EP1212307A1

EP1212307A1 - Unsaturated oxime ethers and the use thereof for control of harmful fungi and veterinary pests

Info

Publication number: EP1212307A1
Application number: EP00966014A
Authority: EP
Inventors: Markus Gewehr; Hubert Sauter; Bernd Müller; Andreas Gypser; Wassilios Grammenos; Jordi Tormo I Blasco; Arne Ptock; Oliver Cullmann; Thomas Grote; Eberhard Ammermann; Siegfried Strathmann; Gisela Lorenz; Volker Harries
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1999-09-15
Filing date: 2000-09-14
Publication date: 2002-06-12
Also published as: JP2003509415A; WO2001019803A1

Abstract

The invention relates to unsaturated oxime ether compounds of formula (1) in which the substituents are as defined in the description. Said compounds are used to control harmful fungi and veterinary pests.

Description

Unsaturated oxime ethers and their use to control harmful fungi and animal pests

5 Description

The present invention relates to unsaturated oxime ethers, intermediates for their preparation and their use for controlling harmful fungi and animal pests.

10

Fungicidal oxime ether compounds are already known. For example in WO 95/14009, WO 96/17851, WO 96/36229, WO 96/36615, WO 96/36616, WO 96/36633, WO 97/0612, WO 98/05652 and WO 98/23155 are strobilurins with triazolone -Pharmacophores of the

15 formula described:

25 wherein Rj ₇ and Ris are H, -CC ₃ -alkyl or phenyl.

Compounds with unsaturated oxime ether side chains are already known from EP 386561A, EP 579124A, EP 585751A, EP 672347A, EP ₃₀ 673923A, WO 97/30032 and WO 97/33874.

Proceeding from this, the present invention is based on the object of providing compounds with improved activity and / or broadened activity spectrum. Surprisingly, it has now been found that this object is achieved with compounds which have a triazolone pharmacophore and an unsaturated oxime ether side chain.

The present invention therefore relates to unsaturated oxime ether 4Q compounds of the formula 1

45 in which the substituents have the following meanings:

W -OCH ₂ -, -C (Rιo) = N-0-CH ₂ - (the CH ₂ end is in each case bound to the phenyl group which carries the triazolone radical);

X halogen, C _! -C ₄ alkyl, C _! -C ₄ alkoxy;

R _x H, Cχ-C ₄ alkyl, halogen, nitro, CN, halogen-C _! -C ₄ alkyl, C _! -C alkoxy;

R ₂ H, -CC ₄ alkyl, halogen, nitro, CN, halogen-C _! -C ₄ alkyl,

Cχ-C -alkoxy;

n 1 or 2;

R ₃ H, -CC-alkyl;

R ₅ H, -CC ₄ alkyl, C ₂ -C alkenyl;

R ₆ H, -C -C alkyl, -C -C haloalkyl, C ₂ -C alkenyl, aryl;

R ₇ H, halogen, -C-C ₆ alkyl, -C-C ₆ haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ haloalkenyl, C ₃ -C ₆ cycloalkyl, C ₃ -C _6- halocycloalkyl, optionally substituted ^aryl;

R ₈ H, halogen, -CC ₆ alkyl, C _! -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, optionally substituted aryl, or

R ₇ and Rs, together with the carbon atoms to which they are attached, form an unsaturated heterocycle with 5 or 6 ring atoms, which has one or two heteroatoms which are selected independently of one another from a nitrogen, oxygen and sulfur atom and which may optionally be substituted by one or two radicals which are selected independently of one another and ter C _! -C ₄ alkyl, halogen, nitro, CN, halo -CC ₄ alkyl, OH, -C -alkoxy, optionally substituted aryl, C ₂ -C alkenyl, halo-C ₂ -C alkenyl, C ₂ -C alkynyl, haloC ₂ -C alkynyl;

R ₉ is H, halogen, Cι-C ₆ -alkyl, C ₆ haloalkyl, C ₂ -C ₆ -Alke- nyl, C ₂ -C ₆ haloalkenyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ -Halogenocycloalkyl, optionally substituted aryl;

Rio H, halogen, -CC alkyl.

The meanings listed above are collective terms for individual enumerations of the individual group members. All carbon chains can be straight-chain or branched. Halogenated substituents preferably carry 1 to 5 identical or different halogen atoms.

Specifically, for example:

- Halogen: fluorine, chlorine, bromine, iodine, preferably fluorine or chlorine;

C _x -C ₄ alkyl: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, preferably methyl;

C _! -C ₆ alkyl: Cχ-C alkyl as mentioned above, and n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1- Dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methylpropyl, l-ethyl- 2-methylpropyl, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl or 1, 1-dimethylethyl;

C ₂ -C ₆ alkenyl: ethenyl, prop-1-en-l-yl, prop-2-en-l-yl, 1-methylethenyl, n-buten-1-yl, n-buten-2-yl, n-buten-3-yl, 1-methylprop-l-en-l-yl, 2-methylprop-l-en-l-yl, 1-methylprop-2-en-l-yl, 2-methylprop- 2-en-l-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-1-en- l-yl, 2-methylbut-l-en-l-yl, 3-methylbut-l-en-l-yl, l-methylbut-2-en-l-yl, 2-methylbut-2-en-l- yl, 3-methylbut-2-en-l-yl, l-methylbut-3-en-l-yl, 2-methylbut-3-en-l-yl, 3-methylbut-3-en-l- yl, 1, l-dimethyl-prop-2-en-l-yl, 1,2-dimethyl-prop-1-en-1-yl, 1, 2-dimethyl-prop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2- en-l-yl, n-hex-1-en-l-yl, n-hex-2-en-l-yl, n-hex-3-en- l-yl, n-hex-4-en- l-yl, n-hex-5-en-l-yl, 1-methylpent-l-en-l-yl, 2-methyl-pent-l-en-l-yl, 3-methylpent-l-en- l-yl,

4-methylpent-l-en-l-yl, l-methylpent-2-en-l-yl,

2-methylpent-2-en-l-yl, 3-methylpent-2-en-l-yl,

4-methylpent-2-en-l-yl, l-methylpent-3-en-l-yl,

2-methylpent-3-en-l-yl, 3-methylpent-3-en-l-yl, 4-methylpent-3-en-l-yl, l-methylpent-4-en-l-yl, 2- Methylpent-4-en-l-yl, 3-methylpent-4-en-l-yl, 4-methylpent-4-en-l-yl, 1, l-dimethyl-but-2-en-l-yl, 1, l-dimethyl-but-3-en-l-yl, 1, 2-dimethyl-but-1-en-l-yl, 1, 2-dimethyl-but-2-en-l-yl, 1, 2-dimethyl-but-3-en-l-yl, 1,3-dimethyl-but-l-en-l-yl, 1, 3-dimethyl-but-2-en-l-yl, 1, 3- Dimethyl-but-3-en-l-yl, 2, 2-dimethyl-but-3-en-l-yl, 2, 3-dimethyl-but-l-en-l-yl, 2, 3-dimethyl but-2-en-l-yl, 2, 3-dimethyl-but-3-en-l-yl, 3, 3-dimethyl-but-l-en-l-yl, 3,3-dimethyl-but- 2-en-l-yl, 1-ethylbut-l-en-l-yl, l-ethylbut-2-en-l-yl, l-ethylbut-3-en-l-yl, 2-ethylbut-l- en-l-yl, 2-ethylbut-2-en-l-yl, 2-ethylbut-3-en-l-yl, 1,1, 2-trimethylprop-2-en-l-yl, l-ethyl- l-methyl-prop-2-en-l-yl, l-ethyl-2-methyl-prop-l-en-l-yl, l-ethyl-2-methyl-prop-2-en-l-yl, preferably ethenyl or prop-2-en-l-yl;

C ₂ -C alkynyl: ethynyl, prop-1-yn-l-yl, prop-2-yl-3-in, n-but-1-yn-l-yl, n-but-l-yn-4 -yl, n-but-2-yn-l-yl, preferably prop-2-yn-yl-yl;

-C-C ₂ haloalkyl: z. B. chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2- fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, preferably difluoromethyl or trifluoromethyl;

Ci _L -Cö-haloalkyl: -C-C ₆ alkyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, that is, for. B. the aforementioned C ₁ -C ₂ haloalkyl radicals, and 3-chloropropyl or heptafluoropropyl, preferably trifluoromethyl, pentafluoroethyl or heptafluoropropyl; CC ₆ haloalkenyl: C ₂ -C ₆ alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, that is, for. B. 2-chloroallyl, 3-chloroallyl or 3,3-dichloroallyl;

C ₂ -C haloalkynyl: C ₂ -C alkynyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, e.g. B. chloroethynyl, 3-chloropropynyl;

- C ₃ -C ₆ cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, preferably cyclopropyl, cyclopentyl or cyclohexyl;

Halogen-C ₃ -C ₆ cycloalkyl: C ₃ -C ₆ as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, that is, for. B. 2-, 3- or 4-chlorocyclopentyl, 2-, 3- or 4-chlorocyclohexyl, 2, 3,4-trichlorocyclopentyl or 2,3,4,5, 6-pentachlorocyclohexyl;

Aryl is preferably phenyl and naphthyl, especially phenyl.

The unsaturated heterocycle with 5 or 6 ring atoms can be aromatic or non-aromatic. An aromatic heterocycle is in particular 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4 -Isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-0xazolyl, 4-0xazolyl, 5-0xazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4 Imidazolyl, l, 2,4-0xadiazol-3-yl, l, 2,4-0xadiazol-5-yl, l, 2,4-thiadiazol-3-yl,

1,2, 4-thiadiazol-5-yl, 1,2, 4-triazol-3-yl, 1,3, 4-0xadiazol-2-yl, l, 3,4-thiadiazol-2-yl, l, 3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, in particular furanyl , Thienyl, oxazolyl and thiazolyl.

If the aryl radical is substituted, it preferably has one or two substituents which are selected independently of one another from halogen, in particular fluorine or chlorine, C ₁ -C alkyl, C ₁ -C 4 -haloalkyl, C ₁ -C 4 alkoxy, nitro , OH and CN. Halogen and / or -CC ₄ alkyl is preferred.

The substituents in formula 1 preferably have the following meaning:

X Cχ-C alkoxy or halogen, in particular -C-C alkoxy; R _λ H, Cχ-C ₄ alkyl, halogen, halo -CC ₄ alkyl, in particular

H or -CC alkyl;

R _{2 is} H, -CC alkyl, halogen, halogen-Cχ-alkyl, especially H or -CC alkyl;

R ₃ Cχ-C-alkyl;

R _{5 is} H or Cx-d-alkyl;

R ₆ H, -CC-alkyl or halogen -CC-C-alkyl, especially H or Cχ-C alkyl;

R ₇ is H, halogen, _Cι-C6 alkyl, halo-Cι-C ₆ alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ halocycloalkyl or phenyl, especially H, halogen, Cι-C ₆ alkyl and particularly preferably H or halogen;

R ₈ is H, halogen, _Cι-C6 alkyl, halo-Cι-C ₆ alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₂ -C ₆ alkenyl or phenyl, in particular H, halogen, -CC ₆ alkyl; or

R ₇ and Rβ together with the carbon atoms to which they are attached represent thienyl, furyl, oxazolyl or thiazolyl _f, where these groups are optionally substituted by Cχ-C-alkyl, halogen or phenyl, which is optionally substituted by one or two halogen can be substituted and in particular for thienyl or oxazolyl, these groups optionally being substituted by one or two halogen or phenyl and the phenyl substituent in turn being substituted by one or two halogen;

Rg is H, halogen, _Cι-C6 alkyl, halo-Cι-C ₆ alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ halocycloalkyl or phenyl, especially H, halogen, Cι-C ₆ Alkyl and particularly preferably H or halogen;

Rio H or -CC ₄ alkyl;

The oxime side chain can be attached to the phenyl ring in the o, m or p position to W. The p position is preferred.

The radical R is preferably in the 6 position. If the oxime side chain is bonded to W in the p-position, the radical R _{2 is} preferably in the 2- and / or 5-position.

Preferred embodiments are the compounds of formula 1, in which the substituents have the following meanings:

W -OCH ₂ -, -C (Rιo) = N-0-CH ₂ ;

X halogen, -C ₄ alkyl, -C ₄ alkoxy;

R _x H, -CC ₄ alkyl, halogen, halo -CC ₄ alkyl;

R ₂ H, -CC ₄ alkyl, halogen, halo -CC alkyl;

R ₃ H, -CC ₄ alkyl;

n 1 or 2;

R ₅ H or -CC ₄ alkyl;

R ₆ H, -CC ₄ alkyl, halo -CC ₄ alkyl;

R ₇ H, halogen, -CC ₆ alkyl, halogen -CC ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, phenyl;

R ₈ is H, halogen, _Cι-C6 alkyl, halo-Cι-C ₆ alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₂ -C ₆ alkenyl, phenyl; or

R and R ₈ together with the carbon atoms to which they are attached form an unsaturated heterocycle with 5 or 6 ring atoms, which has one or two heteroatoms which are selected independently of one another from a nitrogen, oxygen and sulfur atom and that can optionally be substituted with one or two radicals which are selected independently of one another from C -C -alkyl, halogen, halogen -CC-C -alkyl, Cι-C -alkoxy and phenyl, which is optionally substituted by one or two halogen or Cι- C alkyl is substituted;

Rg H, halogen, -CC ₆ alkyl, halogen-C _! -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, phenyl;

Rio H, halogen, -CC alkyl. B)

W -OCH ₂ -, -C (Rιo) = N-0-CH ₂ ;

X halogen, -CC alkoxy;

Ri H, -CC ₄ alkyl;

R ₂ H, -CC ₄ alkyl;

n 1 or 2;

R ₃ -CC ₄ alkyl;

R ₅ H, -CC alkyl;

R ₆ H, -CC ₄ alkyl;

R ₇ H, halogen, -CC ₆ alkyl;

R ₈ H, halogen, -CC ₆ alkyl; or

R ₇ and Rg together with the carbon atoms to which they are attached form thienyl, furanyl, oxazolyl, thiazolyl, where these groups may have one or two substituents which are selected independently of one another from C 1 -C 4 -alkyl, halogen and Phenyl which is optionally substituted by one or two halogen;

R ₉ H, halogen, -CC ₆ alkyl;

Rio H, -CC ₄ alkyl;

C)

W -OCH ₂ -, -C (Rιo) = N-0-CH ₂ ;

X -C-C ₄ alkoxy;

Ri H;

R ₂ H, -CC alkyl;

n 1 or 2;

^R ₃ -CC ₄ alkyl; R ₅ H, -CC alkyl;

Re H, -CC ₄ alkyl;

R ₇ H, halogen;

R ₈ H, -CC alkyl, halogen; or

R and Rg together with the carbon atoms to which they are attached form thiophenyl or oxazolyl, these groups optionally being substituted by one or two halogen or phenyl and the phenyl optionally being substituted by one or two halogen;

Rg H, halogen;

Rio H, -CC ₄ alkyl.

Other embodiments are

D) Compounds of the formula la:

where the substituents have the following meanings:

X chlorine, methoxy;

R ₂ chlorine, methyl;

n 1 or 2, where R _{2 is} in the 2-position to the oxygen substituent if n = 1 and in the 2,5-position if n = 2;

Rs H, methyl, ethyl;

R ₇ H, methyl, chlorine; R ₈ H, methyl, ethyl, chlorine, phenyl, ethenyl, prop-1-en-1-yl;

Rg H, methyl, chlorine;

E) Compounds of the formula Ib:

wherein the substituents have the following meanings:

Chlorine, methoxy;

Rs H, methyl, ethyl;

? H, methyl, chlorine;

Rs H, methyl, ethyl, chlorine, phenyl, ethenyl, prop-1-en-1-yl;

Rg H, methyl, chlorine.

The oxime side chain is preferably bound in the p-position.

F) Compounds of the formula lc:

where R means:

Thiophene-2-yl, thiophene-3-yl, furan-2-yl, furan-3-yl, 5-chloro-thiophene-2-yl, 5-bromo-thiophene-2-yl, 5-chloro-furan 2-yl, 5-bromo-furan-2-yl, 5-methyl-thiophene-2-yl, 5-phenyl-thiophene-2-yl, 5-methyl-furan-2-yl, 5-phenyl furan-2-yl, oxazol-4-yl, oxazol-5-yl, 2- (chlorophenyl) oxazol-4-y1, 2- (p-bromophenyl) oxazol-4-yl, thiazol-4 -yl, thiazol-5-yl.

The radicals X, R ₂ and R ₅ have the meanings given above or preferably the following meanings:

X chlorine, methoxy;

R ₂ 2-methyl, 2-chloro, 2,5-dimethyl;

R5 H, methyl, ethyl,

G) Compounds of the formulas ld, le and lf:

where R means:

Thiophene-2-yl, thiophene-3-yl, furan-2-yl, furan-3-yl, 5-chloro-thiophene-2-yl, 5-bromo-thiophene-2-yl, 5-chloro-furan 2-yl, 5-bromo-furan-2-yl, 5-methyl-thiophene-2-yl, 5-phenyl-thiophene-2-yl, 5-methyl-furan-2-yl, 5-phenyl furan-2-yl, oxazol-4-yl, oxazol-5-yl, 2- (p-chlorophenyl) oxazol-4-yl, 2- (p-bromophenyl) oxazol-4-yl, thiazole 4-yl, thiazol-5-yl.

The radicals X and R ₅ have the meanings given above or preferably the following meanings:

Chlorine, methoxy;

Rs H, methyl, ethyl.

In particular, in view of their use, the compounds of the formulas lc to lf compiled below are preferred. The groups mentioned for a substituent, independently of the combination in which they are mentioned, also represent a particularly preferred embodiment of the substituent in question:

a) Compounds of the general formula Ic in which R _{2 is} 2-methyl (based on the oxygen substituent), X is chlorine and R _{5 is} hydrogen and R corresponds to one row of Table 1.

b) Compounds of the general formula Ic in which R _{2 is} 2-methyl (based on the oxygen substituent), X is methoxy ^and ^R _{5 is} hydrogen and R corresponds to one row of Table 1.

c) Compounds of the general formula Ic in which R _{2 is} 2-chlorine (based on the oxygen substituent), X is chlorine and R _{5 is} hydrogen and R corresponds to one row of Table 1. d) Compounds of the general formula Ic in which R _{2 is} 2-chlorine (based on the oxygen substituent), X is methoxy and R _{5 is} hydrogen and R corresponds to one row of Table 1.

e) Compounds of the general formula Ic in which R _{2 is} 2,5-dimethyl (based on the oxygen substituent), X is chlorine and R _{5 is} hydrogen and R corresponds to one row of Table 1.

f) Compounds of the general formula Ic in which R _{2 is} 2,5-dimethyl (based on the oxygen substituent), X is methoxy and R _{5 is} hydrogen and R corresponds to one row of Table 1.

g) Compounds of the general formula Ic in which R _{2 is} 2-methyl (based on the oxygen substituent), X is chlorine and R _{5 is} methyl and R corresponds to one row of Table 1.

h) Compounds of the general formula Ic in which R _{2 is} 2-methyl (based on the oxygen substituent), X is methoxy and R _{5 is} methyl and R corresponds to one row of Table 1.

i) Compounds of the general formula Ic in which R _{2 is} 2-chlorine (based on the oxygen substituent), X is chlorine and R _{5 is} methyl and R corresponds to one row of Table 1.

j) Compounds of the general formula Ic in which R _{2 is} 2-chlorine (based on the oxygen substituent), X is methoxy and R _{5 is} methyl and R corresponds to one row of Table 1.

k) Compounds of the general formula Ic in which R _{2 is} 2,5-dimethyl (based on the oxygen substituent), X is chlorine and R _{5 is} methyl and R corresponds to one row of Table 1.

1) Compounds of the general formula Ic in which R _{2 is} 2,5-dimethyl (based on the oxygen substituent), X is methoxy and R _{5 is} methyl and R corresponds to one row of Table 1. m) Compounds of the general formula Ic in which R _{2 is} 2-methyl (based on the oxygen substituent), X is chlorine and R _{5 is} ethyl and R corresponds to one row of Table 1.

n) Compounds of the general formula Ic in which R _{2 is} 2-methyl (based on the oxygen substituent), X is methoxy and R _{5 is} ethyl and R corresponds to one row of Table 1.

o) Compounds of the general formula Ic in which R _{2 is} 2-chlorine (based on the oxygen substituent), X is chlorine and R _{5 is} ethyl and R corresponds to one row of Table 1.

p) Compounds of the general formula Ic in which R _{2 is} 2-chlorine (based on the oxygen substituent), X is methoxy and R _{5 is} ethyl and R corresponds to one row of Table 1.

q) Compounds of the general formula Ic in which R is 2,5-dimethyl (based on the oxygen substituent), X is chlorine and R _{5 is} ethyl and R corresponds to one row of Table 1.

r) Compounds of the general formula Ic in which R _{2 is} 2, 5-dimethyl (based on the oxygen substituent), X is methoxy and R _{5 is} ethyl and R corresponds to one row of Table 1.

s) compounds of the general formula Id in which X is chlorine and R _{5 is} hydrogen and R corresponds to one row of Table 1.

t) Compounds of the general formula Id in which X is methoxy and R5 is hydrogen and R corresponds to one row of Table 1.

u) Compounds of the general formula Id in which X is chlorine and R _{5 is} methyl and R corresponds to one row of Table 1.

v) Compounds of the general formula Id in which X is methoxy and R _{5 is} methyl and R corresponds to one row of Table 1. w) compounds of the general formula Id in which X is chlorine and R _{5 is} ethyl and R corresponds to one row of Table 1.

x) Compounds of the general formula Id, in which X is methoxy and R _{5 is} ethyl and R corresponds to one row of Table 1.

y) compounds of the general formula le in which X is chlorine and R _{5 is} hydrogen and R corresponds to one row of Table 1.

z) Compounds of the general formula le, in which X is methoxy and R _{5 is} hydrogen and R corresponds to one row of Table 1.

aa) Compounds of the general formula le, in which X is chlorine and R _{5 is} methyl and R corresponds to one row of Table 1.

ab) compounds of the general formula le in which X is methoxy and R _{5 is} methyl and R corresponds to one row of Table 1.

ac) compounds of the general formula le, in which X is chlorine and R _{5 is} ethyl and R corresponds to one row of Table 1.

ad) compounds of the general formula le, in which X is methoxy and R _{5 is} ethyl and R corresponds to one row of Table 1.

ae) compounds of the general formula lf in which X is chlorine and R _{5 is} hydrogen and R corresponds to one row of Table 1.

af) compounds of the general formula If in which X is methoxy and R _{5 is} hydrogen and R corresponds to one row of Table 1.

ag) compounds of the general formula lf in which X is chlorine and R _{5 is} methyl and R corresponds to one row of Table 1. ah) Compounds of the general formula If in which X is methoxy and R _{5 is} methyl and R corresponds to one row of Table 1.

5 ai) compounds of the general formula lf in which X is chlorine and R _{5 is} ethyl and R corresponds to one row of Table 1.

aj) Compounds of the general formula If in which X is methoxy 10 and R _{5 is} ethyl and R corresponds to one row of Table 1.

Table 1

15 The mention of (E), (E, E) and (Z) refers to the substituents on the double bond specified in R.

The compounds of the invention can be prepared by several methods. The preparation is preferably carried out according to one of the synthesis routes A or B, which are explained in the formula scheme below. The starting point for the synthesis is a compound of the formula 2 in which Xi in the case of route A is CH ₃ or SGOCH ₂ -, where SG is a protective group for benzyl ether. After the triazolone ring has been built up, the protective group is split off and the benzyl alcohol obtained is converted into X ₂ CH ₂ - using methods known from the literature, where X _{2 is} a nucleophilically cleavable group (cf. TW Greene: "Protective Groups in Organic Synthesis", 2. Edition 1991, John Wiley, New York). In the case of route B, Xi = X ₂ CH ₂ -, where X ₂ denotes a nucleophilically cleavable group, such as chlorine, fluorine, bromine, nitro, alkyl or aryl sulfonate, such as mesylate, tosylate or triflate. The preparation of these compounds is known and is described, for example, for the synthesis from the corresponding nitro compounds in Houben-Weyl, Vol. IV / lc, 4th edition, pp. 506ff, Thieme Verlag, Stuttgart 1980.

The amino function of the compounds 2 is first converted into a thiazolone group, the compounds 3 being obtained. The reaction sequence leading to this conversion is described in detail in WO 95/14009 (compounds No. 21 → 19 → 17 → 1) and in WO 96/26191 and DE 198 09 995.

The group Xi is then converted into a reactive group which can react with the radical V in the compound 7 or the radical _x in the compound of the formula 8 by linking the two phenyl rings and forming the group W. Group V is a phenolic OH group or the group C (Rιo) = N-OH. Thus, a leaving group is introduced into group Xi, which is split off with the hydrogen atom of the phenolic or oximic OH group in the presence of a base. Examples of such leaving groups are chloride, bromide, p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate. These leaving groups are introduced in a manner known to the person skilled in the art, for example by reacting the compound 3 with X 1 = CH ₃ with N-bromosuccinimide or N-chlorosuccinimide.

The reaction of compound 3 with compound 7 or 8 takes place, for example, in an inert solvent or diluent, such as acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone etc., using a base (for example sodium carbonate, potassium carbonate) , Sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride etc.). The bases are generally used in equimolar amounts or in excess. It may also be advantageous to add a catalytic amount of a crown ether (e.g. 18-crown-6 or 15-crown-5). The reaction temperature is generally in the range from 0 to 80 ° C., preferably 20 to 60 ° C.

The preparation of compounds 7 and 8 is known to the person skilled in the art and is described, for example, in Organikum, 17th edition, VEB Deutscher Verlag der Wissenschaften, Berlin 1988, pp. 323ff, and Angewandte Chemie 1972, 84, 295 and Zh. Org. Khim 1995, 31, 601, Chem. Pharm. Bull. 1988, 36, 3134, Indian J. Chem., Sect. B, 1992, 31, 495.

Compound 4 obtained by reacting 3 with 7 is then oximated with an O-alkenylhydroxylamine or a salt thereof. The preparation of the O-alkenylhydroxylamine is known to the person skilled in the art and is described, for example, in Chem. Pharm. Bull. 1983, 91, 2601 and J. Am. Chem. Soc. 1949, 71, 3423. Alternatively, a compound 3 can be reacted directly with an oxime 8 to form a compound 1. All steps of route A, including the preparation of the intermediates or analog intermediates, are described in EP 386 581A (for W = OCH ₂ ) and in EP 585 751A (for W = C (Rι ₀ ) = NOCH ₂ ).

Route B also starts from a compound 2. Reaction with the oxime 8 under the etherification conditions mentioned above gives a compound 6 (Y = NH ₂ ). The thiazolone ring is then built up in the same way as in route A.

Alternatively, a compound 2 is reacted with a compound 7 under the etherification conditions mentioned above to give a compound 5. This is, in the same way as in route A, oximized with O-alkenylhydroxylamine or a salt thereof, giving compound 6, into which, as already described, the thiazolone ring is subsequently introduced.

The compounds according to the invention can be obtained as E / Z isomer mixtures in the preparation owing to the C = C or C = N double bonds. These can be separated into the individual components in a conventional manner, for example by crystallization or chromatography. The invention encompasses both the individual isomer compounds and their mixtures and all enantiomers, racemates and diastereomers.

The new compounds 1 are notable for excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidio mycetes, and can be used as leaf and soil fungicides. Some of them have remarkably high systemic mobility and effectiveness after soil application and especially after leaf application.

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

They are particularly suitable for combating the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Shaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines,

Puccinia species on cereals,

Rhizoctonia species on cotton and lawn,

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

Helminthosporium species on cereals,

Septoria nodorum on wheat,

Botrytis cinerea (gray mold) on strawberries, vines,

Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley,

Pyricularia oryzae on rice,

Phytophthora infestans on potatoes and tomatoes,

Fusarium and Verticillium species on different plants,

Plasmopara viticola on vines, Alternaria species on vegetables and fruits.

The compounds 1 are applied by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds. It is used before or after the infection of the materials, plants or seeds by the fungi.

They can be converted into the usual formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend on the purposes; in any case, they should ensure a fine and uniform distribution of the connections 1. The formulations are prepared in a known manner, e.g. B. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as a diluent other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol) ), Ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; Carriers such as natural rock flours (e.g. kaolins, clays, talc, chalk) and synthetic rock flours (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient. Depending on the type of effect desired, the application rates are between 0.01 and 3 kg of active ingredient per ha.

In the case of seed treatment, amounts of active ingredient of 0.001 to 50 g, preferably 0.01 to 10 g, per kg of seed are generally required.

The agents according to the invention can also be present in the use form as fungicides together with other active ingredients which, for. B. with herbicides, insecticides, growth regulators, fungicides or with fertilizers.

When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.

The compounds of the formula Ia are also suitable for effectively controlling pests from the class of the insects, arachnids and nematodes. They can be used as pesticides in crop protection as well as in the hygiene, storage protection and veterinary sectors.

From the order of the butterflies (Lepidoptera), the harmful insects include, for example, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana fata, Cheimatobone bria , Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea gran-diosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterraneaella, Graphitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaella funeral nasal artery Graphella mellitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaolitaella funnelia gera, Heliothis virescens, Heliothis zea, Hellula undalis, Hiber- nia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Litharocolla scitella, Litharobarana blitella, Litharobella scotella, Litharobolla scotella, Litharobella blitella sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkel la, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicaabyliaiaplanaiaia, Plathypaellaia, Plathypaellaia, Plathypaellaia, Plathypaellaia, Plathypaellaia, Plathypaia, Plathypia - pula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeiraphera canadensis. From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Byus Bruchus pisorusum , Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica, abbritica, epilutinisilotis, hyperbolic, epileptic, hyperbolic, epithelial, hyperbolic , Ips typographus, Lema bilineata, Lema melanopus, Lepti- notarsa decemlineata, Limonius californicus, Lissorhoptrus oryzo- philus, Melanotus communis, Meligethes aeneus, Melolontha hippo-castani, Melolontha melolontha, Oulema orynhiachonouscatuliachyochinachyochinachyochinachyochiochiochiochinachyochina, Oulema orynhochinacho chrysoce phala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.

From the order of the two-winged species (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthulucuceaphacaceacita phacaceacia phacaceacia phacaceacia phacaceacia phacaceacia phacaceacia phacaceacia phacaceacia phacaceacia phaceaceaceaceapeaceacophaceaceaceaceaceacophaceaceaceacophaceapeaceaceacophaceacophaceacophaceacophaceae Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia cuprina, Lucilia sericata, Musculoma domicans, Muscle, Musculoskeletal System, Muscle , Oscinella frit, Pegomya hyoscyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa.

From the order of the thrips (Thysanoptera) for example

Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.

From the order of the hymenoptera (Hymenoptera), for example, Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.

From the order of the bugs (Heteroptera), for example Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Eus- chistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor.

From the order of the plant suckers (Homoptera), for example, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Bemisia tabaci, Brachy- caudus cardui, Brevicoryne brassicae, Dreosiafiaiaiaiaiaia, Dreosusphiaiaiausiaia, Cerosiphayiaypia radicola, Dysau- lacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae,

Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nephotettix cincticeps, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psyllaopalsi asylum, Psyllaumidi asi mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus vitifolii.

From the order of the termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Retuculitermes lucifugus, Termes natalensis.

From the order of the straight-winged wing (Orthoptera), for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanusus, Melanoplus sanguinisusptipisipei, Melanoplasci, melanoplasmic , Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.

From the class of the arachnoid, for example arachnids (Acarina) such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, shedelodi, iodine eroniophus, Iotetroniiuncus, Iotetranyius, Iotetronii Ixodes rubicundus, Metatetranychus (Phanonychus) ulmi, Ornithodorus moubata, Otobins megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemusususus Tar, Tice, Rhipicephultsiabi pacificus, Tetranychus telarius, Tetranychus urticae.

From the class of the nematodes, for example, root gall nematodes, e.g. B. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, for example Globodera rosto- chiensis, Heterodera avenae, Heterodera glycinae, Heterodera schachtii, Heterodera trifolii, stick and leaf whale, e.g. B. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchusus Prubus neglechatatylusus, Prenate, prenovate, Prid.

The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, for. B. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The active substance concentrations in the ready-to-use preparations can be varied over a wide range.

Generally they are between 0.0001 and 10%, preferably between 0.01 and 1%.

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

The application rate of active ingredient for controlling pests is 0.1 to 2.0, preferably 0.2 to 1.0 kg / ha under field conditions.

To produce directly sprayable solutions, emulsions, pastes or oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, distant coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. B. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. B. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water into consideration. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.

Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers tiertem, condensation products of sulfonated Naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenylpolyglycol ether, alkylaryl ethoxylated alcohol ether, alkylaryl ethoxylated alcohol ether, alkylaryl ethoxylated alcohol ether, alkylaryl ethoxylated alcohol ether, alkylaryl ethoxylated alcohol, alkylaryl ethoxylated alcohols ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin sulfite waste liquors and methyl cellulose.

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

The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of formulations are:

Granules, e.g. B. coating, impregnation and homogeneous granules; they can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. B. mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, Magnesium oxide, ground plastics, fertilizers, such as. B. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

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

The agents according to the invention can also be present in these use forms together with other active ingredients, such as, for. B. herbicides, insecticides, growth regulators and fungicides, or mixed with fertilizers and applied. When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.

example 1

Synthesis of 1,4-diacetylbenzene monoxime 9

25 g (0.154 mol) of 1,4-diacetylbenzene and 12.2 g (0.154 mol) of pyridine are dissolved in 80 ml of methanol. A solution of 10.7 g (0.154 mol) of hydroxylammonium chloride in 50 ml of water is slowly added under reflux. The mixture is stirred under reflux for 6 h and at room temperature for 15 h. Then it is filtered, the residue is washed three times with water and dried in vacuo. 24.7 g (90%) of the product are obtained as colorless crystals. Melting point: 162-169 ° C.

Example 2 Synthesis of 10

10

Synthesis of 1, l-dimethyl-4- (ortΛo-tolyl) semicarbazide 6:

23.7 g (0.395 mol) of 1,1-dimethylhydrazine are slowly added to a solution of 50 g (0.376 mol) of ortho-tolyl isocyanate in 400 ml of absolute toluene at 10-15 ° C. After stirring at room temperature for 16 h, the mixture is concentrated in vacuo and the residue is suspended in 100 ml of cyclohexane. After filtration and washing of the residue with pentane, 69.2 g (95%) of the product are obtained in the form of colorless crystals. Mp: 134-136 ° C.

Synthesis of 5-chloro-2,4-dihydro-2-methyl-4- (ortήo-tolyl) -3H-l, 2,4-triazol-3-one 7:

At 0 ° C 106 g (0.359 mol) triphosgene (bis (trichloromethyl) carbonate) to a solution of 69.2 g (0.358 mol) 1,1-dimethyl-4- (ortΛo-tolyl) -semicarbazid 6 given. The reaction mixture is stirred for 72 h at room temperature, concentrated in vacuo and the residue is taken up in 150 ml of ethyl acetate. After cooling to 0 ° C, 39.2 g of product precipitate. The mother liquor is concentrated in vacuo and taken up in 1.5 l of ethyl acetate. It is washed three times with water, dried over sodium sulfate, concentrated in vacuo and a total of 49.5 g (65%) of product in the form of a colorless sen powder. 400 MHz ^J H NMR (CDC1 ₃ ), δ [ppm]: 2.21 (s, 3H, Ar-CH ₃ ); 3.52 (s, 3H, _N-CH3); 7.13-7.44 (m, 4H, Ar-H).

Synthesis of 2,4-dihydro-5-methoxy-2-methyl-4- (ortho-tolyl) -JH-l, 2,4-triazol-3-one 8:

To a solution of 49.5 g (0.22 mol) of 5-chloro-2, 4-dihydro-2-methyl-4- (orthotolyl) -3if-l, 2,4-triazol-3- on 7 in 620 ml of a mixture of methanol and ethylene glycol dimethyl ether (1: 1) 79.2 g (0.44 mol) of a 30% sodium methylate solution are added. After stirring under reflux for 6 h, the mixture is concentrated in vacuo and the residue is taken up in ethyl acetate. It is washed three times with water, dried over sodium sulfate and concentrated in vacuo. The crude product is taken up in 100 ml MTBE, mixed with 150 ml hexane and cooled to 0 ° C. The precipitate is separated off and dried in vacuo at 40 ° C. for 1 h. 37.6 g (78%) of the product are obtained as a light beige powder. Mp .: 127-130 ° C.

Synthesis of 4- (ortΛo-bromomethylenephenyl) -2, 4-dihydro-5-methoxy-2-methyl-3.ϊ-l, 2,4-triazol-3-one 10:

A solution of 10.7 g (60 mmol) of IV-bromosuccinimide in 150 ml of absolute 1,2-dichloroethane is converted into a solution of 10.9 g (50 mmol) of 2,4-dihydro-5-methoxy-2-methyl 4- (ortho-tolyl) -3H-1, 2, 4-triazol-3-one 8 and 0.4 g of azobisisobutyronitrile in 150 ml of absolute 1,2-dichloroethane. The mixture is stirred under reflux for 1 h and irradiated with UV light. The mixture is then washed three times with water, dried over sodium sulfate and concentrated in vacuo. After the residue has been purified by flash chromatography, 4.1 g (28%) of the product are obtained as a colorless powder. Mp .: 113-115 ° C.

Example 3: Synthesis of 11

4.2 g (23 mmol) of 1,4-diacetylbenzene monoxime 9 are added to 0.62 g (26 mmol) of sodium hydride in 30 ml of absolute acetonitrile. The mixture is stirred under reflux for 1 h and then a solution of 7 g (23 mmol) 10 in 50 ml of absolute aceto- nitrile added. After stirring at room temperature for 15 h, the reaction mixture is taken up in dilute NaCl solution and extracted three times with methyl tert-butyl ether. The combined organic phase is washed with water, dried over sodium sulfate and concentrated in vacuo. The residue is purified by chromatography. 7.2 g (79%) of the product are obtained as colorless crystals. Melting point 102-106 ° C.

Example 4: Synthesis of 12

0.44 g (3.6 mmol) of O-2-trans-butene-hydroxylammonium chloride and 1 g of molecular sieve 3 Å are added to a solution of 1.1 g (2.8 mmol) 11 in 40 ml of methanol. The mixture is stirred at room temperature for 15 h. The molecular sieve is filtered off, the reaction mixture is taken up in ethyl acetate, washed twice with water, dried with sodium sulfate and concentrated in vacuo. After chromatographic purification of the residue, 840 ml (65%) of the residue are obtained as colorless crystals. Melting point 101-105 ° C.

30

Example 5: Synthesis of 13

40

1.33 g (55 mmol) of sodium hydride are added to a solution of 8.3 g (50 mmol) of 2,5-dimethyl-4-hydroxy-aceto-phenone in 120 ml of absolute DMF (dimethylformamide). After stirring for 1 h at room temperature, a solution of 15 g (50 mmol) 10 in 45 80 ml of absolute DMF is added and the mixture is stirred for 19 h at room temperature. It is then taken up in dilute NaCl solution and extracted three times with ethyl acetate. The combined organic phase is washed with water, dried over sodium sulfate and concentrated in vacuo. After chromatographic purification, 13.9 g (73%) of the product are obtained.

Example 6: Synthesis of 14

1 g (6 mmol) 13 are dissolved in 40 ml of methanol. 0.42 g (2.9 mmol) of 0- (3-chloropropene-2) -hydroxylammonium chloride and 1 g of molecular sieve 3 Å are added and the mixture is stirred for 15 h at room temperature. The mixture is filtered, the filtrate is taken up in ethyl acetate, the mixture is washed with water, dries with sodium sulfate, evaporates in vacuo and receives 1.1 g (89%) of the product (see Table 9 below).

The other compounds listed in Tables 2 and 3 below were obtained in an analogous manner.

Table 2: Physical data of compounds of the formula:

Table 3: Physical data of compounds of the formula:

45

applications

Experiment 1 - Activity against powdery mildew

Leaves of potted wheat seedlings of the "Frühgold" variety were sprayed to runoff point with aqueous active ingredient preparation, which was prepared from a stock solution consisting of 10% active ingredient, 63% cyclohexanone and 27% emulsifier, and 24 hours after the spray coating had dried on dusted with spores of powdery mildew (Erysiphe graminis forma specialis tritici). The test plants were then placed in a greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity. After 7 days, the extent of mildew development was determined visually in% infestation of the entire leaf area.

!) see tables 2 and 3

Experiment 2 - Efficacy against Plasmopara viticola

Leaves of pot vines of the "Müller-Thurgau" variety were sprayed to runoff point with aqueous preparation of active compound, which was prepared with a stock solution of 10% active compound, 63% cyclohexanone and 27% emulsifier. The following day the leaves were inoculated with an aqueous suspension of zoospores from Plasmopara viticola. The vines were then placed for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a humid chamber for 16 hours to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.

^l ) see tables 2 and 3

Experiment 3 - Activity against Pyricularia oryzae (protective)

Leaves of "Tai-Nong 67" rice seedlings grown in pots were sprayed to runoff point with aqueous active compound preparation which was prepared with a stock solution of 10% active compound, 63% cyclohexanone and 27% emulsifier. The following day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were then placed in climatic chambers at 22 to 24 ° C and 95 to 99% relative humidity for 6 days. The extent of the development of the infestation on the leaves was then determined visually.

^!) see tables 2 and 3

Claims

claims

Oxime ether compounds of the formula 1

in which the substituents have the following meanings:

W -OCH ₂ -, -C (Rι ₀ ) = NO-CH ₂ -;

X halogen, -C ₄ alkyl, -C ₄ alkoxy;

R _x H, -CC alkyl, halogen, nitro, CN, halo -CC alkyl, -CC alkoxy;

R ₂ H, Cχ-C alkyl, halogen, nitro, CN, halo -CC ₄ alkyl, -CC ₄ alkoxy;

n 1 or 2;

R ₃ H, -CC ₄ alkyl;

R ₅ H, C _! -C ₄ alkyl, C ₂ -C ₄ alkenyl;

R ₆ H, -CC ₄ alkyl, -C -C haloalkyl, C ₂ -C ₄ alkenyl, aryl;

H, halogen, Cι-C ₆ -alkyl, C ₆ haloalkyl, C ₂ -C ₆ -Alke- nyl, C ₂ -C ₆ haloalkenyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ - Halocycloalkyl, optionally substituted aryl;

R ₈ H, halogen, -CC ₆ -alkyl, Cx-C _ß -haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -haloalkenyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -Halogenocycloalkyl, optionally substituted aryl, or R ₇ and RQ together with the carbon atoms to which they are attached form an unsaturated heterocycle with 5 or 6 ring atoms, which has one or two heteroatoms which are selected independently of one another from a nitrogen, oxygen and sulfur atom and which can optionally be substituted with one or two radicals which are selected independently of one another from Cχ-C-alkyl, halogen, nitro, CN, halogen-Cι-C ₄ alkyl, OH, Cι-C alkoxy, optionally substituted aryl, C ₂ -C alkenyl, halo-C ₂ -C alkenyl, C ₂ -C ₄ alkynyl, halo-C ₂ -C alkynyl;

Rio H, halogen, -CC ₄ alkyl.

2. Compounds of formula 1 according to claim 1, wherein the substituents have the following meanings:

W -0CH ₂ -, -C (Rιo) = N-0-CH ₂ ;

X halogen, -C ₄ alkyl, -C ₄ alkoxy;

Ri H, -CC ₄ alkyl, halogen, halo -CC ₄ alkyl;

R ₂ H, -CC alkyl, halogen, halo -CC alkyl;

R ₃ H, -CC-alkyl;

n 1 or 2;

R ₅ H or C _! -C ₄ alkyl;

R ₆ H, -CC alkyl, halogen -CC ₄ alkyl;

R ₈ is H, halogen, _Cι-C6 alkyl, halo-Cι-C ₆ alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₂ -C ₆ alkenyl, phenyl, which can be substituted by one or two halogen or -CC alkyl; or R ₇ and Rs together with the carbon atoms to which they are attached form an unsaturated heterocycle with 5 or 6 ring atoms, which has one or two heteroatoms which are selected independently of one another from a nitrogen, oxygen and sulfur atom and that may optionally be substituted with one or two radicals which are selected independently of one another from C 1 -C ₄ alkyl, halogen, halogen C 1 -C ₄ alkyl, C 1 -C 4 alkoxy and phenyl, which are substituted by one or two halogen or -CC can be substituted;

Rg H, halogen, C _! -C ₆ alkyl, halogen-C _! -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, phenyl;

Rio H, halogen, C -C ₄ alkyl.

3. Compounds of formula 1 according to claim 1 or 2, wherein the substituents have the following meanings:

W -0CH ₂ -, -C (Rιo) = N-0-CH ₂ ;

X halogen, -CC alkoxy;

R _x H, -CC ₄ alkyl;

R ₂ H, -CC ₄ alkyl;

n 1 or 2;

R ₃ -CC ₄ alkyl;

R ₅ H, -CC ₄ alkyl;

R ₆ H, -CC ₄ alkyl;

R ₇ H, halogen, -CC ₆ alkyl;

R ₈ H, halogen, -CC ₆ alkyl, C ₂ -C ₆ alkenyl; or

R ₇ and R ₈ together with the carbon atoms to which they are attached form thiophenyl, furanyl, oxazolyl, thiazolyl, where these groups can have one or two substituents which are selected independently of one another from —CC alkyl, halogen and phenyl, which may be substituted by one or two halogen; R ₉ H, halogen, -CC ₆ alkyl;

Rio H, -CC ₄ alkyl.

4. Compounds of formula 1 according to any one of the preceding claims, wherein the substituents have the following meanings:

W -0CH ₂ -, -C (Rιo) = N-0-CH ₂ ;

X -C -alkoxy;

Rl H;

R ₂ H, -CC ₄ alkyl;

n 1 or 2;

R ₃ -CC ₄ alkyl;

R ₅ H, -CC ₄ alkyl;

R ₆ H, -CC ₄ alkyl;

R ₇ H, halogen;

R ₈ H, -CC ₄ alkyl, halogen; or

R ₇ and R ₈ together with the carbon atoms to which they are attached form thiophenyl or oxazolyl, these groups optionally being substituted by one or two halogen or phenyl and the phenyl may be substituted by one or two halogen;

Rg H, halogen;

Rio H, Ci-Cj alkyl.

5. Use of the compounds of formula 1 according to one of claims 1 to 4 as fungicides or for controlling pests.

6. Fungicidal composition comprising solid and / or liquid carriers and a fungicidally effective amount of at least one compound of the formula 1 according to claim 1.

7. A method for combating fungi, wherein the fungi or the materials, plants, seeds or the soil threatened by fungal attack are treated with a fungicidally effective amount of at least one compound of the formula 1 according to claim 1.

8. Pesticides containing inert additives and a pesticidally effective amount of at least one compound of formula 1 according to claim 1.

9. A method for controlling pests, the pests and / or their habitat being treated with a pesticidally effective amount of at least one compound of the formula 1 according to claim 1.

10. Compounds of formula 6

wherein

W, R 1, R ₂ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and n have the meanings given in one of Claims 1 to 4 and Y represents NH ₂ .