JP2003509415A - Unsaturated oxime ethers and their use for controlling harmful fungi and livestock pests - Google Patents

Abstract

(57) [Summary] The present invention relates to a compound represented by the formula (1): Wherein the substituents are as defined in the specification. The compounds are used for controlling harmful fungi and livestock pests.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to unsaturated oxime ethers, intermediates for producing them, and the use of unsaturated oxime ethers for controlling harmful fungi and animal pests.

[0002] Oxime ether compounds having a background bactericidal activity of the invention are already known. For example, WO
95/14009, WO96 / 17851, WO96 / 36229, WO96 /
36615, WO96 / 36616, WO96 / 36633, WO97 / 061
2, WO98 / 05652, and WO98 / 23155 have the formula:

[Chemical 3] [Wherein R ₁₇ and R ₁₈ are H, C _1-3 -alkyl, or phenyl]
, A triazolone pharmacologically active structure-containing strobilurins is described.

Compounds having unsaturated oxime ether side chains are described in EP-386561A, EP
-579124A, EP-585751A, EP-672347A, EP-67
3923A, WO 97/30032, and WO 97/33874.

The object of the present invention is to provide compounds having an improved activity and / or a broader spectrum of activity.

The present inventors have found that a compound having a triazolone pharmacologically active structure and an unsaturated oxime ether side chain achieves the above object.

[0006]   Therefore, the present invention provides formula (1):

[Chemical 4] [In the formula,   W is -OCH_Two-Or-C (R₁₀) = N-O-CH_Two-(Where CH _Two The end is in each case bonded to a phenyl group with a triazolone group)
Yes;   X is halogen, C_1-4-Alkyl, or C_1-4-Alkoxy;   R₁Is H, C_1-4-Alkyl, halogen, nitro, CN, halo-C_1-4 -Alkyl, or C_1-4-Alkoxy;   R_TwoIs H, C_1-4-Alkyl, halogen, nitro, CN, halo-C_1-4 -Alkyl, or C_1-4-Alkoxy;   n is 1 or 2;   R_ThreeIs H or C_1-4-Alkyl;   R₅Is H, C_1-4-Alkyl, or C_2-4-Alkenyl;   R₆Is H, C_1-4-Alkyl, C_1-4-Haloalkyl, C_2-4-Al
Alkenyl or aryl;   R₇Is H, halogen, C_1-6-Alkyl, C_1-6-Haloalkyl, C_{Two ~ 6} -Alkenyl, C_2-6-Haloalkenyl, C_3-6-Cycloalkyl, C _3-6 -Halocycloalkyl, or unsubstituted or substituted aryl;   R₈Is H, halogen, C_1-6-Alkyl, C_1-6-Haloalkyl, C_{Two ~ 6} -Alkenyl, C_2-6-Haloalkenyl, C_3-6-Cycloalkyl, C _3-6 -Halocycloalkyl, or unsubstituted or substituted aryl; Alternatively,   R₇And R₈Together with the carbon atom to which they are attached, has 5 or 6
Forming an unsaturated heterocycle having one or two heteroatoms having ring atoms, wherein
, The heteroatoms independently of one another are selected from nitrogen, oxygen and sulfur,
Is C_1-4-Alkyl, halogen, nitro, CN, halo-C_1-4-Alkyl
, OH, C_1-4-Alkoxy, unsubstituted or substituted aryl, C_2-4-Al
Kenyl, halo-C_2-4-Alkenyl, C_2-4-Alkynyl and halo-C_{2 to Four} -With one or two groups independently selected from the group consisting of alkynyl
May have been replaced;   R₉Is H, halogen, C_1-6-Alkyl, C_1-6-Haloalkyl, C_{Two ~ 6} -Alkenyl, C_2-6-Haloalkenyl, C_3-6-Cycloalkyl, C _3-6 -Halocycloalkyl, or unsubstituted or substituted aryl;   R₁₀Is H, halogen, or C_1-4-Is alkyl] And an unsaturated oxime ether compound represented by

The meaning of the above list is an alternative set name that individually lists the members of each group.
All hydrocarbon chains can be straight or branched. Halogenated substituents preferably have 1 to 5 identical or different halogen atoms.

For example, specific meanings are as follows: halogen: fluorine, chlorine, bromine, iodine, preferably fluorine or chlorine; C _1-4 alkyl: methyl, ethyl, n-propyl, 1-methyl. ethyl,
n- butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, preferably methyl; _{C 1 to 6} - alkyl: the above _{C 1 to 4} - in addition to the alkyl, 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-dimethyl Butyl, 2,3-dimethylbutyl,
3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl , Preferably methyl, ethyl, n-
Propyl, 1-methylethyl, n- butyl, or 1,1-dimethylethyl; _{C 2 to 6} - alkenyl: ethenyl, prop-1-en-1-yl, prop-2-en-1-yl, 1- Methylethenyl, n-buten-1-yl, n-buten-2-yl, n-buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-ene-1-
2-methylprop-2-en-1-yl, n-penten-1-yl, n-
Penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-
Methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-
Methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-
Methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-
Methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-
Methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2
-En-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-ene -1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-
Yl, n-hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-ene-1
-Yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-
En-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-
3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4- En-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1
, 1-Dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1
-Yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2
-En-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1 ,
3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-ene-1
-Yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2
-En-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1
-Ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1
-Ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2
-Ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1
, 1,2-Trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl, 1- ethyl-2-methylprop-2-en-1-yl, preferably, ethenyl or prop-2-en-1-yl; _{C 2 to 4} - alkynyl: ethynyl, prop-1-yn-1-yl, prop - 2-in-3-yl, n-but-1-in-1-yl, n-but-1-in-
4-yl, n-but-2-yn-1-yl, preferably prop-2-in-1
-Yl; C _1-2 -haloalkyl: for example, 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; _C1-6 -haloalkyl: said C partially or completely substituted with fluorine, chlorine and / or bromine. _1-6 -alkyl, ie, for example, in the above _C1-2 -haloalkyl. In addition, 3-chloropropyl or heptafluoropropyl, preferably trifluoromethyl, pentafluoroethyl or heptafluoropropyl; _C2-6 -haloalkenyl: partially or completely substituted with fluorine, chlorine and / or bromine. have been the _{C 2 to 6} - alkenyl, i.e., for example, 2-chloroallyl, 3-chloroallyl, or 3,3-dichloro-allyl; _{C 2 to 4} - haloalkynyl: fluorine, partially or with chlorine and / or bromine Fully substituted _C2-4 -alkynyl, for example chloroethynyl, 3-chloropropynyl; _C3-6 -cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, preferably cyclopropyl, cyclopentyl, or cyclohexyl. ; halo _{-C 3~6} - cycloalkyl : Fluorine, said partially or fully substituted by chlorine and / or bromine C _{3 to 6 -} cycloalkyl, i.e., for example, 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 Or naphthyl, especially phenyl.

Unsaturated heterocycles having 5 or 6 ring atoms can be aromatic or non-aromatic. Aromatic heterocycles are especially 2-furyl, 3-furyl, 2-thienyl, 3-furyl.
Thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl,
5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-
Oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-
Oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,
4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,
4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,
4-thiadiazol-2-yl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5- Pyrimidinyl, 2-pyrazinyl, especially furanyl, thienyl, oxazolyl, and thiazolyl.

If the aryl group is substituted, it is preferably halogen, especially fluorine or chlorine, C _1-4 -alkyl, C _1-4 -haloalkyl, C _1-4 -alkoxy, nitro, OH, And CN having 1 or 2 substituents independently selected from each other. Preferred substituents are halogen and / or C _1-4-
It is alkyl.

[0011]   The substituents in formula (1) preferably have the following meanings.

[0012]   X is C_1-4-Alkoxy, or halogen, especially C_1-4-With alkoxy
Yes;   R₁Is H, C_1-4-Alkyl, halogen, halo-C_1-4-Alkyl, special
, H, or C_1-4-Alkyl;   R_TwoIs H, C_1-4-Alkyl, halogen, halo-C_1-4-Alkyl, special
, H, or C_1-4-Alkyl;   R_ThreeIs C_1-4-Alkyl;   R₅Is H or C_1-4-Alkyl;   R₆Is H, C_1-4-Alkyl, or halo-C_1-4-Alkyl, especially H
, Or C_1-4-Alkyl;   R₇Is H, halogen, C_1-6-Alkyl, halo-C_1-6-Alkyl, C _3-6 -Cycloalkyl, C_3-6-Halocycloalkyl, or phenyl, especially
, H, halogen, C_1-6-Alkyl, particularly preferably H, or halogen
R;   R₈Is H, halogen, C_1-6-Alkyl, halo-C_1-6-Alkyl, C _3-6 -Cycloalkyl, C_3-6-Halocycloalkyl, C_2-6-Arkeni
Or phenyl, especially H, halogen, or C_1-6-Alkyl; Alternatively,   R₇And R₈Together with the carbon atom to which they are attached, a thienyl group,
Represents a ryl group, an oxazolyl group, or a thiazolyl group, wherein the group is C_1-4 -Alkyl, halogen, or optionally substituted with 1 or 2 halogens
Optionally substituted with phenyl, especially R₇And R₈They are bound
Together with the carbon atom, it represents a thienyl group or an oxazolyl group, the
The group may be substituted with 1 or 2 halogens or phenyl, said
Phenyl may be substituted with 1 or 2 halogens;   R₉Is H, halogen, C_1-6-Alkyl, halo-C_1-6-Alkyl, C _3-6 -Cycloalkyl, C_3-6-Halocycloalkyl, or phenyl, especially
, H, halogen, C_1-6-Alkyl, particularly preferably H, or halogen
R;   R₁₀Is H or C_1-4-Alkyl.

The oxime side chain may be attached to the phenyl ring in the ortho, meta, or para position relative to W. Preferably, it is attached at the para position.

The R ₁ group is preferably in the 6-position.

When the oxime side chain is attached para to W, the R ₂ group is preferably present in the 2 and / or 5 position.

[0016]   A preferred embodiment is a compound of formula (1) defined below.

[0017]   (A)   W is -OCH_Two-Or-C (R₁₀) = N-O-CH_Two-Is;   X is halogen, C_1-4-Alkyl, or C_1-4-Alkoxy;   R₁Is H, C_1-4-Alkyl, halogen, or halo-C_1-4-Alkyl
And   R_TwoIs H, C_1-4-Alkyl, halogen, or halo-C_1-4-Alkyl
And   R_ThreeIs H or C_1-4-Alkyl;   n is 1 or 2;   R₅Is H or C_1-4-Alkyl;   R₆Is H, C_1-4-Alkyl, or halo-C_1-4-Alkyl;   R₇Is H, halogen, C_1-6-Alkyl, halo-C_1-6-Alkyl, C _3-6 -Cycloalkyl, C_3-6-Halocycloalkyl, or phenyl
;   R₈Is H, halogen, C_1-6-Alkyl, halo-C_1-6-Alkyl, C _3-6 -Cycloalkyl, C_3-6-Halocycloalkyl, C_2-6-Arkeni
Or phenyl; Alternatively,   R₇And R₈Together with the carbon atom to which they are attached, has 5 or 6
Forming an unsaturated heterocycle having one or two heteroatoms having ring atoms, wherein
, The heteroatoms independently of one another are selected from nitrogen, oxygen and sulfur,
Is C_1-4-Alkyl, halogen, halo-C_1-4-Alkyl, C_1-4-A
Lucoxy, and 1 or 2 halogens or C_1-4-Substituted with alkyl
One or two independently selected from the group consisting of optionally substituted phenyl
Optionally substituted with 4 groups;   R₉Is H, halogen, C_1-6-Alkyl, halo-C_1-6-Alkyl, C _3-6 -Cycloalkyl, C_3-6-Halocycloalkyl, or phenyl
;   R₁₀Is H, halogen, or C_1-4-Alkyl.

(B) W is —OCH ₂ — or —C (R ₁₀ ) ═N—O—CH ₂ —; X is halogen, or C _1-4 -alkoxy; R ₁ is , H, or C _1-4 -alkyl; R ₂ is H, or C _1-4 -alkyl; n is 1 or 2; R ₃ is C _1-4 -alkyl ; R ₅ is, H, or _{C 1 to 4} - is alkyl; _{R 6} is, H, or _{C 1 to 4} - is alkyl; _{R 7} is, H, halogen, or _{C 1 to 6} - an alkyl ; R ₈ is, H, halogen, or _{C 1 to 6} - alkyl; or, _{R 7} and _{R 8} together with the carbon atoms to which they are attached, a thienyl group, furanyl group, oxazolyl group, or thiazolyl group is formed, in which said _{groups, C 1 to 4} - alkyl, halogen And it may have one or two one or two substituents independently selected from the group consisting of phenyl optionally substituted with halogen; R ₉ is, H, halogen , or _{C 1 to 6} - is alkyl; _{R 10} is, H, or _{C 1 to 4} - alkyl.

(C) W is —OCH ₂ — or —C (R ₁₀ ) ═N—O—CH ₂ —; X is C _1-4 -alkoxy; R ₁ is H R ₂ is H or C _1-4 -alkyl; n is 1 or 2; R ₃ is C _1-4 -alkyl; R ₅ is H or C _{1- 4} - in There alkyl; _{R 6} is, H, or _{C 1 to 4} - is alkyl; _{R 7} is, H, or a halogen; _{R 8} is, _{H, C 1 to 4} - alkyl, or a halogen Or R ₇ and R ₈ together with the carbon atom to which they are attached form a thiophenyl group or an oxazolyl group, wherein said group is one or two halogen or phenyl (here And said phenyl may be substituted with 1 or 2 halogens) R ₉ is H or halogen; R ₁₀ is H or C _1-4 -alkyl.

[0020]   Further embodiments are as follows.

[0021]   (D) Formula (1a):

[Chemical 5] Wherein X is chlorine or methoxy; R ₂ is chlorine or methyl; n is 1 or 2, but when n = 1, R ₂ is relative to the oxygen substituent. At the 2-position and n = 2, R ₂ is at the 2,5-position to the oxygen substituent; R ₅ is H, methyl, or ethyl; R ₇ is H, R ₈ is H, methyl, ethyl, chlorine, phenyl, ethenyl, or prop-1-.
And R ₉ is H, methyl, or chlorine].

[0022]   (E) Formula (1b):

[Chemical 6] [Wherein, X is chlorine, or methoxy; R ₅ is H, methyl, or ethyl; R ₇ is H, methyl, or chlorine; R ₈ is H, methyl, ethyl, Chlorine, phenyl, ethenyl, or prop-1-
And R ₉ is H, methyl, or chlorine].

[0023] The oxime side chain is preferably attached in the para position.

[0024]   (F) Formula (1c):

[Chemical 7] [In the formula, R represents thiophen-2-yl, thiophen-3-yl, furan-2-yl, furan-3-yl, 5-chlorothiophen-2-yl, 5-bromothiophene-2.
-Yl, 5-chlorofuran-2-yl, 5-bromofuran-2-yl, 5-methylthiophen-2-yl, 5-phenylthiophen-2-yl, 5-methylfuran-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, thiazol-4-yl, or thiazol-5-yl].

The groups X, R ₂ and R ₅ here have the meanings given above or preferably have the following meanings: X is chlorine or methoxy; R ₂ is 2-methyl , 2-chloro, or 2,5-dimethyl; R ₅ is H, methyl, or ethyl.

[0026]   (G) Formula (1d), Formula (1e), or Formula (1f):

[Chemical 8] [In the formula, R represents thiophen-2-yl, thiophen-3-yl, furan-2-yl, furan-3-yl, 5-chlorothiophen-2-yl, 5-bromothiophene-2.
-Yl, 5-chlorofuran-2-yl, 5-bromofuran-2-yl, 5-methylthiophen-2-yl, 5-phenylthiophen-2-yl, 5-methylfuran-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, thiazol-4-yl, or thiazol-5-yl].

The groups X and R ₅ here have the meanings given above or preferably have the following meanings: X is chlorine or methoxy; R ₅ is H, methyl or ethyl Is.

Particularly preferred for use are the formulas (1c) to (1) described below.
The compound of f). The groups described herein for the substituents are themselves
Independent of the combination in which they are mentioned, they are particularly preferred embodiments of the individual substituents.

(A) A compound represented by formula (1c), wherein R ₂ is 2-methyl (based on an oxygen substituent), X is chlorine, R ₅ is hydrogen, and R is A compound as described in the vertical column of Table 1.

(B) A compound represented by formula (1c), wherein R ₂ is 2-methyl (based on an oxygen substituent), X is methoxy, R ₅ is hydrogen, and R is A compound as described in the vertical column of Table 1.

(C) A compound represented by formula (1c), wherein R ₂ is 2-chloro (based on an oxygen substituent), X is chlorine, R ₅ is hydrogen, and R is A compound as described in the vertical column of Table 1.

(D) A compound represented by formula (1c), wherein R ₂ is 2-chloro (based on an oxygen substituent), X is methoxy, R ₅ is hydrogen, and R is A compound as described in the vertical column of Table 1.

(E) A compound represented by formula (1c), wherein R ₂ is 2,5-dimethyl (based on an oxygen substituent), X is chlorine, R ₅ is hydrogen, A compound wherein R is as listed in the vertical column of Table 1.

(F) A compound represented by the formula (1c), wherein R ₂ is 2,5-dimethyl (based on an oxygen substituent), X is methoxy, R ₅ is hydrogen, A compound wherein R is as listed in the vertical column of Table 1.

(G) A compound represented by formula (1c), wherein R ₂ is 2-methyl (based on an oxygen substituent), X is chlorine, R ₅ is methyl, and R is A compound as described in the vertical column of Table 1.

(H) A compound represented by formula (1c), wherein R ₂ is 2-methyl (based on oxygen substituent), X is methoxy, R ₅ is methyl, and R is A compound as described in the vertical column of Table 1.

(I) A compound represented by formula (1c), wherein R ₂ is 2-chloro (based on an oxygen substituent), X is chlorine, R ₅ is methyl, and R is A compound as described in the vertical column of Table 1.

(J) A compound represented by formula (1c), wherein R ₂ is 2-chloro (based on an oxygen substituent), X is methoxy, R ₅ is methyl, and R is A compound as described in the vertical column of Table 1.

(K) A compound represented by formula (1c), wherein R ₂ is 2,5-dimethyl (based on an oxygen substituent), X is chlorine, R ₅ is methyl, A compound wherein R is as listed in the vertical column of Table 1.

(L) A compound represented by the formula (1c), wherein R ₂ is 2,5-dimethyl (based on an oxygen substituent), X is methoxy, R ₅ is methyl, A compound wherein R is as listed in the vertical column of Table 1.

(M) A compound represented by formula (1c), wherein R ₂ is 2-methyl (based on oxygen substituent), X is chlorine, R ₅ is ethyl, and R is A compound as described in the vertical column of Table 1.

(N) A compound represented by formula (1c), wherein R ₂ is 2-methyl (based on an oxygen substituent), X is methoxy, R ₅ is ethyl, and R is A compound as described in the vertical column of Table 1.

(O) A compound represented by formula (1c), wherein R ₂ is 2-chloro (based on an oxygen substituent), X is chlorine, R ₅ is ethyl, and R is A compound as described in the vertical column of Table 1.

(P) A compound represented by formula (1c), wherein R ₂ is 2-chloro (based on an oxygen substituent), X is methoxy, R ₅ is ethyl, and R is A compound as described in the vertical column of Table 1.

(Q) A compound represented by the formula (1c), wherein R ₂ is 2,5-dimethyl (based on an oxygen substituent), X is chlorine, R ₅ is ethyl, A compound wherein R is as listed in the vertical column of Table 1.

(R) A compound represented by formula (1c), wherein R ₂ is 2,5-dimethyl (based on an oxygen substituent), X is methoxy, R ₅ is ethyl, A compound wherein R is as listed in the vertical column of Table 1.

(S) A compound of formula (1d), wherein X is chlorine, R ₅ is hydrogen and R is as listed in the vertical column of Table 1.

(T) A compound of formula (1d), wherein X is methoxy, R ₅ is hydrogen, and R is as listed in the vertical column of Table 1.

(U) A compound of formula (1d), wherein X is chlorine, R ₅ is methyl and R is as listed in the vertical column of Table 1.

(V) A compound of formula (1d), wherein X is methoxy, R ₅ is methyl, and R is as listed in the vertical column of Table 1.

(W) A compound of formula (1d), wherein X is chlorine, R ₅ is ethyl and R is as listed in the vertical column of Table 1.

(X) A compound of formula (1d), wherein X is methoxy, R ₅ is ethyl, and R is as listed in the vertical column of Table 1.

(Y) A compound of formula (1e), wherein X is chlorine, R ₅ is hydrogen, and R is as listed in the vertical column of Table 1.

(Z) A compound of formula (1e), wherein X is methoxy, R ₅ is hydrogen and R is as listed in the vertical column of Table 1.

(Aa) A compound of formula (1e), wherein X is chlorine, R ₅ is methyl, and R is as listed in the vertical column of Table 1.

(Ab) A compound of formula (1e), wherein X is methoxy, R ₅ is methyl, and R is as listed in the vertical column of Table 1.

(Ac) A compound of formula (1e), wherein X is chlorine, R ₅ is ethyl, and R is as listed in the vertical column of Table 1.

(Ad) A compound of formula (1e), wherein X is methoxy, R ₅ is ethyl, and R is as listed in the vertical column of Table 1.

(Ae) A compound represented by formula (1f), wherein X is chlorine, R ₅ is hydrogen, and R is as described in the vertical column of Table 1.

(Af) A compound of formula (1f), wherein X is methoxy, R ₅ is hydrogen, and R is as described in the vertical column of Table 1.

(Ag) A compound of formula (1f), wherein X is chlorine, R ₅ is methyl, and R is as listed in the vertical column of Table 1.

(Ah) A compound of formula (1f), wherein X is methoxy, R ₅ is methyl, and R is as listed in the vertical column of Table 1.

(Ai) A compound of formula (1f), wherein X is chlorine, R ₅ is ethyl, and R is as listed in the vertical column of Table 1.

(Aj) A compound of formula (1f), wherein X is methoxy, R ₅ is ethyl and R is as listed in the vertical column of Table 1.

Table 1 (E), (E, E) and (Z) relate to the substituents on the double bond listed in R.

[0066]

[Table 1] The compounds of this invention can be made in a number of ways. Preferably, it is synthesized by either synthetic route A or B as illustrated in the reaction schemes below.
The synthesis starts from the compound of formula (2) and in synthetic route A, X ₁ is CH ₃ or PGOCH ₂ —, where PG is a protecting group for benzyl ether. . After synthesizing the triazolone ring, the protecting group was separated and removed, and the resulting benzyl alcohol was converted to X ₂ CH ₂ — (where X ₂ is a nucleophilically removable group by a method described in the literature). ) (Cf. TW Greene: "Protective Grou
ps in Organic Synthesis ", 2nd Edition 1991, John Wiley, New York). In the case of route B, X ₁ = X ₂ CH _2- (where X ₂ is a nucleophilically removable group, for example, Chlorine, fluorine, bromine, nitro, or alkyl- or aryl sulfonates, such as mesylates, tosylates, or triflates.) The preparation of these compounds is known, eg the synthesis from the corresponding nitro compounds. Regarding Houben-Weyl, Vol. IV / lc, 4th Edition, p. 506ff, Thieme Verla
g, Stuttgart 1980.

[0067]

[Chemical 9] First, the amino functional group of the compound (2) is converted into a triazolone group to give a compound (
3) is obtained. A series of reactions for carrying out this conversion are described in detail in WO95 / 14009 (Compound No. 21 → 19 → 17 → 1) and also WO96 / 26191.
And DE-1980995.

The group X ₁ is then converted into a reactive group capable of reacting with the group V of compound (7) or the group W ₁ of the compound of formula (8), connecting the two phenyl rings to form group W. Let The group V is a phenolic OH group or the group -C (R < ₁₀ >) = N-OH.
A leaving group is introduced into the group X ₁ which is removed at the hydrogen atom of the phenolic OH group or the OH group of the oxime in the presence of base. Examples of such a leaving group include chloride, bromide, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, and the like. These leaving groups are introduced by a method known to those skilled in the art, for example, by reacting the compound (3) in which X ₁ is CH ₃ with N-bromosuccinimide or N-chlorosuccinimide.

The reaction of the compound (3) with the compound (7) or (8) can be carried out by using a base (for example, an acetone, acetonitrile, dimethylsulfoxide, dimethylformamide, or N-methylpyrrolidone or a diluent in an inert solvent or diluent. , Sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride and the like). Generally, the base is used in equimolar or excess molar amounts. It may also be advantageous to add catalytic amounts of crown ethers (eg 18-crown-6, or 15-crown-5). The reaction temperature is generally 0 to 80 ° C, preferably 20 to 60 ° C.

[0070]   The methods for producing the compounds (7) and (8) are known to those skilled in the art, and for example, Orga
nikum, 17th Edition, VEB Deutscher Verlag der Wissenschaften, Berlin 198
8, p. 323ff, and Angewandte Chemie,84 (1972) 295 and Zh. Org. Khim, 31  (1995) 601, Chem. Pharm. Bull.36 (1988) 3134, Indian J. Chem., Sect.
 B,31 (1992) 495.

The compound (4) obtained by reacting the compound (3) with the compound (7) is
It is oxime-ized using O-alkenyl hydroxylamine or its salt. Methods for preparing O-alkenylhydroxylamine are known to those skilled in the art and are described, for example, in
em. Pharm. Bull. 91 (1983), 2601 and J. Am. Chem. Soc. 71 (1949), 3423.
It is described in.

Alternatively, compound (3) can be directly reacted with oxime (8) to obtain compound (1). Route A, including the preparation of the above intermediates and similar intermediates
All steps of EP-386581A (when W is OCH ₂ ) and EP-5
85751A (where W is C (R ₁₀ ) = NOCH ₂ ).

The starting material used in Route B is also compound (2). Reaction with oxime (8) under etherification conditions as described above gives compound (6) (Y = NH ₂ ). The triazolone ring is synthesized as in Route A.

Alternatively, the compound (2) is reacted with the compound (7) under the above etherification conditions to obtain the compound (5). This is oxime-ized using O-alkenyl hydroxylamine or its salt similarly to the method in the route A, and a compound (6) is obtained, and a triazolone ring is introduce | transduced into it as above-mentioned.

Since the compounds of the present invention have C = C or C = N double bonds, they can be prepared as a mixture of E / Z isomers. These mixtures may be separated into their individual components by conventional means, such as crystallization or chromatography. The individual isomeric compounds and mixtures thereof, as well as all enantiomers, racemates and diastereomers, are included in the present invention.

The novel compound (1) has a broad spectrum of phytopathogenic fungi, especially Ascomyce.
It has excellent activity against phytopathogenic fungi of the tes and Basidiomycetes classes and can be used as a foliar and soil treatment fungicide. Some compounds included in the novel compound (1) are
And has a very high systemic effect and systemic action, especially after foliar treatment.

The compound (1) is used in a wide variety of crop plants, for example, wheat, rye, barley, oats, rice, corn, grass, cotton, soybean, coffee, sugar cane, vines, fruits, ornamental plants. , And vegetables, such as cucumbers,
It is of particular importance in controlling beans, and pumpkins, and the numerous types of fungi that develop on the seeds of these plants.

[0078]   The compound (1) is particularly suitable for controlling the following plant diseases.

[0079]   Erysiphe graminis in powdered cereals;   Erysiphe cichoracearum, Sphaerotheca fuliginea in pumpkins;   Podosphaera leucotricha in apples;   Uncinula necator in grapes;   Puccinia sp. In cereals;   Rhizoctonia sp. In cotton and grass;   Ustilago sp. In cereals and sugar cane;   Venturia inaequalis in apples;   Helminthosporium sp. In cereals;   Septoria nodorum in wheat;   Botrytis cinerea (gray mold) in strawberries and grapes;   Cercospora arachidicola in peanuts;   Pseudocercosporella herpotrichoides in wheat and barley;   Pyricularia oryzae in rice;   Phytophthora infestans in potatoes and tomatoes;   Fusarium sp., Verticillium sp. In a wide variety of plant species;   Plasmopara viticola in grapes;   Alternaria sp. In vegetables and fruits.

When using the compound (1), the fungus or a plant, seed, substance or soil to be protected from fungal infection is treated with a fungicidally effective amount of the compound (1). Compound (1
) May be used before or after infection of the substance, plant or seed with fungi.

The compound (1) is a liquid agent, an emulsion, a suspension agent, a fine powder agent (dust), or a powder agent (powd).
er), paste or granules and the like. The use form depends on the particular intended use, but in each case, it should be ensured that the compound (1) of the present invention is finely and homogeneously distributed. The above-mentioned preparation is produced by a known means, for example, by mixing the active ingredient with a solvent and / or a carrier and, if necessary, using an emulsifier or a dispersant. If water is used as the diluent, it is also possible to use other organic solvents as auxiliary solvents. Suitable auxiliary substances for this purpose are essentially solvents such as aromatic compounds (eg xylene), chlorinated aromatic compounds (eg chlorobenzene), paraffins (eg mineral oil fractions), alcohols (
For example, methanol, butanol), ketones (eg, cyclohexanone),
Amines (eg ethanolamine, dimethylformamide), and water; carriers such as powdered natural minerals (eg kaolin, clay, talc, chalk),
And powdered artificial minerals (for example, finely pulverized silica and silicate); emulsifiers such as nonionic emulsifiers and anionic emulsifiers (for example, polyoxyethylene fatty alcohol ether, alkyl sulfonate, aryl sulfonate); and lignin-
It is a dispersant for waste liquid such as sulfite and methyl cellulose.

The disinfectant composition of the present invention usually contains 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of the active ingredient. The application rate depends on the quality of effect desired, and the amount of active ingredient per hectare is from 0.01 to 3 kg.

The amount of the active ingredient in seed treatment is generally 0.00 per 1 kg of seeds.
1 to 50 g, preferably 0.01 to 10 g is required.

In a form of use as a fungicide, the composition according to the invention comprises another active ingredient, for example
It may coexist with herbicides, insecticides, growth regulators, fungicides or with fertilizers.

It is often possible to broaden the bactericidal activity spectrum by mixing with another bactericide.

The compounds of formula (1a) are furthermore suitable for the efficient control of pests contained in insects, arachnids and nematodes. The compounds of formula (1a) can be used as pesticides in crop protection and as pesticides in the fields of hygiene, stored food and veterinary medicine.

[0087]   Examples of harmful insects include the following.

As a Lepidoptera, for example, Agrotis ypsilon, Agrotis segetum,
Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Auto
grapha gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Ch
eimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis,
Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidal
is, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eu
poecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mell
onella, Grapholita funebrana, Grapholita molesta, Heliothis armigera, He
liothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria,
Hyphantria cunea, Hyponomeuta malinellus, Keifferia lycopersicella, Lamb
dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scit
ella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis
, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma ne
ustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Pa
nolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucep
hala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae,
Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Phyacio
nia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothi
s pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera l
itura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeira
phera canadensis.

Examples of Coleoptera include Agrilus sinuatus, Agriotes lineatu.
s, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Antho
nomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus pinip
erda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus len
tis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrh
ynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, Conoderus v
espertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-pu
nctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis,
Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hyp
era postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotar
sa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melan
otus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha me
lolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus,
Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllop
ertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia ja
ponica, Sitona lineatus, Sitophilus granaria.

As a Diptera, for example, Aedes aegypti, Aedes vexans, Anastrep
ha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezzian
a, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, C
ordylobia anthopophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Da
sineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Gloss
ina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia pl
atura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia
cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Mu
sca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya
hyoscyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagol
etis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tip
ula paludosa.

As a thrips (Thysanoptera), for example, Frankliniella fusca, Frank
liniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips
oryzae, Thrips palmi, Thrips tabaci.

As Hymenoptera, for example, Athalia rosae, Atta cephalotes, A
tta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Mono
morium pharaonis, Solenopsis geminata, Solenopsis in victa.

As a heteroptera (Heteroptera), for example, Acrosternum hilare, Blissus leuco
pterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius
, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllo
pus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata
, Solubea insularis, Thyanta perditor.

Examples of the Homoptera include, for example, Acyrthosiphon onobrychis, Adelges l
aricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Bemi
sia tabaci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossyp
ii, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaul
acorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum e
uphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, My
zodes persicae, Myzus cerasi, Nephotettix cincticeps, Nilaparvata lugens
, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psyll
a mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sap
pahis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes va
porariorum, Viteus vitifolii.

Examples of the termite (Isoptera) include Calotermes flavicollis, Leucoter.
mes flavipes, Retuculitermes lucifugus, Termes natalensis.

As an Orthoptera, for example, Acheta domestica, Blatta orientali
s, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa,
Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Mela
noplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris
septemfasciata, Periplaneta americana, Schistocerca americana, Schistoc
erca peregrina, Stauronotus maroccanus, Tachycines asynamorus.

As arachnids, for example, Acarina, for example, Amblyomma americanum,
Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus de
coloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa
, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalo
mma truncatum, Ixodes ricinus, Ixodes rubicundus, Metatetranychus (Phano
nychus) ulmi, Ornithodorus moubata, Otobins megnini, Paratetranychus pil
osus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus
latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus ever
tsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai,
Tetranychus pacificus, Tetranychus telarius, Tetranychus urticae.

Nematodes include, for example, root-knot nematodes such as Meloidogyne hapla, Mel.
oidogyne incognita, Meloidogyne javanica, cyst-forming nemat
oda), for example, Globodera rostochiensis, Heterodera avenae, Heterodera gl
ycinae, Heterodera schachtii, Heterodera trifolii, stem and leaf nematodes (stem ee
lworms and foliar nematodes), for example, Belonolaimus longicaudatus, Dityl
enchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, L
ongidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodor
us primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Praty
lenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Prat
ylenchus goodeyi.

The active ingredient can be used in the form as it is or in the form of preparations or use forms prepared from the preparations, for example spray solutions, powders, suspensions or dispersions, emulsions, oil dispersions, Pastes, dusts, diffusion materials
For spreading or in the form of granules, it can be used by spraying, spraying, dusting, spreading or pouring. The use form depends exclusively on the intended use, but in each case it must be such that the active ingredient according to the invention is distributed in the finest possible manner.

The active ingredient concentrations in the ready-to-use preparations can be varied within the practical range.

Generally, the concentration of active ingredient is from 0.0001 to 10%, preferably from 0.01 to
1%.

The active ingredients of the invention can also be used effectively in the micro-dispersion method (ULV),
In that case, it is possible to use a formulation containing 95% by weight or more of the active ingredient, or it is possible to spray the active ingredient without adding an additive.

Under field conditions, the active ingredient application rate for controlling pests is 0.1-2.0 kg.
/ Ha, preferably 0.2 to 1.0 kg / ha.

Suitable substances for preparing spray solutions, emulsions, pastes or oily dispersions are medium to high boiling fractions of mineral oils, for example kerosene or diesel oils, also coal tar oils, of plant or animal origin. Oils, aliphatic, cycloaliphatic or aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene,
Alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strong polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and Water, etc.

Aqueous use forms are emulsion concentrates, pastes or wettable powders (sprayable powders
ble powders), oily dispersion) can be prepared by adding water. Emulsions, pastes or oily dispersions should be prepared by uniformly dispersing the above substances themselves or those obtained by dispersing the above substances in oils or solvents in water using a wetting agent, tackifier, dispersant or emulsifier. You can However, it is also possible to prepare concentrate forms suitable for dilution with water, consisting of the active ingredient, wetting agent, tackifier, and dispersant or emulsifier, and optionally solvent or oil.

Suitable surfactants are lignosulphonic acid, naphthalenesulphonic acid, phenolsulphonic acid, dibutylnaphthalenesulphonic acid, alkylarylsulphonates,
Alkylsulfates, alkylsulfonates, fatty alcohol sulfates and alkali metal salts of fatty acids, alkaline earth metal salts and ammonium salts, and their alkali metal salts and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, Condensate of sulfonated naphthalene and naphthalene derivative with formaldehyde, condensate of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ether, tributylphenyl poly Glycol ether,
Alkylaryl polyether alcohol, isotridecyl alcohol, fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite waste liquid, and It is methyl cellulose.

Powders, diffusing materials and fine powders can be prepared by mixing or milling the active ingredient and the solid carrier.

In general, the formulations contain 0.01 to 95% by weight, preferably 0.1 to 90% by weight of active ingredient. 90% to 100% active ingredient, preferably 95%
Use one with -100% purity (according to NMR spectrum).

Examples of formulations are granules, such as coated granules, impregnated granules and homogeneous granules, which can be prepared by attaching the active ingredient to a solid carrier. Examples of solid carriers are mineral earths, such as silica gel, silica, silicates, talc, kaolin, attaclay, limestone, lime, chalk, clay, ocher, clay, dolomite, diatomaceous earth, calcium sulphate. , Magnesium sulphate, magnesium oxide, ground synthetics, fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate and urea, products of plant origin such as cereal flour, bark flour, wood flour and nutshell flour, cellulose powder, and Other solid carriers can be mentioned.

Various oils or herbicides, fungicides, other pesticides or bactericides can also be added to the active ingredients according to the invention if appropriate just before use (tank mix).
. The above substances may be admixed with the active ingredients according to the invention in a weight ratio of 1:10 to 10: 1.

In the above use forms, the compositions according to the invention can be present together with other active compounds, for example herbicides, insecticides, growth regulators and fungicides, or else they can be applied together with fertilizers. You can also do it. In many cases, the bactericidal activity spectrum can be broadened by mixing with other bactericides.

Example 1 Synthesis of 1,4-diacetylbenzene monooxime (9)

[Chemical 10] 25 g (0.154 mol) of 1,4-diacetylbenzene and 12.2 g (0.1
Dissolve 54 mol of pyridine in 80 mL of methanol. Under reflux, slowly add an aqueous solution of 10.7 g (0.154 mol) of hydroxylammonium chloride in 50 mL of water. The resulting mixture is stirred under reflux for 6 hours and then at room temperature for 15 hours. The mixture is then filtered and the residue is washed 3 times with water and dried under reduced pressure to give 24.7 g (90%) of product as colorless crystals.

[0113] Melting point: 162-169 [deg.] C.

Example 2 Synthesis of compound (10)

[Chemical 11] Synthesis of 1,1-dimethyl-4- (ortho-tolyl) semicarbazide (6) To a solution of 50 g (0.376 mol) of ortho-tolyl isocyanate dissolved in 400 mL of anhydrous toluene, at 10 to 15 ° C, 23.7 g (0.395 mol)
Slowly add 1,1-dimethylhydrazine. The resulting mixture is stirred at room temperature for 16 hours and then concentrated under reduced pressure. The residue is suspended in 100 mL cyclohexane. The residue obtained by filtration was washed with pentane to give 69.2 g (95%
) Product is obtained as colorless crystals.

[0115] Melting point: 134-136 ° C.

5-chloro-2,4-dihydro-2-methyl-4- (ortho-tolyl) -3H
Synthesis of 1,2,4-triazol-3-one (7) To a solution of 69.2 g (0.358 mol) of 1,1-dimethyl-4- (ortho-tolyl) semicarbazide (6) was added 0 ° C. At this time, 106 g (0.359 mol) of triphosgene (bis (trichloromethyl) carbonate) are added. The reaction mixture is stirred at room temperature for 72 hours and then concentrated under reduced pressure. The residue is taken up in 150 mL ethyl acetate. Cooling to 0 ° C. precipitates out 39.2 g of product. The mother liquor is concentrated under reduced pressure and taken up in 1.5 L of ethyl acetate. The resulting mixture is washed 3 times with water, dried over sodium sulfate and concentrated under reduced pressure to give a total amount of 49.5 g (65%) of product in the form of colorless powder.

[0117] _{^{400MHz- l H-NMR (CDC1 3}} ), δ [ppm]: 2.21 (s, 3
_{H, Ar-CH 3);} 3.52 (s, 3H, N-CH 3); 7.13-7.44 (
m, 4H, Ar-H).

2,4-dihydro-5-methoxy-2-methyl-4- (ortho-tolyl) -3
Synthesis of H-1,2,4-triazol-3-one (8) 620 (1: 1) mixture of methanol and ethylene glycol dimethyl ether
49.5 g (0.22 mol) of 5-chloro-2,4-dihydro-2-methyl-4- (ortho-tolyl) -3H-1,2,4-triazol-3-one in mL (7) 79.2 g (0.44 mol) of 30% sodium methoxide solution are added to the dissolved solution. The resulting mixture is stirred under reflux for 6 hours, concentrated under reduced pressure and the residue taken up in ethyl acetate. The mixture is washed 3 times with water, dried over sodium sulphate and concentrated under reduced pressure. The crude product is taken up in 100 mL MTBE, mixed with 150 mL hexane and cooled to 0 ° C. The precipitate was separated and dried under reduced pressure at 40 ° C. for 1 hour to give 3
7.6 g (78%) of product are obtained as a light beige powder.

[0119] Melting point: 127-130 ° C.

4- (ortho-bromomethylenephenyl) -2,4-dihydro-5-methoxy
Synthesis of 2-methyl-3H-1,2,4-triazol-3-one (10) A solution prepared by dissolving 10.7 g (60 mmol) of N-bromosuccinimide in 150 mL of anhydrous 1,2-dichloroethane was prepared. , 150 mL anhydrous 1,2-dichloroethane, 10.9 g (50 mmol) of 2,4-dihydro-5-methoxy-2-methyl-4- (ortho-tolyl) -3H-1,2,4-triazole- 3-one (8) and 0.4 g of azobisisobutyronitrile are added to the dissolved solution. The resulting mixture is stirred under reflux for 1 hour and irradiated with UV light. The mixture is washed 3 times with water, dried over sodium sulphate and concentrated under reduced pressure. The residue is purified by flash chromatography to give 4.1 g (28%) of product as a colorless powder.

[0121] Melting point: 113-115 ° C.

Example 3 Synthesis of compound (11)

[Chemical 12] 4.2 g (23 mmol) of 1,4-diacetylbenzene monooxime (9)
Add to 0.62 g (26 mmol) sodium hydride in 30 mL anhydrous acetonitrile. The resulting mixture is stirred under reflux for 1 hour and a solution of 7 g (23 mmol) of compound (10) in 50 mL anhydrous acetonitrile is added. The reaction mixture is stirred at room temperature for 15 hours, taken up in dilute NaCl solution and extracted 3 times with methyl t-butyl ether. The combined organic phases are washed with water, dried over sodium sulphate and concentrated under reduced pressure. The residue is purified by chromatography to give 7.2 g (79%) of product as colorless crystals.

[0123] Melting point: 102-106 ° C.

Example 4 Synthesis of compound (12)

[Chemical 13] In a solution prepared by dissolving 1.1 g (2.8 mmol) of compound (11) in 40 mL of methanol, 0.44 g (3.6 mmol) of O-2-trans-butenehydroxylammonium chloride and 1 g of molecular sieves were prepared. Add 3A. The resulting mixture is stirred at room temperature for 15 hours. The molecular sieves are removed by filtration, the reaction mixture is taken up in ethyl acetate, washed twice with water, dried over sodium sulphate and concentrated under reduced pressure. The residue was purified by chromatography, 840 mL (65%)
The product is obtained as colorless crystals.

[0125] Melting point: 101-105 ° C.

Example 5 Synthesis of compound (13)

[Chemical 14] To a solution prepared by dissolving 8.3 g (50 mmol) of 2,5-dimethyl-4-hydroxyacetophenone in 120 mL of anhydrous DMF (dimethylformamide), 1.33
g (55 mmol) sodium hydride is added. The resulting mixture is stirred at room temperature for 1 hour and a solution of 15 g (50 mmol) of compound (10) in 80 mL of anhydrous DMF is added. The resulting mixture is stirred at room temperature for 19 hours. The mixture is taken up in dilute NaCl solution and extracted 3 times with ethyl acetate. The combined organic phases are washed with water, freed from sodium sulphate and concentrated under reduced pressure. Purify by chromatography to give 13.9 g (73%) of product.

Example 6 Synthesis of compound (14)

[Chemical 15] 1 g (6 mmol) of compound (13) is dissolved in 40 mL of methanol. 0.
42 g (2.9 mmol) O- (3-chloroprop-2-ene) hydroxylammonium chloride and 1 g molecular sieve 3A are added. The resulting mixture is stirred at room temperature for 15 hours. The mixture is filtered, the filtrate is taken up in ethyl acetate, washed with water, dried over sodium sulphate and concentrated under reduced pressure to give 1.1 g (89%) of product (cf. Table No. 9 below). .

[0128]   Other compounds described in Tables 2 and 3 below were obtained by the same method.

[0129]   Table 2: Physical data of compounds represented by the following formula

[Table 2] Table 3: Physical data of compounds represented by the following formula

[Table 3] USE EXAMPLES Experiment 1: Activity against wheat powdery mildew An aqueous preparation of active compound prepared from a stock solution consisting of 10% active compound, 63% cyclohexanone and 27% emulsifier, was grown in pots ( The seedlings of the variety Fruhgold) were sprayed until dripping. Twenty-four hours after the spray covering the leaves had dried, the powdery mildew of wheat (Erysiphe graminis forma)
sprinkled with specialis tritici) spores. The test plants were placed in a greenhouse at 20 to 24 ° C. and a relative atmospheric humidity of 60 to 90%. After 7 days, the degree of powdery mildew development was visually measured as an infected area (%) with respect to the total area of leaves.

[0130]

[Table 4] Experiment 2: Activity against downy mildew (Plasmopara viticola) An aqueous preparation of the active compound prepared from a stock solution consisting of 10% of active compound, 63% of cyclohexanone and 27% of emulsifier was applied to potted grapes (variety Mulle
r-Thurgau) was sprayed until it dripped. Next day, the leaves were inoculated with downy mildew (Plasmopara viticola) using an aqueous suspension of zoospores. The potted grapes were placed in a steam saturated chamber at 24 ° C for the first 48 hours, after which
It was placed in a greenhouse at 20-30 ° C for 5 days. The potted grapes were then placed again in a humid chamber for 16 hours to promote sporangiophore growth. The extent of infection on the underside of the leaves was visually measured.

[0131]

[Table 5] Experiment 3: Activity against Pyricularia oryzae (prophylactic activity) An aqueous preparation of the active compound prepared from a stock solution consisting of 10% active compound, 63% cyclohexanone and 27% emulsifier was grown in pots. Rice (variety
Sprayed on the leaves of seedlings of Tai-Nong 67) until it drip. The next day, rice was inoculated with Pyricularia oryzae using an aqueous suspension of sporangiophores. The test plant was allowed to stand in an artificial weather room at 22 to 24 ° C and a relative atmospheric humidity of 95 to 99% for 6 days. The extent of leaf infection was visually measured.

[0132]

[Table 6]

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] November 15, 2001 (2001.11.15)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

[Chemical 1] [In the formula,   W is -OCH_Two-Or-C (R₁₀) = N-O-CH_Two-Is;   X is halogen, C_1-4-Alkyl, or C_1-4-Alkoxy;   R₁Is H, C_1-4-Alkyl, halogen, nitro, CN, halo-C_1-4 -Alkyl, or C_1-4-Alkoxy;   R_TwoIs H, C_1-4-Alkyl, halogen, nitro, CN, halo-C_1-4 -Alkyl, or C_1-4-Alkoxy;   n is 1 or 2;   R_ThreeIs H or C_1-4-Alkyl;   R₅Is H, C_1-4-Alkyl, or C_2-4-Alkenyl;   R₆Is H, C_1-4-Alkyl, C_1-4-Haloalkyl, C_2-4-Al
Alkenyl or aryl;   R₇Is H, halogen, C_1-6-Alkyl, C_1-6-Haloalkyl, C_{Two ~ 6} -Alkenyl, C_2-6-Haloalkenyl, C_3-6-Cycloalkyl, C _3-6 -Halocycloalkyl, or unsubstituted or substituted aryl;   R₈Is H, halogen, C_1-6-Alkyl, C_1-6-Haloalkyl, C_{Two ~ 6} -Alkenyl, C_2-6-Haloalkenyl, C_3-6-Cycloalkyl, C _3-6 -Halocycloalkyl, or unsubstituted or substituted aryl; Alternatively,   R₇And R₈Together with the carbon atom to which they are attached, has 5 or 6
Forming an unsaturated heterocycle having one or two heteroatoms having ring atoms, wherein
, The heteroatoms independently of one another are selected from nitrogen, oxygen and sulfur,
Is C_1-4-Alkyl, halogen, nitro, CN, halo-C_1-4-Alkyl
, OH, C_1-4-Alkoxy, unsubstituted or substituted aryl, C_2-4-Al
Kenyl, halo-C_2-4-Alkenyl, C_2-4-Alkynyl and halo-C_{2 to Four} -With one or two groups independently selected from the group consisting of alkynyl
May have been replaced;   R₉Is H, halogen, C_1-6-Alkyl, C_1-6-Haloalkyl, C_{Two ~ 6} -Alkenyl, C_2-6-Haloalkenyl, C_3-6-Cycloalkyl, C _3-6 -Halocycloalkyl, or unsubstituted or substituted aryl;   R₁₀Is H, halogen, or C_1-4-Is alkyl] An oxime ether compound represented by.

[Chemical 2] _{Wherein, W, R 1, R 2} , R 5, R 6, R 7, R 8, R 9 and n are claims 1-5
And Y is NH ₂ as defined in any one of [1] to [4].

─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Muller, Bernd             Federal Republic of Germany 67227 Frankenta             Le Jean-Gans-Strasse 21 (72) Inventor Gypsar, Andreas             68159 Mannheim, Germany             Base 4.4 (72) Inventors Gran Menos, Wassirius             Germany 67063 Ludwig             Hischafen, Bolschstrasser             SE 5 (72) Inventor Tormoy Brasco, Jordi             Federal Republic of Germany 67117 Limburger             Hoff, Mühlweg 47 (72) Inventor Putok, Arn             Germany 67065 Ludwig             Hischafen, Tyroller Stra             33 (72) Inventor Kalman, Oliver             68199 Mannheim, Germany             Heinrich-Hein-Strasse 27 (72) Inventor Grote, Thomas             Germany 67157 Wachenheim,             Inhaenhausen (72) Inventor Amherman Everhard             Germany 64646 Heppenhai             Mu, von-Gagern-Strasse             Two (72) Inventor Strassman, Siegfried             Federal Republic of Germany 67117 Limberger             Hoff, Donnersbergstrasse 9 (72) Inventor Lorenz, Gicera             Germany 67434 Neustadt               Ahren Wegg 13 (72) Inventor Harrys, Volker             Federal Republic of Germany 67227 Frankenta             Immengerten Wegg 29 A F-term (reference) 4C063 BB07 CC52 CC92 DD41 EE03                 4H011 AA01 BA01 BB09 BC05 DA16

Claims (10)

[Claims] 1. Formula (1): [Chemical 1] [In the formula,   W is -OCH_Two-Or-C (R₁₀) = N-O-CH_Two-Is;   X is halogen, C_1-4-Alkyl, or C_1-4-Alkoxy;   R₁Is H, C_1-4-Alkyl, halogen, nitro, CN, halo-C_1-4 -Alkyl, or C_1-4-Alkoxy;   R_TwoIs H, C_1-4-Alkyl, halogen, nitro, CN, halo-C_1-4 -Alkyl, or C_1-4-Alkoxy;   n is 1 or 2;   R_ThreeIs H or C_1-4-Alkyl;   R₅Is H, C_1-4-Alkyl, or C_2-4-Alkenyl;   R₆Is H, C_1-4-Alkyl, C_1-4-Haloalkyl, C_2-4-Al
Alkenyl or aryl;   R₇Is H, halogen, C_1-6-Alkyl, C_1-6-Haloalkyl, C_{Two ~ 6} -Alkenyl, C_2-6-Haloalkenyl, C_3-6-Cycloalkyl, C _3-6 -Halocycloalkyl, or unsubstituted or substituted aryl;   R₈Is H, halogen, C_1-6-Alkyl, C_1-6-Haloalkyl, C_{Two ~ 6} -Alkenyl, C_2-6-Haloalkenyl, C_3-6-Cycloalkyl, C _3-6 -Halocycloalkyl, or unsubstituted or substituted aryl; Alternatively,   R₇And R₈Together with the carbon atom to which they are attached, has 5 or 6
Forming an unsaturated heterocycle having one or two heteroatoms having ring atoms, wherein
, The heteroatoms independently of one another are selected from nitrogen, oxygen and sulfur,
Is C_1-4-Alkyl, halogen, nitro, CN, halo-C_1-4-Alkyl
, OH, C_1-4-Alkoxy, unsubstituted or substituted aryl, C_2-4-Al
Kenyl, halo-C_2-4-Alkenyl, C_2-4-Alkynyl and halo-C_{2 to Four} -With one or two groups independently selected from the group consisting of alkynyl
May have been replaced;   R₉Is H, halogen, C_1-6-Alkyl, C_1-6-Haloalkyl, C_{Two ~ 6} -Alkenyl, C_2-6-Haloalkenyl, C_3-6-Cycloalkyl, C _3-6 -Halocycloalkyl, or unsubstituted or substituted aryl;   R₁₀Is H, halogen, or C_1-4-Is alkyl] An oxime ether compound represented by. 2. A compound represented by formula (1):   W is -OCH_Two-Or-C (R₁₀) = N-O-CH_Two-Is;   X is halogen, C_1-4-Alkyl, or C_1-4-Alkoxy;   R₁Is H, C_1-4-Alkyl, halogen, or halo-C_1-4-Alkyl
And   R_TwoIs H, C_1-4-Alkyl, halogen, or halo-C_1-4-Alkyl
And   R_ThreeIs H or C_1-4-Alkyl;   n is 1 or 2;   R₅Is H or C_1-4-Alkyl;   R₆Is H, C_1-4-Alkyl, or halo-C_1-4-Alkyl;   R₇Is H, halogen, C_1-6-Alkyl, halo-C_1-6-Alkyl, C _3-6 -Cycloalkyl, C_3-6-Halocycloalkyl, or phenyl
;   R₈Is H, halogen, C_1-6-Alkyl, halo-C_1-6-Alkyl, C _3-6 -Cycloalkyl, C_3-6-Halocycloalkyl, C_2-6-Arkeni
Or one or two halogen or C_1-4-Substituted by alkyl
It is phenyl that may be present; Alternatively,   R₇And R₈Together with the carbon atom to which they are attached, has 5 or 6
Forming an unsaturated heterocycle having one or two heteroatoms having ring atoms, wherein
, The heteroatoms independently of one another are selected from nitrogen, oxygen and sulfur,
Is C_1-4-Alkyl, halogen, halo-C_1-4-Alkyl, C_1-4-A
Lucoxy, and 1 or 2 halogens or C_1-4-Substituted with alkyl
One or two independently selected from the group consisting of optionally substituted phenyl
Optionally substituted with 4 groups;   R₉Is H, halogen, C_1-6-Alkyl, halo-C_1-6-Alkyl, C _3-6 -Cycloalkyl, C_3-6-Halocycloalkyl, or phenyl
;   R₁₀Is H, halogen, or C_1-4-Alkyl, according to claim 1
Compound. 3. In the compound represented by formula (1), W is —OCH ₂ — or —C (R ₁₀ ) ═N—O—CH ₂ —; X is halogen, or C _{1 to 4} - alkoxy; _{R 1} is H, or _{C 1 to 4} - is alkyl; _{R 2} is H, or _{C 1 to 4} - is alkyl; n is 1 or 2; _{R 3} Is C _1-4 -alkyl; R ₅ is H, or C _1-4 -alkyl; R ₆ is H, or C _1-4 -alkyl; R ₇ is H, halogen , Or C _1-6 -alkyl; R ₈ is H, halogen, C _1-6 -alkyl, or C _2-6 -alkenyl; or, R ₇ and R ₈ are attached to them. Together with a carbon atom, a thiophenyl group, a furanyl group, an oxazolyl group, or a thiazolyl group Formed, in which case the group is
It may have 1 or 2 substituents independently selected from the group consisting of C _1-4 -alkyl, halogen, and phenyl optionally substituted with 1 or 2 halogen. Well; R ₉ is H, halogen, or C _1-6 -alkyl; Compound according to claim 1 or 2, wherein R ₁₀ is H or C _1-4 -alkyl. 4. In the compound represented by formula (1), W is —OCH ₂ — or —C (R ₁₀ ) ═N—O—CH ₂ —; X is C _1-4 −. alkoxy; _{R 1} is an H; _{R 2} is H, or _{C 1 to 4} - is alkyl; n is 1 or 2; _{R 3 is C 1 to 4} - alkyl; R ₅ is H or C _1-4 -alkyl; R ₆ is H or C _1-4 -alkyl; R ₇ is H or halogen; R ₈ is H, C _1-4 -alkyl, or halogen; or R ₇ and R ₈ together with the carbon atom to which they are attached form a thiophenyl group or an oxazolyl group, wherein said group is 1 Or 2 halogens or phenyl (wherein the phenyl is 1 or 2 halogen R ₉ is H, or halogen; R ₁₀ is H, or C _1-4 -alkyl. The compound according to any one of 1. 5. Use of the compound of formula (1) according to any one of claims 1 to 4 as a fungicide or for controlling pests. 6. A fungicide, which comprises a solid and / or liquid carrier and a fungicidally effective amount of at least one compound of the formula (1) according to claim 1. 7. A method for controlling fungi, which comprises treating the fungus with at least one compound represented by formula (1) according to claim 1 which is effective as a fungicide, or The above-mentioned control method, which comprises treating an object, plant, seed or soil that is expected to be invaded. 8. A pest control composition comprising an inert additive and an insecticidal effective amount of at least one compound represented by the formula (1) described in claim 1. 9. A method for controlling a pest, which comprises treating the pest and / or its habitat with an effective amount of at least one compound represented by formula (1) as a pesticide. The method for controlling a pest according to the above. 10. Formula (6): _{Wherein, W, R 1, R 2} , R 5, R 6, R 7, R 8, R 9 and n are claims 1-4
And Y is NH ₂ as defined in any one of [1] to [4].