Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
1999-04-07
2002-04-30
Morris, Patricia L. (Department: 1612)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C548S264400
Reexamination Certificate
active
06380231
ABSTRACT:
The present invention relates to compounds of the general formula I
in which the index and the substituents have the following meanings:
n is 0, 1, 2, 3 or 4, it being possible for the substituents R to differ if n is greater than 1;
R is nitro, cyano, halogen,
unsubstituted or substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy or
in the event that n is greater than 1 additionally an unsubstituted or substituted bridge which is bonded to two adjacent ring atoms and which three to four members selected from the group consisting of 3 or 4 carbon atoms, 1, 2 or 3 carbon atoms and 1 or 2 nitrogen, oxygen and/or sulfur atoms, it being possible for this bridge, together with the ring to which it is bonded, to form a partially unsaturated or aromatic radical;
R
1
, R
2
are C
1
-C
4
-alkyl;
R
3
is a pyrazole or triazole radical of the formulae A.1 to A.3
the bond marked with • being the bond to the oxygen and the indices and the substituents having the following meanings:
R
a
is unsubstituted or substituted alkyl, alkenyl or alkynyl;
an unsubstituted or substituted saturated or mono- or diunsaturated ring which, besides carbon atoms, can contain one to three of the following hetero atoms as ring members: oxygen, sulfur and nitrogen; or
a substituted mono- or binuclear aromatic radical which, besides carbon atoms, can contain one to four nitrogen atoms or one or two nitrogen atoms and one or two oxygen or sulfur atoms or one oxygen or one sulfur atom as ring members;
m is 0, 1 or 2, it being possible for the substituents R
b
to differ if m is greater than 1;
R
b
is cyano, nitro, halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy, C
1
-C
4
-alkylthio and C
1
-C
4
-alkoxycarbonyl;
o is 0, 1 or 2, it being possible for the substituents R
c
to differ if o is greater than 1;
R
c
is halogen,
unsubstituted or substituted alkyl, alkenyl or alkynyl;
an unsubstituted or substituted saturated or mono- or diunsaturated ring which, besides carbon atoms, can contain one to three of the following hetero atoms as ring members: oxygen, sulfur and nitrogen; or
an unsubstituted or substituted mono- or binuclear aromatic radical which, besides carbon atoms, can contain one to four nitrogen atoms or one or two nitrogen atoms and one or two oxygen or sulfur atoms or one oxygen or one sulfur atom as ring members;
R
d
is hydrogen, cyano, halogen,
unsubstituted or substituted alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy;
an unsubstituted or substituted saturated or mono- or diunsaturated ring which, besides carbon atoms, can contain one to three of the following hetero atoms as ring members: oxygen, sulfur and nitrogen; and which can be bonded to the skeleton either directly or,via an oxygen or sulfur atom; or
a substituted mono- or binuclear aromatic radical which, besides carbon atoms, can contain one to four nitrogen atoms or one or two nitrogen atoms and one or two oxygen or sulfur atoms or one oxygen or one sulfur atom as ring members.
The invention furthermore relates to processes for the preparation of these compounds, to compositions comprising them, and to their use for controlling animal and fungal pests.
The literature describes hetaryloxybenzylalkoxyacrylic esters having a fungicidal and, in some cases, also insecticidal, acaricidal and nematicidal action in general form (EP-A 278 595; EP-A 254 426; EP-A 358 692; WO-A 94/19,331, WO-A 94/00,436).
It was an object of the present invention to provide compounds with an improved activity.
Accordingly, we have found that this object is achieved by the compounds I defined at the outset. Furthermore, processes for the preparation of these compounds, compositions comprising them, and their use for controlling animal and fungal pests have been found.
The compounds I are accessible via a variety of methods which are known per se from the literature cited.
For example, the compounds I are obtained by reacting the benzyl derivative II with a hydroxyazole of the formula III in the presence of a base.
L in formula II is a nucleophilically exchangeable group, for example halogen, eg. chlorine, bromine and iodine, or an alkyl- or arylsulfonate, eg. methylsulfonate, trifluoromethylsulfonate, phenylsulfonate and 4-methylphenylsulfonate.
The reaction is conventionally carried out at from 0° C. to 100° C., preferably 20° C. to 60° C.
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, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, alcohols, such as methanol, ethanol, n-propanol, i-propanol, n-butanol and tert-butanol, ketones, such as acetone and methyl ethyl ketone, and also ethyl acetate, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, 1,3-dimethylimidazolidin-2-one and 1,2-dimethyltetrahydro-2(1H)-pyrimidine, preferably methylene chloride, acetone, N-methylpyrrolidone and dimethylformamide. Mixtures of these can also be used.
Bases which are generally suitable are inorganic compounds, such as alkali metal hydroxides and alkaline earth metal hydroxides (eg. lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide), alkali metal oxides and alkaline earth metal oxides (eg. lithium oxide, sodium oxide, calcium oxide and magnesium oxide), alkali metal hydrides and alkaline earth metal hydrides (eg. lithium hydride, sodium hydride, potassium hydride and calcium hydride), alkali metal amides (eg. lithium amide, sodium amide and potassium amide), alkali metal carbonates and alkaline earth metal carbonates (eg. lithium carbonate, potassium carbonate and calcium carbonate), and also alkali metal hydrogen carbonates (eg. sodium hydrogen carbonate), organometal compounds, in particular alkali metal alkyls (eg. methyllithium, butyllithium and phenyllithium), alkylmagnesium halides (eg. methylmagnesium chloride) and alkali metal alcoholates and alkaline earth metal alcoholates (eg. sodium methanolate, sodium ethanolate, potassium ethanolate, potassium tert-butanolate and dimethoxymagnesium), 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 also bicyclic amines. Substances which are particularly preferred are sodium hydroxide, sodium methanolate, potassium carbonate, potassium methanolate and potassium tert-butanolate.
The bases are generally used in equimolar amounts, in an excess or, if desired, as the solvent.
It may be advantageous for the reaction to add a catalytic amount of a crown ether (eg. 18-crown-6 or 15-crown-5).
The reaction can also be carried out in two-phase systems composed of a solution of alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides or alkaline earth metal carbonates in water and an organic phase (eg. aromatic and/or halogenated hydrocarbons). Suitable phase transfer catalysts are, for example, ammonium halides and ammonium tetrafluoroborates (eg. benzyltriethylammonium chloride, benzyltributylammonium bromide, tetrabutylammonium chloride, hexadecyltrimethylammonium bromide or tetrabutylammonium tetrafluoroborate) and phosphonium halides (eg. tetrabutylphosphonium chloride and tetraphenylphosphonium bromide).
It may be advantageous for the reaction first to react the hydroxyazole III with the base to give the corresponding hydroxylate, which is then reacted with the benzyl derivative.
Those starting materials II which are required for the preparation of the compounds I which have not already been disclosed in the literature cited at the outset can be prepared by the methods described therein. Those starting materials III which have not already been disclosed in the literature can be prepared by the methods described therein [3-hydroxypyrazoles: J. Heterocycl. Chem. 30, 49 (1993); Chem. Be
Ammermann Eberhard
Harries Volker
Kirstgen Reinhard
König Hartmann
Lorenz Gisela
BASF Aktiengesellscahft
Keil & Weinkauf
Morris Patricia L.
LandOfFree
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