Substituted benzyl oximino compounds

Details Substituted benzyl oximino compounds Substituted benzyl oximino compounds

1999-10-13

2001-12-11

Sololola, T. A. (Department: 1626)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Heterocyclic carbon compounds containing a hetero ring...

C514S475000, C514S640000, C549S523000, C549S551000, C564S256000, C564S264000, C564S265000, C548S965000, C548S967000

Reexamination Certificate

active

06329359

ABSTRACT:

This is a 371 of PCT/EP98/01942 filed Apr. 2, 1998.
The present invention relates to benzyloxyimino compounds of the formula I,
where:
X is N(COOCH
3
)—OCH
3
, C(COOCH
3
)═CH—OCH
3
, C(COOCH
3
)═N—OCH
3
, C(CONHCH
3
)═N—OCH
3
or C(COOCH
3
)═CH—CH
3
;
Y is hydrogen, halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl or C
1
-C
4
-alkoxy;
Z is oxygen, C(R
a
)
2
or NR
a
, where
R
a
is hydrogen or C
1
-C
4
-alkyl and, in the case of C(R
a
)
2
, can be identical or different;
R
1
is halogen, C
1
-C
4
-alkyl, C
l
-C
4
-haloalkyl or C
1
-C
4
-alkoxy;
R
2
is hydrogen, halogen, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy or is phenyl with or without substitution by customary groups;
R
3
is hydrogen, halogen, C
1
-C
4
-alkyl or C
1
-C
4
-alkoxy;
R
4
is C
1
-C
4
-alkyl or
phenyl with or without substitution by 1-3 substituents from the following group: halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy or C(R
b
)═N—OR
c
, where
R
b
is hydrogen or C
1
-C
4
-alkyl and
R
c
is C
1
-C
4
-alkyl, C
3
-C
4
-alkenyl or C
3
-C
4
-alkynyl.
Additionally, the invention relates to processes and intermediates for preparing the compounds I, to compositions and to the use of the compounds I for controlling harmful fungi and animal pests.
Phenylcarbamates having a methoxyimino group in the ortho position are disclosed in WO-A 93/15,046. &agr;-Phenylacrylic acid and &agr;-phenyl-&agr;-methoxyiminoacetic acid derivatives having a methoxyimino group in the ortho position are known from EP-A 426 460, EP-A 460 575, EP-A 472 300, EP-A 585 751, WO-A 92/13,830, WO-A 92/18,487, WO-A 92/18,494, JP-A 05/201,946 and JP-A 05/255,012. The compounds described therein carry a CH
2
O—N═CR′R″ group in the position ortho to the group corresponding to X. The general definitions of the radicals R′ and R″ include the definition of the radical R
1
in formula I and additionally allow cycloalkyl and to some extent heterocyclyl substituents.
EP-A 463 488 and WO-A 90/07,493 disclose by way of example &agr;-phenylacrylic acid and &agr;-phenyl-&agr;-methoxyiminoacetic acid derivatives in which the CH
2
O—N═CR′R″ group carries alkyl and cyclopropyl, oxiranyl, or aziridinyl radicals as substituents R′ and R″.
The compounds described in the abovementioned publications are suitable for use as crop protection agents against harmful fungi and to some extent against animal pests.
However, in many instances their activity is not satisfactory. It is an object of the present invention, therefore, to provide compounds having improved activity.
We have found that this object is achieved by the substituted benzyloxyimino compounds of the formula I. Furthermore, we have found intermediates and processes for preparing the compounds I, and the use of the compounds I and of compositions comprising them for controlling harmful fungi and animal pests. Preference is given to the fungicidal activity.
The compounds of the formula I differ from the compounds disclosed in the abovementioned publications EP-A 463 488 and WO-A 90/07,493 in the substitution of the methoxyimino group by the radical R
4
, which cannot be hydrogen. In comparison to the known compounds, the compounds of the formula I have improved activity against harmful fungi and animal pests.
The compounds of the formula I can be obtained per se by the methods described in EP-A 463 488 and WO-A 90/07,493.
In particular, the compounds of the formula I in which Z is oxygen and C(R
a
)
2
are obtained by reacting an oxime of the formula II with a benzyl compound of the formula III.
In the formula III, L is a nucleophilically replaceable group, for example halogen, such as fluorine, chlorine, bromine or iodine, in particular chlorine or bromine, or alkyl- or arylsulfonates, such as mesylate or tosylate.
1. The reaction of the oxime II with the benzyl compound III is carried out in a known manner at from −10° C. to 80° C., preferably 0° C. to 65° C., in an inert organic solvent in the presence of a base [cf. EP-A 463 488].
In general, the reactants are reacted with one another in equimolar amounts. To improve the yield, it may be advantageous to employ an excess of II, based on III.
The benzyl compounds of the formula III required for preparing the compounds I are known from the literature [EP-A 420 091; EP-A 513 580; WO-A 93/15,046; WO-A 94/05,620] and can be prepared according to the cited literature.
The starting materials IIA required for preparing the compounds I in which Z is oxygen can be prepared as follows:
2A. In the above reaction scheme, R
x
is a C
1
-C
10
-alkyl radical and {circumflex over (P)} in the formula IIc is a phosphoranyl radical such as, for example, triphenylphosphoranyl.
The acetalization of the &agr;,&bgr;-diketone IIa to IIb is usually carried out at from −20° C. to 120° C., preferably 0° C. to 85° C., in an inert organic solvent in the presence of an acid [cf. Khim.-Farm. Zh. (1986), p. 606; J. Chem. Res. Miniprint (1982), p. 2528].
Suitable for use as solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxan, anisole and tetrahydrofuran, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably toluene, methanol, ethanol and dimethylacetamide. It is also possible to use mixtures of the solvents mentioned.
Suitable acids and acid catalysts are inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron(III) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(II) chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid.
In general, the acids are employed in catalytic amounts, but it is also possible to employ them in equimolar amounts, in excess or, if appropriate, as solvent.
In general, the reactants are reacted with one another in equimolar amounts. To improve the yield, it may be advantageous to employ an excess of C(OR
x
)
3
, based on IIa.
The diketones IIa are commercially available or known from the literature [J. Am. Chem. Soc. (1996), p. 12588; J. Chem. Soc. Chem. Commun. (1987), p. 692; Khim.-Farm. Zh. (1986), p. 606], or they can be prepared according to the literature cited.
2B. In a Wittig reaction, the compound IIb is converted into the &agr;,&bgr;-unsaturated acetal IV′ using a phosphorane of the formula IIc.
The Wittig reaction is usually carried out at from −78° C. to 85° C., preferably −10° C. to 65° C., in an inert organic solvent in the presence of a base [cf. EP-A 513 580].
Suitable for use as solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxan, anisole and tetrahydrofuran, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably tetrahydrofuran, tert-butyl methyl ether, dimethylformamide and dimethylacetamide. It is also possible to employ mixtures of the solvents mentioned.
In general, suitable bases are inorganic compounds such as alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride, and alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium tert-butoxide and dimethoxymagne

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