Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-07-11
2002-09-17
Rao, Deepak R. (Department: 1624)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Heterocyclic carbon compounds containing a hetero ring...
C514S211150, C514S360000, C540S544000, C544S065000, C548S124000, C548S263800, C548S264200, C548S366100, C548S366400, C548S368700, C548S369700
Reexamination Certificate
active
06451790
ABSTRACT:
The present invention relates to azadioxacycloalkenes of the formula I,
in which the substituents and the index have the following meanings:
Y is N or CR
a
, where
R
a
is hydrogen, halogen or C
1
-C
4
-alkyl;
n is 0, 1, 2, 3 or 4, where the substituents R
1
may be different if n is greater than 1;
R
1
is nitro, cyano, halogen, C
1
-C
6
-alkyl or,
if n is greater than 1, additionally a bridge which is attached to two adjacent ring atoms and which contains three to four members selected from the group consisting of: 3 or 4 carbon atoms, 2 to 3 carbon atoms and 1 or 2 nitrogen, oxygen and/or sulfur atoms, where this bridge, together with the ring to which it is attached, may form a partially unsaturated or aromatic ring and where furthermore the carbon atoms of the bridge may be partially or fully substituted by halogen atoms or methyl groups;
R
2
is hydrogen, nitro, cyano, halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-alkylthio or C
1
-C
4
-alkoxycarbonyl;
R
3
is C
1
-C
6
-alkyl which is unsubstituted or partially or fully halogenated or may carry one to three groups R
b
,
R
b
is halogen, cyano, nitro, hydroxyl, C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkylcarbonyl, C
3
-C
6
-cycloalkyl, C
1
-C
6
-alkoxy, C
1
-C
6
-haloalkoxy, C
1
-C
6
-alkoxycarbonyl, C
1
-C
6
-alkylthio, C
1
-C
6
-alkyl-amino,
di-C
1
-C
6
-alkylamino, C
2
-C
6
-alkenyl, C
2
-C
6
-alkenyloxy, C
3
-C
6
-alkynyloxy and C
1
-C
4
-alkylenedioxy, which may be halogenated,
C
3
-C
6
-cycloalkyl, aryl or hetaryl,
where the cyclic systems may be partially or fully halogenated or may carry one to three groups R
c
:
R
c
is halogen, cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, where the alkyl groups in these radicals contain 1 to 6 carbon atoms and the abovementioned alkenyl or alkynyl groups in these radicals contain 2 to 8 carbon atoms;
is C(═NOR
d
)-&Ggr;
1
-R
d
, where R
d
is hydrogen or C
1
-C
6
-alkyl, &Ggr; is oxygen, sulfur or NR
d
and 1 is 0 or 1;
and/or one to three of the following radicals: cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, where the cyclic systems contain 3 to 10 ring members; aryl, aryloxy, arylthio, aryl-C
1
-C
6
-alkoxy, aryl-C
1
-C
6
-alkyl, hetaryl, hetaryloxy, hetarylthio, where the aryl radicals preferably contain 6 to 10 ring members and the hetaryl radicals 5 or 6 ring members and where the cyclic systems may be partially or fully halogenated or may be substituted by one to three groups R
b
;
A is ═N—OR
4
, ═CH—OR
4
═CH—SR
4
or ═CH—R
5
, where
R
4
is C
1
-C
4
-alkyl or C
1
-C
4
-haloalkyl,
R
5
is halogen or a group R
4
and
W is C
1
-C
3
-alkylene which is unsubstituted or substituted by one or two groups R
e
, where
R
e
is halogen, cyano, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
2
-C
4
-alkenyl, C
2
-C
4
-haloalkenyl, C
2
-C
4
-alkynyl or C
2
-C
4
-haloalkynyl, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy, C
2
-C
4
-alkenoxy, C
2
-C
4
-haloalkenyloxy, C
2
-C
4
-Alkynyloxy or C
2
-C
4
-haloalkynyloxy, C
1
-C
4
-alkylcarbonyloxy.
Moreover, the invention relates to processes for preparing these compounds, to compositions comprising them and to their use for controlling animal pests or harmful fungi.
EP-A 378 755, EP-A 757 042, WO-A 94/19331, WO-A 95/29896 and WO-A 96/37480 disclose 2-[pyrazolyl-4-oxymethylene]- and 2-[triazolyl-4-oxymethylene]phenyl acetic esters and corresponding amides for controlling animal pests and harmful fungi.
3-Phenylmethyleneazadioxacycloalkenes having substituents in the ortho position of the phenyl radical are disclosed in WO-A 95/04728, WO-A 97/27189, WO-A 98/17653, WO-A 98/25465, WO-A 98/40351, WO-A 98/40365, WO-A 98/45289, EP-A 846 691 and WO-A 97/00866.
It is an object of the present invention to provide compounds having improved activity.
We have found that this object is achieved by the compounds defined at the outset. Furthermore, we have found processes for their preparation, compositions comprising them and methods for controlling animal pests and harmful fungi using the compounds I.
The compounds of the formula I differ from the compounds known from the abovementioned publications WO-A 95/04728, WO-A 97/27189, WO-A 98/17653, WO-A 98/25465, WO-A 98/40351, WO-A 98/40365, WO-A 98/45289, EP-A 846 691 and WO-A 97/00866 in the methyleneoxy, pyrazolyl or triazolyl grouping and the phenyl ring and from the compounds known from EP-A 378 755, EP-A 757 042, WO-A 94/19331, WO-A 95/29896 and WO-A 96/37480 in the azadioxacycloalkene group. The compounds of the formula I have an activity against harmful fungi and animal pests which is higher than that of the known compounds.
The compounds of the formula I can be obtained analogously to the methods described in WO-A 95/04728, WO-A 97/46542 and WO-A 98/17653 or EP-A 378 755, EP-A 757 042, WO-A 94/19331 and WO-A 95/29896.
The compounds of the formula I can be obtained by diff different routes, and it is immaterial for the synthesis whether the group X where # denotes the link to the phenyl ring,
or the pyrazolyl or triazolyl grouping is synthesized first.
The compounds of the formula I are, for example, preferably obtained by reacting benzyl compounds of the formula II with hydroxypyrazols or the corresponding triazols of the formula III. In the formulae II and III, R
1
, n, A, W, Y, R
2
and R
3
are as defined in formula I, in formula II, L is a nucleophilically replaceable group, for example halogen (e.g. chlorine or bromine) or an alkyl- or arylsulfonate (e.g. methylsulfonate, trifluoromethylsulfonate, phenylsulfonate and 4-methylphenylsulfonate).
1) The etherification of the compounds II and III is usually carried out in an inert organic solvent at from 0° C. to 80° C., preferably at from 20° C. to 60° C., if appropriate in the presence of a base.
Suitable solvents are 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 and tetrahydrofuran, nitriles, alcohols, ketones, such as acetone and methyl ethyl ketone, and also dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidin-2-one and 1,2-dimethyltetrahydro-2(1H)-pyrimidine, preferably methylene chloride, acetone, toluene, methyl tert-butyl ether and dimethylformamide. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides (e.g. lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide), alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates (e.g. lithium carbonate and calcium carbonate) and also alkali metal bicarbonates (e.g. sodium bicarbonate), organometallic compounds, in particular alkali metal alkyls, alkylmagnesium halides and also alkali metal and alkaline earth metal alkoxides (e.g. sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium), moreover organic bases, e.g. tertiary amines, such as trimethylamine, triethylamine, tri-isopropylethylamine [sic] and N-methylpiperidine, pyridine, substituted pyridines and also bicyclic amines. Particular preference is given to sodium hydroxide, potassium carbonate and potassium tert-butoxide. The bases are generally employed in equimolar amounts, in excess or, if appropriate, as solvents.
It may be advantageous for the reaction to add a catalytic amount of a crown ether (e.g. 18-crown-6 or 15-crown-5).
The reaction can also be carried out in two-phase systems comprising a solution of alkali metal
Ammermann Eberhard
Blasco Jordi Tormo i
Cullmann Oliver
Gewehr Markus
Götz Roland
BASF - Aktiengesellschaft
Keil & Weinkauf
Rao Deepak R.
LandOfFree
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