Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
1999-12-06
2004-02-17
Morris, Patricia L. (Department: 1626)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C514S384000, C548S243000, C548S263600, C548S263800, C548S264400, C548S264600
Reexamination Certificate
active
06693124
ABSTRACT:
The present invention relates to a bisimino-substituted phenyl compound of the formula I
where the substituents have the following meanings:
X is a group A or B
where
# denotes 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 C
1
-C
4
-alkyl;
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 hydrogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl or substituted or unsubstituted phenyl;
R
4
is ═CR
b
R
c
or ═N—OR
d
where
R
b
, R
c
independently of one another are hydrogen, C
1
-C
6
-alkyl or substituted or unsubstituted phenyl; and
R
d
is one of the radicals mentioned under R
2
.
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.
WO-A 97/02,255 discloses 4-phenyl-2,3-dihydroisoxazolones and 4-phenyl-2,4-dihydrotriazolones with a methoxyimino group in the ortho-position.
WO-A 95/21,153 and WO-A 97/05,103 describe&agr;-phenylacrylic acid and &agr;-phenyl-&agr;-methoxyiminoacetic acid derivatives with a bisoxime ether group in the ortho-position, and PCT/EP 96/04,446 describes such derivatives which have a trisoxime ether group.
The compounds described in the documents mentioned above 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 invention to provide 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 of 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 above document WO-A 97/02,255 in as far as the oximino group is substituted by a radical R
4
which is bonded to a double bond and which cannot be hydrogen. Compared with the known compounds, the compounds of the formula I have a better activity against harmful fungi and animal pests.
In principle, the compounds of the formula I can be obtained using similar methods to those described in WO-A 97/02,255, WO-A 95/21,153 and WO-A 97/05,103 and in PCT/EP 96/04,446.
The compounds I can be obtained by various routes, it being immaterial for the synthesis whether it is the group X or the oxime ether group which is synthesized first. In the descriptions of the reactions which follow, therefore, the term X
#
will be used for the radical X or a suitable precursor of this radical and E
#
for the oxime ether group or a suitable precursor, for reasons of better readability.
In particular, compounds of the formula I.1
are obtained by converting a benzyl compound of the formula II
#
with an oxime of the formula III and converting the resulting oxime ether of the formula IV
#
into the halogen compound of the formula V
#
by means of halogenation, reacting V
#
with a hydroxylamine ether of the formula VI′ to give the bisoxime of the formula VI
#
, oxidizing VI
#
to give the carbonyl compound of the formula VII
#
, and reacting VII
#
with a phosphorus reagent following the principles of Wittig reaction to give a compound of the formula I.1
#
.
In formula II
#
, L is a nucleophilically exchangeable 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.
In the above equation, {circle around (P)} in formula VII′ is a phosphoranyl dical such as, for example, triphenylphosphoranyl.
1. The reaction of the benzyl compound II
#
with the oxime of the formula III
#
is carried out in a manner known per se at from −10° C. to 100° C., preferably 10° C. to 85° C., in an inert organic solvent in the presence of a base [cf. WO-A 97/02,255; WO-A 96/36,229].
Suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably tetrahydro-furan, acetonitrile and dimethylformamide. Mixtures of the solvents mentioned may also be used.
Suitable bases are, generally, inorganic compounds such as alkali metal hydroxides and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal hydrides and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal carbonates and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal alkoxides and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxy-magnesium, furthermore organic bases, eg., tertiary amines such as trimethylamine, triethylamine, triisopropylethyl-amine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particularly preferred are sodium hydride, potassium carbonate and sodium methoxide.
The bases are generally employed in catalytic amounts, but they may also be used in equimolar amounts, in an excess or, if appropriate, as the solvent.
The starting materials are generally reacted with each other in equimolar amounts. It may be advantageous for the yield to employ III in an excess based on II
#
.
The benzyl compounds II
#
which are required for the preparation of the compounds I are disclosed in the literature [cf. WO-A 97/02,255]. They can be obtained by the following synthesis route:
Compounds of the formula IIA
#
where R
a
is alkyl are obtained in the manner disclosed in U.S. Pat. No. 4,952,573 from corresponding phenylacetic acid esters IIc
#
.
This route is not only suitable for the preparation of the benzyl compounds II
#
, but, in principle, suitable for synthesizing the groups A or B at each synthesis level of the oxime ether group E
#
. The group X is particularly preferably synthesized at the level of the compounds IIa or IIe where E
#
is hydrogen.
The benzyl compounds IIB
#
required for the preparation of the compounds IB where R
a
is alkyl which are not known from the literature [cf. WO-A 96/36229] can be obtained using methods similar to those of the literature [cf. J. Org. Chem., Vol. 43 (1978), p. 936]. They can be obtained by reacting the carbamates of the formula IIf
#
with orthoesters:
Those oximes of the formula III which are not already known from the literture [cf. EP-A 95/21,153] can be prepared in accordance with the literature cited.
2. Halogenation of the oxime ether IV
#
is usually carried out at from −10° C. to 80° C., preferably 0° C. to 65° C., in an inert organic solvent in the presence or absence of an acid. J. Org. Chem. (1981), p. 2532; Org, Synth., Vol. 55 (1976), p. 24; Tetrahedron (1970) p. 5611].
Suitable halogenating agents are bromine, chlorine, pyridin*HBr
3
, CuBr
2
and SO
2
Cl
2
, in particular bromine, CuBr
2
and SO
2
Cl
2
. They are generally reacted with each other in equimola
Ammermann Eberhard
Bayer Herbert
Grammenos Wassilios
Grote Thomas
Gypser Andreas
BASF - Aktiengesellschaft
Keil & Weinkauf
Morris Patricia L.
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