Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
2000-01-27
2001-05-15
Oswecki, Jane C. (Department: 1626)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C514S340000, C514S374000, C514S378000, C514S380000, C514S383000, C514S384000, C514S406000, C548S215000, C548S240000, C548S243000, C548S263200, C548S264600, C548S265800, C548S265800, C548S333500, C548S364100, C548S365700
Reexamination Certificate
active
06232317
ABSTRACT:
The present invention relates to imino-substituted phenyl compounds of the formula I
where the substituents have the following meanings:
z is a group A or B
where
# signifies the bond with the phenyl ring and
R
a
is halogen, C
1
-C
4
-alkyl or C
1
-C
4
-alkoxy;
Y is halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl or C
1
-C
4
-alkoxy;
n is 0, 1 or 2, it being possible for the radicals Y to be different if n=2;
R
1
is halogen, C
1
-C
4
-haloalkyl or C
1
-C
4
-alkoxy;
R
2
is C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
3
-C
4
-alkenyl, C
3
-C
4
-haloalkenyl, C
3
-C
4
-alkynyl or C
3
-C
4
-haloalkynyl;
R
3
is cyano, C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkoxy, C
3
-C
6
-cycloalkoxy, C
2
-C
6
-alkoxyalkyl;
C
3
-C
6
-cycloalkyl, which can be partially or fully halogenated and/or have attached to it one to three C
1
-C
4
-alkyl groups;
phenyl which, in turn, can be partially or fully halogenated and/or have attached to it one to three of the following groups: cyano, nitro, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy and C
1
-C
4
-haloalkoxy;
aryl, aryloxy or arylmethylene which can be partially or fully halogenated in the aryl moiety and/or can have attached to it one to three of the following radicals: cyano, nitro, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy and C
1
-C
4
-haloalkoxy;
unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, C(R
3a
)═N—OR
3b
or C(R
3a
)═CR
3c
R
3d
, where
R
3a
, R
3b
, R
3c
, R
3d
independently of one another are hydrogen, C
1
-C
6
-alkyl or unsubstituted or substituted phenyl.
In addition, the invention relates to processes and intermediates for the preparation of the compounds I, and to compositions and to the use of the compounds I for controlling harmful fungi and animal pests.
4-phenyl-2,3-dihydroisoxazolones and 4-phenyl-2,4-dihydrotriazolones having a methyleneoximino group in the ortho position are disclosed in WO-A 95/14,009 and those which have a bisoxime ether group in the ortho position are disclosed in WO-A 97/02,255.
&agr;-Phenylacrylic acid derivatives and &agr;-phenyl-&agr;-methoximinoacetic acid derivatives having an oxime ether group in the ortho position are described in DE-A 40 20 384 and such derivatives which have a bisoxime ether group are described in WO-A 95/21,154.
The compounds described in the abovementioned documents are suitable as crop protection agents against harmful fungi and, in some cases, against animal pests.
However, their action is not satisfactory in many cases. It is an object of the present invention to find compounds with an improved activity.
We have found that this object is achieved by the phenyl compounds of the formula I. We have furthermore found intermediates and processes for the preparation of the compounds I and the use of the compounds I and compositions comprising them for controlling harmful fungi and animal pests. The fungicidal action is preferred.
The compounds of the formula I differ from the compounds disclosed in the abovementioned document WO-A 97/02,255 in context with the substitution of the oximino group by the radical
R
1
which is bonded to a double bond and which has specific features. In contrast to the known compounds, the compounds of the formula I have an improved activity against harmful fungi and animal pests.
The compounds of the formula I per se can be obtained by methods similar to those described in WO-A 95/14,009, WO-A 97/02,255, and WO-A 95/21,153.
The compounds I can be obtained in various ways, it being irrelevant for the synthesis whether the group Z or the oxime ether group is synthesized first. For reasons of better clarity, the term Z# is used for the radical Z or a suitable precursor of this radical, and E# is used for the oxime ether group or a suitable precursor thereof, in the reactions described hereinbelow.
Compounds I where R
1
is halogen are especially advantageously obtained by first converting a carboxylic ester IIIa with hydroxylamine to give the corresponding hydroxambic acid IIIb, subsequently reacting IIIb with a benzyl compound IIa# to give the corresponding hydroxambic ester IVa# and converting IVa# with a halogenating agent [HAL] to give I# [cf. DE-Anm. No. 197 08 940.2].
R
x
in formula IIIa is the radical of a customary leaving group. Customary leaving groups for the purposes of the present reaction are to be understood as meaning especially the following groups: C
1
-C
4
-alkyl (especially methyl or ethyl) or phenyl.
L in formula IIa# is a nucleophile leaving group. For the purposes of this reaction, this is to be understood as meaning especially the following: halogen or alkyl- or arylsulfonate, especially chlorine, bromine, iodine, mesylate, tosylate and triflate.
1. The reaction of the carboxylic ester IIIa with hydroxylamine is normally carried out at from −20° C. to 50° C., preferably 0° C. to 20° C., in an inert organic solvent, preferably in the presence of a base (cf. Lit. Houben-Weyl, 4th Edition, Vol. E5, p. 1141 et seq.).
Suitable 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, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethyl formamide and dimethylacetamide, especially preferably alcohols such as methanol and ethanol. Mixtures of these can also be used.
Bases which are suitable are, generally, inorganic compounds such as alkali metal hydroxide and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal oxides and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal carbonates and alkaline earth metal carbonates such as lithium carbonate and calcium carbonate, and alkali metal alkoxides and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, and furthermore organic bases, eg. tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, and by bicyclic amines. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal alkoxides such as sodium methoxide and sodium ethoxide, are especially preferred.
The bases are generally used in equimolar amounts or in an excess.
The starting materials are generally reacted with each other in equimolar amounts. It may be advantageous for the yield to employ hydroxylamine in an excess based on IIIa.
Those carboxylic esters IIIa required for the preparation of the compounds I which are not already known from the literature [DE-A 28 08 317; DE-A 22 65 234; J. Chem. Soc. PT 1 (1975), 2340 et seq.; Chem. Ber. 16 (1883), 2987 et seq.; J. Org. Chem. 37 (1972), 139] can be prepared in accordance with the literature cited.
2. The reaction of the hydroxambic acid IIIb with the benzyl compound IIa# is normally carried out at from 0° C. to 130° C., preferably 10° C. to 60° C., in an inert organic solvent in the presence of a base [cf. Liebigs Ann. Chem. 10 (1992), 997 et seq.; Synth. Commun. 19 (1989), 339 et seq.]. Suitable 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, dioxane, anisole and tetrahydrofuran, nitriles such as aceto
Ammermann Eberhard
Bayer Herbert
Gotz Norbert
Grammenos Wassilios
Grote Thomas
BASF - Aktiengesellschaft
Keil & Weinkauf
Oswecki Jane C.
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