e.g. Dimethylformamide. Suitable bases for the reaction according to the invention are all customary organic and inorganic bases. These include, preferably, alkali carbonates, e.g. Sodium or potassium carbonate; Alkali hydroxides, e.g. sodium hydroxide; Alkali alcoholates, e.g. Sodium and potassium methylate and ethylate; Alkali hydrides, e.g. sodium hydride; as well as lower tertiary alkylamines, cycloalkylamines and aralkylamines, in particular triethylamine. Particular preference is given to using sodium hydride.

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, one works at temperatures between 0 ⁰ C and 200 ⁰ C, preferably between 60 ⁰ C and 150 ⁰ C. The reaction according to the invention may optionally be carried out under elevated pressure. In general, one works between 1 and 50 bar, preferably between 1 and 25 bar.

In carrying out the process B according to the invention is used for 1 mol of oxirane of the general formula (IV) is preferably 1 to 2 moles (thio) phenol of the formula (V) and optionally 1 to 2 moles of base. The isolation of the end products takes place in a generally customary manner.

Method C

Some of the phenyl (oxy / thio) ketones of the formula (VI) required as starting materials for carrying out the process C according to the invention are known. They can be prepared in a known manner (cf EP-A 0040 345, EP-A 0 001 399). The halides of the formula (VII) are known. In formula (VII), Hal is preferably chlorine or bromine.

The process C of the invention is carried out in the presence of a diluent and in the presence of an alkali metal-organic compound. Optionally, an acid or a metal salt is then added to the resulting compound of formula (I-i) (see below).

Suitable inert diluents for the inventive implementation are preferably inert organic solvents. These preferably include those which have a low fixed point, in particular ethers, such as diethyl ether or tetrahydrofuran. Preferably, one works with mixtures of these two ethers.

Alkali metal-organic compounds used in the reaction according to the invention are preferably alkali metal alkyls, in particular n-butyl lithium; However, it is also possible to use alkali metal aryls, such as phenyl-lithium.

The reaction temperatures can be varied within a certain range in the process according to the invention. In general, it is carried out between -150 ⁰ C and -50 ⁰ C, preferably between -120 ⁰ C and -80 ⁰ C.

The reaction according to the invention is preferably carried out under inert gas, in particular nitrogen or argon.

When carrying out the process according to the invention, the phenyloxy (thio) ketones of the formula (VI) and the halides of the formula (VII) are added in approximately equimolar amounts, but under or overshoots of up to about 20 mole percent are possible. The alkali metal-organic compound is advantageously used in excess of from 5 to 75 mole percent, preferably from 10 to 50 mole percent. It can be done by first reacting the alkali metal-organic compound with the halide of the formula (VII) and then adding the keto compound of the formula (VI); But you can also submit the keto compound and the halide and then at low temperature (eg at -100 ⁰ C to -130 ⁰ C) to add the alkali metal organic compound. The isolation tion of the compounds of formula (Ib) is carried out in such a way that the alkali alkoxide initially formed in the reaction (for example, lithium alkoxide) is hydrolyzed with water. The further work-up then takes place in the usual way.

Method D

The bromides of the formula (VIII) are known. The (thio) phenols of formula (V) are also known.

The phenol (oxy / thio) ketones of the formula (DC) which occur as intermediates in carrying out the process D according to the invention are novel. They can be prepared in a known manner (cf JP-A 62- 084061, WO 01/87878).

The organometallic compounds of the formula (X) are known, where M in the formula (X) is preferably lithium or magnesium.

The inventive method D (step 1) is carried out in the presence of a diluent and optionally in the presence of a base. Suitable diluents for the reaction according to the invention are all inert organic solvents. These include, preferably, alcohols, e.g. Ethanol and methoxyethanol; Ketones, e.g. 2-butanone; Nitriles, e.g. acetonitrile; Esters, e.g. Essigester; Ethers, e.g. dioxane; aromatic hydrocarbons, e.g. benzene and toluene; or amides, e.g. Dimethylformamide.

The reaction temperatures can be varied within a relatively wide range when carrying out the process according to the invention. In general, one works at temperatures between 0 ⁰ C and 200 ⁰ C, preferably between 20 ⁰ C and 100 ⁰ C. The reaction of the invention may optionally be carried out under elevated pressure. In general, one works between 1 and 50 bar, preferably between 1 and 25 bar.

When carrying out the process D according to the invention (step 1), 1 to 2 mol of (thio) phenol of the formula (V) and, if appropriate, 1 to 3 mol of base are used per mole of bromoketone of the general formula (VIII). The isolation of the end products takes place in a generally customary manner. The inventive method D (step 2) is carried out in the presence of a diluent and in the presence of an alkali metal-organic compound. Optionally, an acid or a metal salt is then added to the resulting compound of formula (Id) (see below). For the inventive reaction of compounds of the formula (DC) to give compounds of the formula (Id), suitable diluents are preferably inert organic solvents. These include, in particular, ethers, such as diethyl ether or tetrahydrofuran. Alkaline-organic compounds used in the reaction according to the invention are preferably alkaline earth metal alkyls, in particular t-butyl magnesium chloride; however, it is also possible to use alkali metal alkyls, such as t-butyllithium.

The reaction temperatures can be varied within a certain range in the process according to the invention. Generally carried out between -100 ° C and +20 ⁰ C, preferably between -78 ⁰ C and 0 ⁰ C. The reaction of the invention is preferably under an inert gas, in particular nitrogen or argon made.

When carrying out the process according to the invention, the ketones of the formula (IX) and the organometallic compounds of the formula (X) are added in approximately equimolar amounts, but under or overshoots of up to about 20 mol% are possible. The organometallic compound is advantageously used in excess of from 5 to 75 mole percent, preferably from 10 to 50 mole percent.

In this case, it is possible to initially introduce the ketone (DC) and then add the organometallic compound of the formula (X) at a suitable temperature (eg 0 ^° C.). The isolation of the compounds of the formula (Id) is carried out in such a way that the metal lalkanolate (for example magnesium alkoxide) initially formed in the reaction is hydrolyzed with water. The further work-up then takes place in the usual way.

Method E

The reaction of the phenyl (oxy / thio) alkanol derivatives of the formula (I-c) to give phenyl (oxy / thio) alkanol

Derivatives of the formula (I-e) can be carried out in two different ways (cf., EP-A 0 793 657).

One sets phenyl (oxy / thio) alkanol derivatives of the formula (I-c) either

(α) successively with strong bases and sulfur in the presence of a diluent and then hydrolyzed with water, optionally in the presence of an acid, or

(ß) with sulfur in the presence of a high-boiling diluent and then treated optionally with water and optionally with acid.

Suitable bases when carrying out process E, variant (α) according to the invention, are all strong alkali metal bases customary for such reactions. Preference is given to using n-butyl lithium, lithium diisopropylamide, sodium hydride, sodium amide and also potassium tert-butoxide in a mixture with tetramethylethylenediamine (= TMEDA).

When carrying out process E according to the invention, variant (α), all inert organic solvents customary for such reactions are suitable as diluents. Preferably, reversible are ethers, such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane, furthermore liquid ammonia or even strongly polar solvents, such as dimethyl sulfoxide.

Sulfur is preferably used in the form of powder. When carrying out the process E according to the invention, variant (α), water is used for the hydrolysis, if appropriate in the presence of an acid. In this case, all customary for such reactions customary inorganic or organic acids. Preferably usable are acetic acid, dilute sulfuric acid and dilute hydrochloric acid. However, it is also possible to carry out the hydrolysis with aqueous ammonium chloride solution.

The reaction temperatures can be varied within a certain range when carrying out variant (α). In general, temperatures between -70 ⁰ C and +20 ⁰ C, preferably between -70 ⁰ C and 0 ⁰ C.

In carrying out the process E according to the invention is generally carried out under atmospheric pressure. But it is also possible to work under increased or reduced pressure. Thus, especially when carrying out the variant (α) working under increased pressure in question.

When carrying out the process E according to variant (α) according to the invention, in general from 2 to 3 equivalents, preferably from 2.0 to 2.5 equivalents, are employed per mole of phenyl (oxy / thio) alkanol derivatives of the formula (Ic) strong base and then an equivalent amount or an excess of sulfur. The reaction may be carried out under a protective gas atmosphere, e.g. under nitrogen or argon. The workup is carried out by conventional methods.

When carrying out the process E according to variant (β) according to the invention, suitable diluents are all high-boiling organic solvents customary for such reactions. Preference is given to using amides, such as dimethylformamide and dimethylacetamide, furthermore heterocyclic compounds, such as N-methylpyrrolidone, and also ethers, such as diphenyl ether.

Sulfur is also used in carrying out the process E according to the invention variant (ß) generally in the form of powder. After the reaction, a treatment with water and _^ may optionally be carried out, if appropriate, with acid. This is carried out as the hydrolysis in carrying out the variant (α).

The reaction temperatures can also be varied within a substantial range when carrying out process E, variant (β) according to the invention. In general, temperatures of between 15O ⁰ C and 300 ⁰ C, preferably between 180 ° C and 250 ⁰ C. When carrying out the process E according to the invention according to variant (SS) is set to 1 mole of phenyl (oxy / thio) alkanol Derivatives of formula (Ic) generally 1 to 5 moles, preferably 1.5 to 3 moles of sulfur. The workup is carried out by conventional methods. - -

The compounds of the general formula (I) obtainable by the processes A and B according to the invention can be converted into acid addition salts or metal salt complexes.

For the preparation of physiologically acceptable acid addition salts of the compounds of the general formula (I), preference is given to the following acids: hydrohalic acids, such as e.g. Hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. Acetic, maleic, succinic, fumaric, tartaric, citric, salicylic, sorbic, lactic and sulfonic acids, e.g. p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

The acid addition salts of the compounds of general formula (I) can be easily prepared by conventional salt formation methods, e.g. by dissolving a compound of general formula (I) in a suitable inert solvent and adding the acid, e.g. Hydrochloric acid, and in a known manner, e.g. by filtration, isolated and optionally purified by washing with an inert organic solvent.

For the preparation of metal salt complexes of the 65 compounds of general formula (I) are preferably salts of metals of II. To IV. Main group and the I. and IL and FV. to VIII. Subgroup of the Periodic Table in question, copper, zinc, manganese, magnesium, tin, iron and nickel are exemplified.

Suitable anions of the salts are those which are preferably derived from the following acids: hydrohalic acids, e.g. Hydrochloric acid and hydrobromic acid, and also phosphoric acid, nitric acid and sulfuric acid.

The metal salt complexes of compounds of the general formula (I) can be obtained in a simple manner by conventional methods, e.g. by dissolving the metal salt in alcohol, e.g. Ethanol and adding to the compound of general formula I. Metal salt complexes can be prepared in known manner, e.g. isolate by filtration and optionally purified by recrystallization. The present invention further relates to an agent for controlling unwanted microorganisms comprising the active compounds according to the invention. Preferably, it is a fungicidal agent containing agriculturally useful auxiliaries, solvents, excipients, surfactants or extenders.

In addition, the invention relates to a method for controlling unwanted microorganisms, characterized in that the active compounds according to the invention are applied to the phytopathogenic fungi and / or their habitat.

According to the invention, the carrier means a natural or synthetic, organic or inorganic substance, with which the active ingredients for better applicability, especially for application planting or Plant parts or seeds, mixed or connected. The carrier, which may be solid or liquid, is generally inert and should be useful in agriculture.

Suitable solid or liquid carriers are: e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially Butanol, organic solvents, mineral and vegetable oils and derivatives thereof. Mixtures of such carriers can also be used. Suitable solid carriers for granules are: e.g. Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours, as well as granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems.

Suitable liquefied gaseous diluents or carriers are those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-type polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as

Xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water.

The compositions of the invention may additionally contain other ingredients, such as surfactants. Suitable surface-active substances are emulsifying and / or foam-forming agents, dispersants or wetting agents having ionic or nonionic properties or mixtures of these surface-active substances. Examples thereof are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylarylpolyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates, protein hydrolysates, lignin-sulphite liquors and methylcellulose. The presence of a surface-active substance is necessary if one of the active ingredient and / or one of the inert carriers is not soluble in water and when applied in water. The proportion of surface-active substances is between 5 and 40 percent by weight of the agent according to the invention.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Optionally, other additional components may also be included, e.g. protective colloids, binders, adhesives, thickeners, thixotropic substances, penetration promoters, stabilizers, sequestering agents, complexing agents. In general, the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes. In general, the agents and formulations according to the invention contain between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, particularly preferably between 0.5 and 90%. Active ingredient, most preferably between 10 and 70 weight percent.

The active compounds or compositions according to the invention can be used as such or as a function of their respective physical and / or chemical properties in the form of their formulations or the use forms prepared therefrom, such as aerosols, capsule suspensions, cold mist concentrates, hot mist concentrates, encapsulated granules, fine granules, flowable concentrates for the treatment of seed, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, foams, pastes , Pesticide-coated seeds, suspension concentrates, suspension-emulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water-soluble granules or tablets, water-soluble powders for seed treatment, wettable powders, active substance impregnation natural and synthetic substances as well as very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV-KaIt and warm mist formulations. The formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active compounds with at least one customary diluent, solvent or diluent, emulsifier, dispersing and / or binding or fixing agent, wetting agent, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments, defoaming agents, preservatives, secondary thickeners, adhesives, gibberellins and other processing aids. The compositions according to the invention comprise not only formulations which are already ready for use and which can be applied to the plant or the seed with a suitable apparatus, but also commercial concentrates which have to be diluted with water before use.

The active compounds according to the invention can be used as such or in their (commercially available) formulations and in the formulations prepared from these formulations in admixture with other (be) known), such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners or semiochemicals.

The treatment according to the invention of the plants and plant parts with the active ingredients or agents is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, spraying, sprinkling, evaporating, atomizing, atomizing, sprinkling, foaming, brushing, spreading, drenching, drip irrigation and propagating material, in particular for seeds By dry pickling, wet pickling, slurry pickling, encrusting, single or multi-layer wrapping, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.

The invention further comprises a method of treating seed.

The invention further relates to seed which has been treated according to one of the methods described in the previous paragraph. The seeds according to the invention are used in methods for the protection of seed from undesirable microorganisms. In these, a seed treated with at least one active substance according to the invention is used.

The active compounds or compositions according to the invention are also suitable for the treatment of seed. Much of the crop damage caused by harmful organisms is caused by infestation of the seed during storage or after sowing, and during and after germination of the plant. This phase is particularly critical because the roots and shoots of the growing plant are particularly sensitive and may cause only a small damage to the death of the plant. There is therefore a great interest in protecting the seed and the germinating plant by using suitable means.

The control of phytopathogenic fungi by the treatment of the seed of plants has long been known and is the subject of constant improvement. Nevertheless, there are a number of problems in the treatment of seeds that can not always be satisfactorily resolved. Thus, it is desirable to develop methods for protecting the seed and the germinating plant, which eliminate or at least significantly reduce the additional application of crop protection agents after sowing or after emergence of the plants. It is furthermore desirable to optimize the amount of the active ingredient used in such a way that the seed and the germinating plant are best protected against attack by phytopathogenic fungi, without, however, damaging the plant itself by the active ingredient used. In particular, methods for treating seed should also include the intrinsic fungicidal properties of transgenic plants in order to achieve optimum protection of the seed and the germinating plant with a minimum of pesticides.

The present invention therefore also relates to a process for the protection of seeds and germinating plants from the infestation of phytopathogenic fungi, in which the seed is treated with an inventive appropriate means is treated. The invention also relates to the use of the seed treatment agents according to the invention for the protection of the seed and of the germinating plant from phytopathogenic fungi. Furthermore, the invention relates to seed which has been treated with an agent according to the invention for protection against phytopathogenic fungi. The control of phytopathogenic fungi, which damage plants after emergence, takes place primarily through the treatment of the soil and the above-ground parts of plants with pesticides. Due to concerns about the potential impact of crop protection products on the environment and human and animal health, efforts are being made to reduce the amount of active ingredients applied. One of the advantages of the present invention is that due to the particular systemic properties of the active compounds or compositions according to the invention, the treatment of the seeds with these active ingredients or agents protects not only the seed itself, but also the resulting plants after emergence from phytopathogenic fungi , In this way, the immediate treatment of the culture at the time of sowing or shortly afterwards can be omitted. Likewise, it is to be regarded as advantageous that the active compounds or agents according to the invention can also be used in particular in the case of transgenic seed, wherein the plant growing from this seed is capable of expressing a protein which acts against pests. By treating such seeds with the active compounds or agents according to the invention, certain pests can already be controlled by the expression of the insecticidal protein, for example. Surprisingly, a further synergistic effect can be observed, which additionally increases the effectiveness for protection against pest infestation.

The compositions according to the invention are suitable for the protection of seed of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture and viticulture. In particular, these are seeds of cereals (such as wheat, barley, rye, triticale, millet and oats), corn, cotton, soya, rice, potatoes, sunflower, bean, coffee, turnip (eg sugar beet and fodder beet), peanut, Rapeseed, poppy, olive, coconut, cocoa, sugarcane, tobacco, vegetables (such as tomato, cucumber, onions and lettuce), turf and ornamental plants (see also below). Of particular importance is the treatment of the seeds of cereals (such as wheat, barley, rye, triticale and oats), corn and rice.

As also described below, the treatment of transgenic seed with the active compounds or agents according to the invention is of particular importance. This relates to the seed of plants containing at least one heterologous gene which allows expression of a polypeptide or protein having insecticidal properties. The heterologous gene in transgenic seed can be derived, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or GIi- ocladium. Preferably, this heterologous gene is derived from Bacillus sp., Wherein the gene product has an activity against the European corn borer and / or Western Com Rootworm. Most preferably, the heterologous gene is from Bacillus thuringiensis. In the context of the present invention, the agent according to the invention is applied to the seed alone or in a suitable formulation. Preferably, the seed is treated in a condition that is so stable that no damage occurs during the treatment. In general, the treatment of the seed can be done at any time between harvesting and sowing. Usually, seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp. For example, seed may be used which has been harvested, cleaned and dried to a moisture content below 15% by weight. Alternatively, seed can also be used, which after drying, for example, treated with water and then dried again.

In general, care must be taken in the treatment of the seed that the amount of the agent and / or other additives applied to the seed is chosen so that germination of the seed is not impaired or the resulting plant is not damaged. This must be taken into account, above all, with active ingredients which can show phytotoxic effects at certain application rates.

The agents according to the invention can be applied directly, ie without containing further components and without being diluted. In general, it is preferable to apply the agents to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described e.g. in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2. The active compounds which can be used according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, as well as ULV formulations.

These formulations are prepared in a known manner by mixing the active ingredients with conventional additives, such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and water.

Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, CI. Pigment Red 112 and CI. Solvent Red 1 known dyes.

Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds. Preference is given to using alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates. Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds. Preference is given to using nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide, block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives. Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.

Defoamers which may be present in the seed dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds. Preferably usable are silicone defoamers and magnesium stearate.

Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal. Suitable secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.

Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents. Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.

Suitable gibberellins which may be present in the seed dressing formulations which can be used according to the invention are preferably the gibberellins Al, A3 (= gibberellic acid), A4 and A7, particularly preferably gibberellic acid. The gibberellins are known (see R. Wegler "Chemie der Pflanzenschutz- und Schädlingsbekungsmittel", Vol. 2, Springer Verlag, 1970, pp. 401-412).

The seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds, including seed of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression. For the treatment of seed with the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water, all mixing devices customarily usable for the dressing can be considered. Specifically, in the pickling procedure, the seed is placed in a mixer which adds the desired amount of seed dressing formulations, either as such or after prior dilution with water, and mixes until evenly distributed the formulation on the seed. Optionally, a drying process follows. The active compounds or compositions according to the invention have a strong microbicidal action and can be used for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.

Fungicides can be used for the control of Plasmodiophoromycetes, Oomycetes, Chytriomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, En- terbacteriaceae, Corynebacteriaceae and Streptomycetaceae.

The fungicidal compositions according to the invention can be used curatively or protectively for controlling phytopathogenic fungi. The invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the active compounds or agents according to the invention, which is applied to the seed, the plant or plant parts, the fruits or the soil in which the plants grow.

The compositions of the invention for controlling phytopathogenic fungi in crop protection comprise an effective but non-phytotoxic amount of the active compounds of the invention. "Effective but non-phytotoxic amount" means an amount of the agent of the invention sufficient to sufficiently control the fungal disease of the plant This rate of application may generally vary over a wide range, depending on several factors, including the fungus to be controlled, the plant, the climatic conditions and the ingredients of the plant The good plant compatibility of the active ingredients in the concentrations necessary for controlling plant diseases allows a treatment of aboveground plant parts, of planting and seed, and of the soil.

According to the invention, all plants and parts of plants can be treated. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant variety protection rights. Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes become. The plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.

The active compounds according to the invention are suitable for plant tolerance, favorable warm-blooded toxicity and good environmental compatibility for the protection of plants and plant organs, for increasing them the crop yields, improving the quality of the crop. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.

As plants which can be treated according to the invention, mention may be made of the following: cotton, flax, grapevine, fruits, vegetables, such as Rosaceae sp. (for example, pomes such as apple and pear, but also drupes such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries), Rissesidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp. , Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example, banana trees and plantations), Rubiaceae sp. (for example, coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for example, lemons, organs and grapefruit); Solanaceae sp. (for example tomatoes), Liliaceae sp., Asteraceae sp. (for example, lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (for example cucumber), Alliaceae sp. leek, onion), Papilionaceae sp. (for example, peas); Main crops, such as Gramineae sp. (for example corn, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (for example sunflower), Brassicaceae sp. (for example, white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes and rapeseed, mustard, horseradish and cress), Fabacae sp. (for example, bean, peanuts), Papilionaceae sp. (for example, soybean), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example, sugar beet, fodder beet, Swiss chard, beet); Useful plants and ornamental plants in the garden and forest; and each genetically modified species of these plants. As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, wild-type or plant species obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and plant cultivars and their parts are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The term "parts" or "parts of plants" or "parts of plants" has been explained above.Propes of the respective commercial or in use plant varieties are particularly preferably treated according to the invention.PV plants are understood as meaning plants with new properties ("traits") Both have been grown by conventional breeding, by mutagenesis or by recombinant DNA techniques. These may be varieties, breeds, biotypes and genotypes.

The treatment method of the invention may be used for the treatment of genetically modified organisms (GMOs), e.g. As plants or seeds are used. Genetically modified plants (or transgenic plants) are plants in which a heterologous gene has been stably integrated into the genome. The term "heterologous gene" essentially means a gene which is provided or assembled outside the plant and which upon introduction into the nuclear genome, the chloroplast genome or the hypochondria genome confers new or improved agronomic or other properties to the transformed plant expressing a protein or polypeptide of interest or that it is another gene that is present in the plant or down-regulates or shuts down other genes that are present in the plant (for example by means of antisense technology, cosuppression technology or RNAi technology [RNA Interference]). A heterologous gene present in the genome is also referred to as a transgene. A transgene defined by its specific presence in the plant genome is referred to as a transformation or transgenic event.

Depending on the plant species or plant cultivars, their location and their growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention can also lead to superadditive ("synergistic") effects.For example, the following effects are possible expected effects: reduced application rates and / or extended spectrum of activity and / or increased efficacy of the active ingredients and compositions that can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or water or soil salt content , increased flowering efficiency, harvest relief, maturation acceleration, higher yields, larger fruits, greater plant height, intense green color of the leaf, earlier flowering, higher quality and / or higher nutritional value of the harvested products, higher sugar concentration in the Fruits, better shelf life and / or processability of the harvested products.

At certain application rates, the active compounds according to the invention can also exert a strengthening effect on plants. They are therefore suitable for mobilizing the plant defense system against attack by undesirable phytopathogenic fungi and / or microorganisms and / or viruses. This may optionally be one of the reasons for the increased effectiveness of the combinations according to the invention, for example against fungi. Plant-strengthening (resistance-inducing) substances in the present context should also mean those substances or substance combinations capable of stimulating the plant defense system in such a way that the treated plants, when subsequently inoculated with undesirable phytopathogenic fungi, have a considerable degree of resistance to these undesired ones exhibit phytopathogenic fungi. The substances according to the invention can therefore be employed for the protection of plants against attack by the mentioned pathogens within a certain period of time after the treatment. The period of time over which a protective effect is achieved generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active substances. Plants and plant varieties which are preferably treated according to the invention include all plants which have genetic material conferring on these plants particularly advantageous, useful features (whether obtained by breeding and / or biotechnology).

Plants and plant varieties which are also preferably treated according to the invention are resistant to one or more biotic siress factors, ie these plants have an improved defense against animal and microbial pests such as nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and / or viroids , Plants and plant varieties which can also be treated according to the invention are those plants which are resistant to one or more abiotic stress factors. Abiotic stress conditions may include, for example, drought, cold and heat conditions, osmotic stress, waterlogging, increased soil salinity, increased exposure to minerals, ozone conditions, high light conditions, limited availability of nitrogen nutrients, limited availability of phosphorous nutrients or avoidance of shade.

Plants and plant varieties which can also be treated according to the invention are those plants which are characterized by increased yield properties. An increased yield can in these plants z. These include improved plant physiology, improved plant growth and improved plant development, such as water utilization efficiency, water retention efficiency, improved nitrogen utilization, increased carbon assimilation, improved photosynthesis, increased germination power and accelerated maturation. Yield can be further influenced by improved plant architecture (under stress and non-stress conditions), including early flowering, control of flowering for hybrid seed production, seedling vigor, plant size, internode number and spacing, root growth, seed size, fruit size, Pod size, pod or ear number, number of seeds per pod or ear, seed mass, increased seed filling, reduced seed drop, reduced pod popping and stability. Other yield-related traits include seed composition such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in nontoxic compounds, improved processability, and improved shelf life. Plants which can be treated according to the invention are hybrid plants which already express the properties of the heterosis or of the hybrid effect, which generally leads to higher yields, higher growth, better health and better resistance to biotic and abiotic stress factors. Such plants are typically produced by crossing an inbred male sterile parental line (the female crossover partner) with another inbred male fertile parent line (the male crossover partner). The hybrid seed is typically harvested from the male sterile plants and sold to propagators. Pollen sterile plants can sometimes be produced (eg in the case of maize) by means of removal (ie mechanical removal of the male genitalia or the male flowers); however, it is more common for male sterility to be due to genetic determinants in the plant genome. In this case, especially when the desired product, as one wants to harvest from the hybrid plants, is the seeds, it is usually beneficial to ensure that the plant is fertile in hybrid plants that are responsible for the genetic susceptibility to male sterility Contain determinants, is completely restorated. This can be accomplished by ensuring that the male crossing partners possess appropriate fertility restorer genes capable of restoring pollen fertility in hybrid plants containing the genetic determinants responsible for male sterility. Genetic determinants of pollen sterility may be localized in the cytoplasm. Examples of cytoplasmic male sterility (CMS) have been described, for example, for Brassica species. However, genetic determinants of male sterility may also be localized in the cell nucleus. Pollen sterile plants can also be obtained using plant biotechnology methods such as genetic engineering. One A particularly favorable means of producing male sterile plants is described in WO 89/10396, wherein, for example, a ribonuclease such as a barnase is selectively expressed in the tapetum cells in the stamens. The fertility can then be restorated by expression of a ribonuclease inhibitor such as barstar in the tapetum cells. Plants or plant varieties (obtained by methods of plant biotechnology, such as genetic engineering) which can be treated according to the invention are herbicidally tolerant plants, ie plants that have been tolerated to one or more given herbicides. Such plants can be obtained either by genetic transformation or by selection of plants containing a mutation conferring such herbicide tolerance. Herbicide-tolerant plants are, for example, glyphosate-tolerant plants, ie plants that have been tolerated to the herbicide glyphosate or its salts. Thus, for example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium, the CP4 gene of the bacterium Agrobacterium sp., The genes which are suitable for an EPSPS from the petunia, for an EPSPS from the tomato or encode for an EPSPS from Eleusine. It can also be a mutated EPSPS. Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate oxidoreductase enzyme. Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate acetyltransferase enzyme. Glyphosate-tolerant plants can also be obtained by selecting plants which select for naturally occurring mutations of the above mentioned genes.

Other herbicide-resistant plants are, for example, plants which have been tolerated to herbicides which inhibit the enzyme glutamine synthase, such as bialaphos, phosphinotricin or glufosinate. Such plants can be obtained by expressing an enzyme which detoxifies the herbicide or a mutant of the enzyme glutamine synthase, which is resistant to inhibition. Such an effective detoxifying enzyme is, for example, an enzyme encoding a phosphinotricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphitricin acetyltransferase have been described.

Further herbicide-tolerant plants are also plants tolerant to the herbicides which inhibit the enzyme hydroxyphenylpyruvate dioxygenase (HPPD). The hydroxyphenyl pyruvate dioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogentisate. Plants tolerant to HPPD inhibitors can be transformed with a gene encoding a naturally occurring resistant HPPD enzyme or a gene encoding a mutant HPPD enzyme. Tolerance to HPPD inhibitors can also be achieved by transforming plants with genes encoding certain enzymes that allow the formation of homogentisate despite inhibition of the native HPPD enzyme by the HPPD inhibitor. The tolerance of plants to HPPD inhibitors may also be be improved by transforming plants in addition to a gene which encodes a HPPD-tolerant enzyme ^'with a gene encoding a prephenate dehydrogenase enzyme.

Other herbicide-resistant plants are plants that have been tolerated to acetolactate synthase (ALS) inhibitors. Examples of known ALS inhibitors include sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy (thio) benzoates and / or sulfonylaminocarbonyltriazolinone herbicides. It is known that various mutations in the enzyme ALS (also known as acetohydroxy acid synthase, AHAS) confer tolerance to different herbicides or groups of herbicides. The preparation of sulfonylurea tolerant plants and imidazolinone tolerant plants is described in International Publication WO 1996/033270. Other sulfonylurea and imidazolinone tolerant plants are also disclosed in e.g. WO 2007/024782 described.

Other plants tolerant to imidazolinone and / or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or by mutation breeding.

Plants or plant varieties (obtained by plant biotechnology methods such as genetic engineering) which can also be treated according to the invention are insect-resistant transgenic plants, i. Plants that have been made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such insect resistance.

The term "insect-resistant transgenic plant" as used herein includes any plant containing at least one transgene comprising a coding sequence encoding:

1) an insecticidal crystal protein from Bacillus thuringiensis or an insecticidal part thereof, such as the insecticidal crystal proteins, available online at:

http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/, or insecticidal parts thereof, e.g. Cry protein class proteins CrylAb, CrylAc, Cry1F, Cry2Ab, Cry3Ae or Cry3Bb or insecticidal portions thereof; or

2) a Bacillus thuringiensis crystal protein or a part thereof which is insecticidal in the presence of a second crystal protein other than Bacillus thuringiensis or a part thereof, such as the binary toxin consisting of the crystal proteins Cy34 and Cy35; or

3) an insecticidal hybrid protein comprising parts of two different insecticidal crystal proteins from Bacillus thuringiensis, such as a hybrid of the proteins of 1) above or a hybrid of the proteins of 2) above, e.g. The protein CrylA.105 produced by the corn event MON98034 (WO 2007/027777); or

4) a protein according to any of items 1) to 3) above, in which some, in particular 1 to 10, amino acids have been replaced by another amino acid in order to achieve a higher insecticidal activity against a target insect species and / or the spectrum of the corresponding Target species and / or due to changes in the coding DNA during the Cloning or transformation were induced, such as the protein Cry3Bbl in maize events MON863 or MON88017 or the protein Cry3A in the maize event MIR 604;

5) an insecticidal secreted protein from Bacillus thuringiensis or Bacillus cereus or an insecticidal part thereof, such as the vegetative insecticidal proteins (VIPs) described in U.S. Pat

http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/vip.html are listed, for. B. Proteins of protein class VIP3Aa; or

6) a secreted protein from Bacuus thuringiensis or BacUlus cereus, which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or B.cereus, such as the binary toxin consisting of the proteins VIP IA and VIP2A.

7) a hybrid insecticidal protein comprising parts of various secreted proteins of Bacillus thuringiensis or Baculus cereus, such as a hybrid of the proteins of 1) or a hybrid of the proteins of 2) above; or

8) a protein according to any one of items 1) to 3) above, in which some, in particular 1 to 10, amino acids have been replaced by another amino acid in order to achieve a higher insecticidal activity against a target insect species and / or the spectrum of the corresponding target insect species, and / or due to changes induced in the coding DNA during cloning or transformation (preserving the coding for an insecticidal protein), such as the protein VIP3Aa in the cotton event COT 102. Of course, it counts the insect-resistant transgenic plants in the present context also any plant comprising a combination of genes encoding the proteins of any of the above classes 1 to 8. In one embodiment, an insect resistant plant contains more than one transgene encoding a protein of any one of the above 1 to 8 in order to extend the spectrum of the corresponding target insect species or to delay the development of resistance of the insects to the plants by use different proteins which are insecticidal for the same target insect species, but have a different mode of action, such as binding to different receptor binding sites in the insect.

Plants or plant varieties (obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are tolerant to abiotic stressors. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such stress resistance. Particularly useful plants with stress tolerance include the following:

a. Plants which contain a transgene which is able to reduce the expression and / or activity of the gene for the poly (ADP-ribose) polymerase (PARP) in the plant cells or plants. b. Plants containing a stress tolerance-enhancing transgene capable of reducing the expression and / or activity of the PARG-encoding genes of the plants or plant cells; c. Plants containing a stress tolerance enhancing transgene which is functional in plants

Enzyme of the nicotinamide adenine dinucleotide salvage biosynthesis pathway, including nico- tinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyltransferase, nicotinamide adenine dinucleotide synthetase or nicotinamide phosphoribosyltransferase.

Plants or plant varieties (obtained by plant biotechnology methods such as genetic engineering), which can also be treated according to the invention, have an altered amount, quality and / or shelf life of the harvested product and / or altered properties of certain components of the harvested product on, such as:

1) Transgenic plants which synthesize a modified starch with respect to their chemical-physical properties, in particular the amylose content or the amylose / amylopectin ratio, the degree of branching, the average chain length, the distribution of the side chains, the viscosity behavior, the gel strength, the starch grain size and / or starch morphology in comparison to the synthesized starch in wild-type plant cells or plants, so that this modified starch is better suited for certain applications.

2) Transgenic plants that synthesize non-starch carbohydrate polymers or non-starch carbohydrate polymers whose properties are altered compared to wild-type plants without genetic modification. Examples are plants that polyfructose, especially the inulin and

Levantyps, plants that produce alpha-1,4-glucans, plants that produce alpha-1,6-branched alpha-1,4-glucans, and plants that produce alternan.

3) Transgenic plants that produce hyaluronan.

Plants or plant varieties (obtained by plant biotechnology methods such as genetic engineering), which can also be treated according to the invention, are plants such as cotton plants with altered fiber properties. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such altered fiber properties; these include:

a) plants, such as cotton plants, containing an altered form of cellulose synthase genes, b) plants, such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids;

c) plants such as cotton plants having increased expression of sucrose phosphate synthase; d) plants such as cotton plants with increased expression of sucrose synthase;

e) plants such as cotton plants in which the timing of the passage control of the Plasmodes- men at the base of the fiber cell is changed, z. By down-regulating the fiber-selective β-1,3-glucanase;

f) plants such as cotton plants with modified reactivity fibers, e.g. By expression of the N-acetylglucosamine transferase gene, including nodC, and chitin synthase genes.

Plants or plant varieties (obtained by plant biotechnology methods such as genetic engineering) which can also be treated according to the invention are plants such as oilseed rape or related Brassica plants with altered oil composition properties. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such altered oil properties; these include:

a) plants, such as oilseed rape plants, which produce oil of high oleic acid content;

b) plants such as oilseed rape plants, which produce oil with a low linolenic acid content.

c) plants such as rape plants that produce oil with a low saturated fatty acid content.

Particularly useful transgenic plants that can be treated according to the invention are plants having one or more genes encoding one or more toxins, and are the transgenic plants offered under the following tradenames: YIELD GARD® (for example, corn, cotton , Soybeans), KnockOut® (for example corn), BiteGard® (for example maize), BT-Xtra® (for example maize), StarLink® (for example corn), Bollgard® (cotton), Nucotn® (cotton), Nutcotn 33B® (cotton), NatureGard® (for example corn), Protecta® and NewLeaf® (potato). Herbicide-tolerant crops to be mentioned include, for example, corn, cotton and soybean varieties sold under the following tradenames: Roundup Ready® (glyphosate tolerance, for example, corn, cotton, soybean), Liberty Link® (phosphinotricin tolerance, for example - rapeseed), MI® (imidazolinone tolerance) and SCS® (Sylfonylurea Tolerance), for example corn. The herbicide-resistant plants (plants traditionally grown for herbicide tolerance) to be mentioned include the varieties sold under the name Clearfeld® (for example corn).

Particularly useful transgenic plants that can be treated according to the invention are plants that contain transformation events, or a combination of transformation events, and that are listed, for example, in the files of various national or regional authorities (see, for example, http : //gmoinfo.jrc.it/gmp_browse.aspx and http://www.agbios.com/dbase.php).

The active compounds or compositions according to the invention can also be used in the protection of materials for the protection of industrial materials against attack and destruction by undesired microorganisms, such as e.g. Mushrooms and insects, are used. Furthermore, the compounds according to the invention can be used alone or in combinations with other active substances as antifouling agents.

Technical materials as used herein mean non-living materials that have been prepared for use in the art. For example, technical materials to be protected from microbial alteration or destruction by the active compounds of the present invention may be adhesives, glues, paper, wallboard and board, textiles, carpets, leather, wood, paints and plastics, coolants and other materials used by Microorganisms can be attacked or decomposed. The materials to be protected also include parts of production plants and buildings, eg cooling water circuits, cooling and heating systems and ventilation and air conditioning systems, which may be affected by the proliferation of microorganisms. In the context of the present invention, as technical materials it is preferable to use adhesives, glues, papers and cardboard, leather, wood, paints, cooling lubricants and heat exchangers. tragungsflüssigkeiten called, more preferably wood. The active compounds or compositions according to the invention can prevent adverse effects such as decay, deterioration, decomposition, discoloration or mold. In addition, the compounds of the invention for protection against fouling of objects, in particular of hulls, screens, nets, structures, quays and signal systems, which come in contact with seawater or brackish water, can be used.

The inventive method for controlling unwanted fungi can also be used for the protection of so-called storage goods. Under "Storage Goods" are understood natural substances of plant or animal origin or their processing products, which were taken from nature and for long-term protection is desired Storage goods of plant origin, such as plants or plant parts, such as stems, leaves, tubers, seeds , Fruits, grains, can be protected in freshly picked condition or after processing by (pre-) drying, moistening, crushing, grinding, pressing or roasting.Storage goods also includes lumber, whether unprocessed, such as lumber, SttOmleitungsmasten and Barriers, or in the form of finished products, such as furniture.Storage goods of animal origin are, for example, skins, leather, furs and hair.The active compounds according to the invention can prevent disadvantageous effects such as decay, deterioration, disintegration, discoloration or mold.

By way of example, but not by way of limitation, some pathogens of fungal diseases which can be treated according to the invention are named:

Diseases caused by powdery mildews such as e.g. Blumeria species, such as Blumeria graminis; Podosphaera species, such as Podosphaera leucotricha; Sphaerotheca species, such as Sphaerotheca fuliginea; Uncinula species, such as Uncinula necator; Diseases caused by causative agents of rust diseases, such as Gymnosporangium species, such as Gymnosporangium sabinae; Hemileia species, such as Hemileia vastatrix; Phocopsora species, such as Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, such as Puccinia recondita or Puccinia triticina; Uromyces species, such as Uro- myces appendiculatus;

Diseases caused by pathogens of the group of Oomycetes, e.g. Bremia species, such as Bremia lactucae; Peronospora species such as Peronospora pisi or P. brassicae; Phytophthora species, such as Phytophthora infestans; Plasmopara species, such as Plasmopara viticola; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species such as Pythium ultimum;

Leaf spot diseases and leaf wilt caused by, for example, Alternaria species such as Alternaria solani; Cercospora species, such as Cercospora beticola; Cladiosporum species, such as Cladiosporium cucumerinum; Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, Syn: Hehninthosporium); Colletotrichum species, such as Colle totrichum Lindemuthanium; Cycloconium species such as cycloconium oleaginum; Slide types such as Diaporthe citri; Elsinoe species, such as Elsinoe fawcettii; Globeosporium species, such as, for example, Gloeosporium laeticolor; Glomerella species, such as Glomerella cingulata; Guignardia species, such as Guignardia bidwelli; Leptosphaeria species, such as Leptosphaeria maculans; Magnaporthe species, such as Magnaporthe grisea; Microdochium species such as Microdochium nivale; Mycosphaerella species, such as Mycosphaerella graminicola and M. fijiensis; Phaeosphaeria species, such as Phaeosphaeria nodorum; Pyrenophora species, such as, for example, Pyrenophora teres; Ramularia species, such as Ramularia collo-cygni; Rhynchosporium species, such as Rhynchosporium secalis; Septoria species, such as Septoria apii; Typhula species, such as Typhula incarnata; Venturia species, such as Venturia inaequalis;

Root and stem diseases caused by e.g. Corticium species, such as Corticium graminearum; Fusarium species such as Fusarium oxysporum; Gaeumannomyces species such as Gaeumannomyces graminis; Rhizoctonia species, such as Rhizoctonia solani; Tapesia species, such as Tapesia acuformis; Thielaviopsis species, such as Thielaviopsis basicola; Ear and panicle diseases (including corncob) caused by e.g. Alternaria species, such as Alternaria spp .; Aspergillus species, such as Aspergillus flavus; Cladosporium species, such as Cladosporium cladosporioides; Claviceps species, such as Claviceps puφurea; Fusarium species such as Fusarium culmorum; Gibberella species, such as Gibberella zeae; Monographella species, such as Monographella nivalis; Septoria species such as Septoria nodorum;

Diseases caused by fire fungi, e.g. Sphacelotheca species, such as, for example, Sphace- lotheca reiliana; Tilletia species such as Tilletia caries, T. controversa; Urocystis species, such as Urocystis occulta; Ustilago species such as Ustilago nuda, U. nuda tritici;

Fruit rot caused by e.g. Aspergillus species, such as Aspergillus flavus; Botrytis species, such as Botrytis cinerea; Penicillium species such as Penicillium expansum and P. puφurogenum; Sclerotinia species, such as Sclerotinia sclerotiorum;

Verticilium species such as Verticilium alboatrum;

Seed and soil rots and wilts, as well as seedling diseases caused by e.g. Fusarium species such as Fusarium culmorum; Phytophthora species, such as Phytophthora cactorum; Pythium species such as Pythium ultimum; Rhizoctonia species, such as Rhizoctonia solani; Sclerotium species, such as Sclerotium rolfsii;

Cancers, galls and witches brooms caused by e.g. Nectria species, such as Nectria galligena;

Wilt diseases caused by e.g. Monilinia species such as Monilinia laxa;

Deformations of leaves, flowers and fruits caused by e.g. Taphrina species, such as Taphrina deformans;

Degenerative diseases of woody plants caused by e.g. Esca species such as Phaemoniella clamydospora and Phaeoacremonium aleophilum and Fomitiporia mediterranea;

Floral and seed diseases caused by, for example, Botrytis species such as Botrytis cinerea; Diseases of plant tubers caused by, for example, Rhizoctonia species, such as Rhizoctonia solani; Helminthosporium species, such as Helminthosporium solani;

Diseases caused by bacterial agents such as e.g. Xanthomonas species, such as Xanthomonas campestris pv. Oryzae; Pseudomonas species, such as Pseudomonas syringae pv. Lachrymans; Erwinia species, such as Erwinia amylovora;

Preferably, the following diseases of soybean beans can be controlled:

Fungal diseases on leaves, stems, pods and seeds caused by e.g. Alternaria leaf spot (Alternaria spec. Atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. Truncatum), Brown spot (Septoria glycines), Cercospora leaf spot and blight (Cercospora kikuchii), Choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)) , Dactuliophora leaf spot (Dactuliophora glycines), Downy Mildew (Peronospora manshurica), Drechslera blight (Drechslera glycini), Frogeye leaf spot (Cercospora sojina), Leptosphaerulina leaf spot (Leptosphaerulina trifolii), Phyllostica leaf spot (Phyl- losticta sojaecola), Pod and Stem Blight (Phomopsis sojae), Powdery Mildew (Microsphaera diffusa), Pyrenochaeta Leaf Spot (Pyrenochaeta glycines), Rhizoctonia Aerial, Foliage, and Web Blight (Rhizoctonia solani), Rust (Phakopsora pachyrhizi, Phakopsora meibomiae), Scab (Sphaceloma glycines), Stemphylium Leaf Blight (Stemphylium botryosum), Target Spot (Corynespora cassiicola).

Fungal diseases on roots and stem base caused by e.g. Black Root Red (Calonectria crotalariae), Charcoal Red (Macrophomina phaseolina), Fusarium Blight or WiIt, Root Red, and Pod and Collar Red (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), Mycoleptodiscus Root Red (Mycoleptodiscus terrestris ), Neocosmospora (Neocosmopspora vasinfecta), Pod and Stem Blight (Diaporthe phaseolorum), Stem Canker (Diaporthe phaseolorum var. Caulivora), Phytophthora red (Phytophthora megasperma), Brown Stem Red (Phialophora gregata), Pythium red (Pythium aphanidermatum, Pythium irregular, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), Rhizoctonia Root Red, Stem Decay, and Damping Off (Rhizoctonia solani), Sclerotinia Stem Decay (Sclerotinia sclerotiorum), Sclerotinia Southern Blight (Sclerotinia rolfsii), Thielaviopsis Root Red (Thielaviopsis basicola).

As microorganisms that can cause degradation or a change in the technical materials, for example, bacteria, fungi, yeasts, algae and mucus organisms may be mentioned. The active compounds according to the invention preferably act against fungi, in particular molds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae. For example, microorganisms of the following genera are mentioned: Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, like Chaetomium globosum; Coniophora, such as Coniophora pentana; Lentinus, like Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride; Escherichia, like Escherichia coli; Pseudomonas, such as Pseudomonas aeruginosa; Staphylococcus, such as Staphylococcus aureus. In addition, the active compounds according to the invention also have very good antifungal effects. They have a very broad antimycotic spectrum of activity, in particular against dermatophytes and yeasts, mold and diphasic fungi (eg against Candida species such as Candida albicans, Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, microsporon species such as Microsporon canis and audouinii. The list of these fungi is by no means a limitation of the detectable mycotic spectrum, but has only an explanatory character.

The active compounds according to the invention can therefore be used both in medical and non-medical applications. When using the active compounds according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the mode of administration. The application rate of the active compounds according to the invention is

In the treatment of plant parts, e.g. Leaves: from 0.1 to 10,000 g / ha, preferably from 10 to 1,000 g / ha, more preferably from 50 to 300 g / ha (when used by pouring or drop, the application rate can even be reduced, especially if inert substrates as

Rockwool or perlite are used);

In the case of seed treatment: from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed, more preferably from 2.5 to 25 g per 100 kg of seed, most preferably from 2.5 to 12, 5 g per 100 kg of seed;

In the case of soil treatment: from 0.1 to 10,000 g / ha, preferably from 1 to 5,000 g / ha.

These application rates are given by way of example only and not by way of limitation within the meaning of the invention.

The active compounds or compositions according to the invention can therefore be used to protect plants within a certain period of time after the treatment against attack by the mentioned pathogens. The period of time within which protection is afforded generally ranges from 1 to 28 days, preferably from 1 to 14 days, more preferably from 1 to 10 days, most preferably from 1 to 7 days after treatment of the plants with the active ingredients or up to 200 days after seed treatment.

In addition, can be reduced by the treatment according to the invention, the mycotoxin content in Emtegut and the food and feed produced therefrom. Specifically, but not exclusively, mycotoxins include: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2 and HT2 toxin, fumonisins, zearalenone, moniliformin, fusarin, diaceotoxyscirpenol (DAS) , Beauvericin, enniatine, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins, which may be caused, for example, by the following fungi: Fusarium spec., Such as Fusarium acatumum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberella zeae), F. equiseti, F. fujiko-roi, F. musarum, F. oxysporum, F. proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi, - -

F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides, et al. as well as of Aspergillus spec., Penicillium sp., Claviceps puφurea, Stachybotrys spec. et al

The compounds according to the invention may optionally also be used in certain concentrations or application rates as herbicides, safeners, growth regulators or agents for improving plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including antiproliferative agents) or as agents MLO (Mycoplasma-like-organism) and RLO (Rickettsia-like-organism) are used. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active ingredients.

The active compounds according to the invention intervene in the metabolism of the plants and can therefore also be used as growth regulators.

Plant growth regulators can exert various effects on plants. The effects of the substances depend essentially on the time of application, based on the stage of development of the plant and on the amounts of active substance applied to the plants or their surroundings and on the mode of administration. In any case, growth regulators should influence the crop plants in a specific way.

Plant growth-regulating substances can be used, for example, for inhibiting the vegetative growth of the plants. Such growth inhibition is of economic interest among grasses, among other things, because this can reduce the frequency of grass clippings in ornamental gardens, parks and sports facilities, on roadsides, at airports or in orchards. Also of importance is the inhibition of the growth of herbaceous and woody plants on roadsides and near pipelines or overland pipelines, or more generally in areas where a high growth of the plants is undesirable.

Also important is the use of growth regulators to inhibit grain elongation. This reduces or completely eliminates the risk of crop stagnation before harvesting, and crop growth regulators can produce a straw boost that also counteracts storage, and the use of growth regulators for crop shortening and stalk augmentation allows for higher fertilizer levels to increase the yield without the risk of storing the grain.

An inhibition of vegetative growth enables a denser planting in many crops, so that multi-carrier can be achieved based on the soil surface. An advantage of the smaller plants thus obtained is that the culture can be more easily processed and harvested.

An inhibition of the vegetative growth of the plants can also lead to increased yields that the nutrients and assimilates benefit the flower and fruit formation to a greater extent than the vegetative plant parts. Growth regulators can often be used to promote vegetative growth. This is of great benefit when harvesting the vegetative plant parts. Promoting vegetative growth can, however, simultaneously promote generative growth by producing more assimilates so that more or more fruits are produced. Yield increases can in some cases be achieved through an intervention in the plant metabolism, without any noticeable changes in vegetative growth. Furthermore, with growth regulators, a change in the composition of the plants can be achieved, which in turn can lead to an improvement in the quality of the harvested products. For example, it is possible to increase the sugar content in sugar beets, sugar cane, pineapple and citrus fruits, or to increase the protein content in soya or cereals. It is also possible, for example, the degradation of desirable ingredients such. Sugar in sugar beet or cane, with growth regulators before or after harvesting. In addition, the production or the discharge of secondary plant ingredients can be positively influenced. An example is the stimulation of latex flow in gum trees.

Under the influence of growth regulators, parthenocarp fruits may develop. Furthermore, the sex of the flowers can be influenced. Also, a sterility of the pollen can be produced, which has a great importance in the breeding and production of hybrid seed.

Through the use of growth regulators, the branching of the plants can be controlled. On the one hand, the development of side shoots can be promoted by breaking the apicoid dominance, which can be very desirable, especially in ornamental plant cultivation, also in connection with growth inhibition. On the other hand, it is also possible to inhibit the growth of the lateral shoots. For this effect there is e.g. great interest in growing tobacco or planting tomatoes.

Under the influence of growth regulators, the foliage of the plants can be controlled so that a defoliation of the plants is achieved at a desired time. Such defoliation plays a major role in the mechanical harvesting of cotton, but is also important in other plastics such as cotton. in viticulture to facilitate the harvest of interest. Defoliation of the plants may also be done to reduce the transpiration of the plants before transplanting.

Likewise can be controlled with growth regulators the fruit case. On the one hand, a premature fruit drop can be prevented. On the other hand, the fruit fall or even the fall of the flowers can be promoted to a desired mass ("thinning out") to break the alternation.Old age refers to the peculiarity of some fruit species, endogenously conditioned from year to year Finally, it is possible with growth regulators to reduce the forces required to detach the fruits at the time of harvest to facilitate mechanical harvesting or facilitate manual harvesting.

Growth regulators can also be used to accelerate or retard the ripeness of the crop before or after harvesting. This is of particular advantage because it creates a optimal adaptation to the needs of the market. In addition, growth regulators may in some cases improve fruit colouration. In addition, with growth regulators, a temporal concentration of maturity can be achieved. This creates the prerequisites for complete mechanical or manual harvesting of tobacco, tomatoes or coffee in a single operation.

By employing growth regulators, furthermore, the seed or bud dormancy of the plants can be influenced, so that the plants, such as e.g. Pineapples or ornamental plants in nurseries to germinate, sprout or flower at a time when they normally do not show any willingness to do so. Delaying bud sprouting or seed germination using growth regulators may be desirable in areas prone to frost to prevent damage from late frosts.

Finally, growth regulators can induce plant resistance to frost, dryness or high soil salinity. This makes it possible to cultivate plants in areas that are normally unsuitable for this purpose.

The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the agents according to the invention. The preferred ranges given above for the active compounds or agents also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the compounds or agents specifically mentioned in the present text.

The invention is illustrated by the following examples. However, the invention is not limited to the examples.

Preparation Examples

Preparation of Compound No. 12 (Method C)

A mixture of 4.0 g (14.0 mmol) of 1- (4-bromo-2-methylphenoxy) -3,3-dimethylbutan-2-one and 2.57 g (16.1 mmol) of 5-bromopyrimidine in 20 ml of dry tetrahydrofuran and 20 ml of dry diethyl ether is cooled to -120 ° C under argon atmosphere. With stirring, n-butyllithium (10.5 ml, 1.6M, 16.8 mmol) is then added slowly. When the addition is complete, the reaction mixture is warmed slowly to room temperature overnight. The reaction mixture is mixed with 20 ml of a 10% aqueous ammonium chloride solution and the organic phase separated. The organic phase is then washed with 1N hydrochloric acid and saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered and concentrated. The crude product is then purified by column chromatography (cyclohexane / ethyl acetate 1: 1). This gives 0.7 g (13%) of the desired product. Preparation of Compound No. 13 (Method B)

To 0.90 g (4.32 mmol) of 2,3-difluoro-4-bromophenol dissolved in 20 ml of N, N-dimethylformamide are added at room temperature under an argon atmosphere 0.17 g (60%, 4.32 mmol) of sodium hydride and the reaction mixture for 1 h at Room temperature stirred. Subsequently, 0.7 g (3.92 mmol) 5- (2-tert-butyloxirane-2-yl)) pyrimidine was added and the reaction mixture stirred for 12 h at 100 ⁰ C. After cooling to room temperature, the solvent is removed under reduced pressure and the residue is treated with saturated aqueous sodium chloride solution and ethyl acetate. The organic phase is separated, dried over sodium sulfate, filtered and concentrated. The crude product is then purified by column chromatography (cyclohexane / ethyl acetate 1: 1). 0.33 g (22%) of the desired product are obtained.

Preparation of 5- (2-tert-buryloxiran-2-yl) pyrimidine

Under an argon atmosphere, 0.96 g (4.3 mmol) of trimethylsulfoxonium iodide and 0.17 g of sodium hydride (60%, 4.3 mmol) are slowly added dropwise to 10 ml of dimethyl sulfoxide. The reaction mixture is then stirred for 15 minutes at room temperature and 0.65 g (3.9 mmol) of 2,2-dimethyl-1- (5-pyrimidinyl) -1-propanone, dissolved in 2 ml of tetrahydrofuran, are added. The reaction mixture is stirred for 90 min at 50 ^° C. The reaction mixture is then concentrated under reduced pressure and the residue is treated with saturated aqueous sodium chloride solution and ethyl acetate. The organic phase is separated, dried over sodium sulfate, filtered and concentrated. This gives 0.70 g (99%) of the desired product, which is reacted without further purification.

Preparation of Compound No. 1 (Method B)

124 mg (60%, 3.09 mmol) of sodium hydride are added at room temperature under argon atmosphere to 0.72 g (3.39 mmol) of 2-chloro-5-trifluoromethylthiophenol dissolved in 25 ml of N, N-dimethylformamide, and the reaction mixture is stirred for 1 h at RT , Subsequently, 0.56 g (3.09 mmol) of l - [[2- (1, 1-dimethylethyl) -2-oxiranyl] methyl] -1H-l, 2,4-triazole (preparation see DE 3111238) are added and the reaction mixture is stirred for 12 Stirred at 100 ⁰ C h. After cooling to room temperature, the solution is Removed - solvent under reduced pressure and the residue with saturated aqueous sodium chloride solution and ethyl acetate. The organic phase is separated, dried over sodium sulfate, filtered and concentrated. The crude product is then purified by column chromatography (cyclohexane / ethyl acetate 1: 1). 0.21 g (18%) of the desired product are obtained. Analogously to the preceding examples and according to the general descriptions of the processes according to the invention, the compounds of the formula (I) mentioned in Table 1 below can be obtained.

Table 1

- -

The measurement of the logP values was carried out according to EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversed-phase columns (C 18), using the following methods: [a] The determination by LC-MS in acid Range at pH 2.7 with 0.1% aqueous formic acid and acetonitrile (containing 0.1% formic acid) as an eluent linear gradient of 10% acetonitrile to 95% acetonitrile

Example A: Sphaerotheca test (cucumber) / protective

Solvent: 49 parts by weight of N, N-dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young cucumber plants are sprayed with the preparation of active compound in the stated application rate. One day after the treatment, the plants are inoculated with a spore suspension of Sphaerotheca fiiliginea. Subsequently, the plants are placed in a greenhouse at 70% relative humidity and a temperature of 23 ° C. 7 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. In this test, the following compounds 1, 4, 5, 7, 8, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55 and 56 at an active ingredient concentration of 500 ppm have an efficiency of 70% or more.

Example B: Venturia test (apple) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkyl-aryl-polyglycol ether - -

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on the advertising nokuliert the plants with an aqueous conidia suspension of the apple scab Venturia inaequalis and then remain i- 1 day at about 20 ⁰ C and 100% relative humidity in an incubation cabinet. The plants are then placed in the greenhouse at about 21 ⁰ C and a relative humidity of about 90%. 10 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. In this test, the following compounds of the invention show 7, 8, 11, 12, 13, 18, 19, 22, 25, 26, 28, 29, 30, 31, 40, 41, 43, 47, 50, 51, 52 and 53 at an active ingredient concentration of 100 ppm, an efficiency of 70% or more.

Example C: Uromvces test (bean) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkyl-aryl-polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the active substance preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of bean rust pathogen, Uromyces appendiculatus and then remain for 1 day at about 20 ⁰ C and 100% relative humidity in an incubation cabinet. The plants are then placed in the greenhouse at about 21 ⁰ C and a relative humidity of about 90%. 10 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. In this test, the following compounds 7, 8, 11, 12, 13, 14, 18, 19, 22, 25, 26, 28, 29, 30, 31, 33, 40, 41, 43, 47, 50, 51, 52 and 53 at an active ingredient concentration of 100 ppm, an efficiency of 70% or more.

Example D: Blumeria graminis test (barley) / protective

Solvent: 49 parts by weight of N, N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried, the plants are planted with spores of Blumeria graminis f.sp. hordei pollinated. The plants are placed in a greenhouse at a temperature of about 18 ° C and a relative humidity of about 80% to promote the development of mildew pustules. 7 days after inoculation, the Evaluation. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. In this test, the following compounds 7, 8, 11, 11, 12, 13, 14, 19, 22, 25, 28, 29, 30, 31 and 37 according to the invention show an efficiency of 70% at an active ingredient concentration of 500 ppm. or more. Example E: Leptosphaeria nodorum test (wheat ^" ) / protective

Solvent: 49 parts by weight of N, N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are sprayed with spores with a spore suspension of Leptosphaeria nodorum. The plants remain for 48 hours at 20 ° C and 100% relative humidity in an incubation cabin. The plants are placed in a greenhouse at a temperature of about 22 ° C and a relative humidity of about 80%. 8 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. In this test, the following compounds of the invention, 7, 8, 11, 12, 13, 14, 19, 22, 25, 28, 29, 30, 31 and 37 showed an efficacy of 70% or more at 500 ppm active ingredient concentration , Example F: Pyricularia test (rice) / protective

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration. To test for protective activity, young rice plants are sprayed with the preparation of active compound in the stated application rate. 1 day after the

Treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae.

Subsequently, the plants are placed in a greenhouse at 100% relative humidity and 25 ⁰ C. 7 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. In this test, the compound of the invention exhibited 12 at a concentration

Active ingredient of 500 ppm has an efficiency of 80% or more.

Example G: Rhizoctonia test (rice) / protective

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound with the stated amount of solvent and the concentrate is diluted with water and the indicated Amount of emulsifier to the desired concentration. To test for protective activity, young rice plants are sprayed with the preparation of active compound in the stated application rate. One day after the treatment, the plants are inoculated with hyphae of Rhizoctonia solani. Subsequently, the plants are placed in a greenhouse at 100% relative humidity and 25 ° C. 4 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. In this test, the compound 12 of the invention showed an efficiency of 80% or more at a concentration of active ingredient of 500 ppm:

Example H: Cochliobolus test (rice / protective

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration. To test for protective activity, young rice plants are sprayed with the preparation of active compound in the stated application rate. One day after the treatment, the plants are inoculated with an aqueous spore suspension of Cochliobolus miyabeanus. Subsequently, the plants are placed in a greenhouse at 100% relative humidity and 25 ° C. 7 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. In this test, the compound 12 of the invention showed an efficiency of 80% or more at a concentration of active ingredient of 500 ppm:

Example I: Phakopsora test (soy) / protective

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 parts by weight of polyoxyethylene alkylphenyl ether (polyoxyethylene (16) tristearyl phenyl ether)

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. One day after spraying, the plants are sprayed with an aqueous spore suspension of Phakopsora pachyrhizi. The plants remain at 20 ⁰ C and 80% relative humidity in the greenhouse. 11 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. In this test, the compound 8 of the invention showed an efficiency of 80% or more at a concentration of 250 ppm. Example J: Production of fumonisin FB1 by Fusarium proliferatum

The compounds were plated in microtiter plates in a fumonisin-inducing liquid medium (0.5 g malt extract, 1 g yeast extract, 1 g bactopeptone, 20 g fructose, 1 g KH ₂ PO ₄ , 0.3 g MgSO ₄ .7H ₂ O, 0.3 g - -

KCl, 0.05 g ZnSO ₄ × 7 H ₂ O and 0.01 g CuSO ₄ × 5 H ₂ O per liter) were tested with DMSO (0.5%). The inoculation was carried out with a concentrated spore suspension of Fusarium proliferatum at a final concentration of 2000 spores / ml. The plate was incubated at high humidity for 5 days at 20 ⁰ C. At the beginning and after 5 days, an OD measurement was made at OD620 (multiple measurement: 3 x 3 measurements per hole) to calculate growth inhibition. After 5 days, a sample of the liquid medium was removed and diluted 1: 1000 in 50% acetonitrile. The concentration of FB1 of the diluted samples was analyzed by HPLC-MS / MS and the measurements used to calculate the inhibition of fumonisin FB1 production compared to a drug-free control.

HPLC-MS / MS was carried out with the following parameters:

Ionization Type: ESI Positive

Ion spray voltage: 5500V

Spray gas temperature: 500 ⁰ C

Dekluster potential: 114V

Collision energy: 5IeV

Collision gas: N ₂

NMR trace: 722.3> 352.3; dwell time 100ms

HPLC column: Waters Atlantis T3 (trifunctional C18 bond, sealed)

Particle size: 3μm

Column dimensions: 50 x 2 mm

Temperature: 40 ° C

Solvent A: water + 0.1% HCOOH (v / v)

Solvent B: acetonitrile-K) .l% HCOOH (v / v)

Flow: 400 μL / minute

Injection volume: 5 μL

Gradient:

Examples of inhibition of fumonisin FB1 production

Examples Nos. 4, 5, 9, 7, 8, 10, 11, 12 and 13 showed activity> 80% in the inhibition of fumonisin FB1 production at a concentration of 50 μM. The inhibition of the growth of Fusarium proliferatum of the examples mentioned varied from 0 to 98% at 50 μM. - -

Example K: Production of DON / acetyl-DON by Fusarium graminearum

The compounds were grown in microtiter plates in a DON-inducing liquid medium (I g (NH ₄ ) ₂ HPθ ₄ , 0.2 g MgSO ₄ .7H ₂ O, 3 g KH ₂ PO ₄ , 10 g glycerol, 5 g NaCl and 40 g sucrose per liter) and DMSO (0.5%). The inoculation was carried out with a concentrated spore suspension of Fusarium graminearum at a final concentration of 2000 spores / ml. The plate was incubated for 7 days at 28 ⁰ C at high humidity. At the beginning and after 3 days an OD measurement at OD620 (multiple measurement: 3 x 3 measurements per hole) was made to calculate the growth inhibition. After 7 days, 1 volume of a 84/16 acetonitrile / water mixture was added and from each well, a sample of the liquid medium was then withdrawn and diluted 1: 100 in 10% acetonitrile. The proportions of DON and acetyl-DON of the samples were analyzed by HPLC-MS / MS and the measurements were used to calculate the inhibition of DON / AcDON production compared to a drug-free control.

The HPLC-MS / MS measurements were carried out with the following parameters:

Ionization Type: ESI negative

Ion spray voltage: - 4500 V

Spray gas temperature: 500 ⁰ C

Dekluster potential: - 40 V

Collision Energy: -22eV

Collision gas: N ₂

NMR trace: 355.0> 264.9;

HPLC column: Waters Atlantis T3 (trifunctional C18 bond, sealed)

Particle size: 3μm

Column dimensions: 50 x 2 mm

Temperature: 40 ° C

Solvent A: water / 2.5 mM NH ₄ OAc + 0.05% CH ₃ COOH (v / v)

Solvent B: methanol / 2.5mM NH ₄ θAc-K) .05% CH ₃ COOH (v / v)

Flow: 400 μL / minute

Injection volume: 11 μL

Gradient:

- -

Examples of DON inhibition

Examples Nos. 9, 7, 8, 10, 11, 12 and 13 showed> 80% activity in inhibiting DON / AcDON production at 50 μM. The inhibition of the growth of Fusarium graminearum of the examples mentioned varied from 60 to 98% at 50 μM.

Example L Pre-emergence phytoregulatory effect Phytoregulatory effect in pre-emergence

Seeds of monocotyledonous or dicotyledonous crops are placed in sandy loam in wood fiber pots and covered with soil. The formulated in the form of wettable powders (WP) test compounds are then applied as an aqueous suspension with a water application rate of 600 L / ha with the addition of 0.2% wetting agent in different dosages on the surface of the cover soil. After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the test plants. The visual assessment of the growth depression on the test plants is carried out after a test time of about 3 weeks compared to untreated controls (phytoregulatory effect in percent: 100% effect = plants are maximally inhibited in growth, 0% effect = plant growth equal untreated control.)

Results: pre-emergence phytoregulatory effect in%

BRSNW = Brassica napus (Rape), VIOTR = Viola tricolor (Wild pansy), ABUTH = Abuthilon theopharasti (Chinese hemp).

Claims

claims

1. phenyl (oxy / thio) alkanol derivatives of the formula (I)

in which

X is 5-pyrimidinyl, 1H-1, 2,4-triazol-1-ylmethyl, 3-pyridinyl, 1H-1,3-imidazolylmethyl or 2,4-dihydro-3H-1, 2,4-triazole 3-thion-1-ylmethyl,

Y is O, S, SO, SO ₂ or CH ₂ ,

Z ^{1 is} bromine, iodine or trifluoromethyl,

Z ² and Z ³ independently of one another are halogen, methyl or trifluoromethyl,

n is 0 or 1,

R is tert-butyl, isopropyl, 1-halocyclopropyl, 1- (C 1 -C ₄ -alkyl) cyclopropyl, 1- (C 1 -C ₄ -

Alkoxy) cyclopropyl and 1- (C 1 -C ₄ -alkylthio) cyclopropyl,

and their agrochemically active salts,

the connections

1 - (3-Bromo-2-chlorophenoxy) -3,3-dimethyl-2- (IH-1,2,4-triazol-1-ylmethyl) butan-2-ol, 1- (4-bromo-2-) chloφhenoxy) -3,3-dimethyl-2- (lH-l, 2,4-triazol-l-ylmethyl) butan-2-ol,

4- (3-Bromo-4-fluoro-phenyl) -2- (1-chlorocyclopropyl) -1- (1H-l, 2,4-triazol-1-yl) -butan-2-ol 1- [3,5-bis (Trifluoromethyl) phenyl] -4,4-dimethyl-3- (1H-l, 2,4-triazol-1-ylmethyl) pentan-3-ol are excluded. 2. phenyl (oxy / thio) alkanol derivatives of the formula (I) according to claim 1, in which

X is 5-pyrimidinyl, 1H-1, 2,4-triazol-1-ylmethyl, 3-pyridinyl or 2,4-dihydro-3H-1,

2,4-triazole-3-thion-1-ylmethyl,

Y is O, S or CH ₂ ,

Z ^{1 is} bromine or iodine,

Z ^{2 is} fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-, i-, s- or t-butyl,

Methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, trichloromethyl, difluoromethyl, dichloromethyl, trifluoromethoxy or trifluoromethylthio,

Z ^{3 is} fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, trichloromethyl, difluoromethyl, dichloromethyl, Trifluoromethoxy or trifluoromethylthio,

R is tert-butyl, isopropyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl, 1-methylcyclopropyl,

1-methoxycyclopropyl and 1-methylthiocyclopropyl.

3. Compounds of the formula (I-a)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given above.

4. Compounds of the formula (I-c)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given above.

5. Compounds of the formula (I-e)

in which Y, Z, Z, Z, n and R have the meanings given above.

6. A method for controlling phytopathogenic harmful fungi, characterized in that one carries out phenyl (oxy / thio) alkanol derivatives of the formula (I) according to claim 1 or 2, on the phytopathogenic harmful fungi and / or their habitat.

7. A composition for controlling phytopathogenic harmful fungi, characterized by a content of at least one of phenyl (oxy / thio) alkanol derivatives of the formula (I) according to claim 1 or 2, in addition to extenders and / or surface-active substances.

8. Use of phenyl (oxy / thio) alkanol derivatives of the formula (I) according to claim 1 or 2 for controlling phytopathogenic harmful fungi.

9. A process for the preparation of agents for controlling phytopathogenic harmful fungi, characterized in that one mixes phenyl (oxy / thio) alkanol derivatives of the formula (I) according to claim 1 or 2 with extenders and / or surface-active substances.

10. A process for preparing phenyl (oxy / thio) alkanol derivatives of the formula (I) according to claim 1 or 2, characterized in that

(A) in the case where X ^{1 is} 1H, 2,4-triazol-1-ylmethyl or 1H-1,3-imidazol-1-ylmethyl, Oxirane derivatives of the formula (II)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given in claim 1, with 1,2,4-triazole or 1,3-imidazole of the formula (III)

in which A is CH or N,

in the presence of a diluent; or

(B) in the event that X ^{2 is} 1H-l, 2,4-triazol-1-ylmethyl, 1H-l, 3-imidazol-1-ylmethyl, 5

Pyrimidinyl or 3-pyridinyl,

Oxirane derivatives of the formula (IV)

in which R has the meanings given in claim 1,

with a (thio) phenol of the formula (V)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given in claim 1, in the presence of a diluent; or

(C) in the case where X ^{3 is} 5-pyrimidinyl or 3-pyridinyl,

Phenyl (oxy / thio) ketones of the formula (VI)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given in claim 1, with a halide of the formula (VII)

HaI-X ³ (V)

in which Hal is halogen,

in the presence of a diluent and in the presence of an alkali metal-organic compound; or (D) for the case that X ⁴ is 5-pyrimidinyl or 3-pyridinyl,

in a first step, bromides of the formula (VIII)

O

B ^r ^^ _χ 4 (VIII)

with a (thio) phenol of the formula (V)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given in claim 1, in the presence of a diluent, and the resulting phenyl (oxy / thio) ketones of the formula (IX)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given in claim 1, in a second step with organometallic compounds of the formula (X) RM (X)

in which R has the meanings given in claim 1 and M is metal, in the presence of a diluent and in the presence of an alkali metal-organic compound is reacted; or

(E) Phenyl (oxy / thio) alkanol derivatives of the formula (Ic)

in which Y, Z ¹ , Z ² , Z ³ , n and R have the meanings given in claim 1, reacted with sulfur.

11. Oxirane derivatives of the formula (II)

in which Y, Z ¹ , Z, Z, n and R have the meanings given in claim 1, the compound excluding 2- {2- [3,5-bis (trifluoromethyl) phenyl] ethyl} -2-tert-butyloxirane is.

12. Oxirane derivatives of the formula (IV-a)

in which

R ^{a is} isopropyl, 1-halogenocyclopropyl, C 1 -C ₄ -alkyl) cyclopropyl, C 1 -C ₄ -alkoxy-cyclopropyl and C 1 -C ₄ -alkylthio) cyclopropyl,

A is CH or N

13. Oxirane derivatives of the formula (IV-b)

in which

R has the meanings given above and

A is CH or N,

where R is not tert-butyl when A is CH.

14. Phenyl (oxy / thio) ketones of the formula (DC)

in which X ^{4 is} 5-pyrimidinyl or 3-pyridinyl and Y, Z ¹ , Z ² , Z ³ , n and R to the claim

1 have given meanings.