2-[1′,2′,4′-Triazol-3′-yloxymet...

Details 2-[1′,2′,4′-Triazol-3′-yloxymet... 2-[1′,2′,4′-Triazol-3′-yloxymet...

1997-03-17

2001-03-27

Morris, Patricia L. (Department: 1625)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Having -c-, wherein x is chalcogen, bonded directly to...

C548S263400, C548S263600, C548S263800, C548S264400

Reexamination Certificate

active

06207692

ABSTRACT:

The present invention relates to 2-[1′,2′,4′-triazol-3′-yloxy-methylene]anilides of the formula I
where the index and the substituents have the following meanings:
n is 0, 1, 2, 3, or 4, it being possible for the substituents R
1
to be different if n is greater than 1;
X is a direct bond, O or NR
a
;
R
a
is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl;
R
1
is nitro, cyano, halogen,
unsubstituted or substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy or
in the case where n is 2, additionally is an unsubstituted or substituted bridge bonded to two adjacent ring atoms and containing three to four members from the group consisting of 3 or 4 carbon atoms, 1 to 3 carbon atoms and 1 or 2 nitrogen, oxygen and/or sulfur atoms, this bridge together with the ring to which it is bonded being able to form a partly unsaturated or aromatic radical;
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 unsubstituted or substituted alkyl, alkenyl, alkynyl;
an unsubstituted or substituted, saturated or mono- or diunsaturated ring which, in addition to carbon atoms, can contain one to three of the following heteroatoms as ring members: oxygen, sulfur and nitrogen, or
an unsubstituted or substituted, mono- or binuclear aromatic radical which, in addition to carbon atoms, can contain one to four nitrogen atoms or one or two nitrogen atoms and one oxygen or sulfur atom or one oxygen or sulfur atom as ring members;
R
4
is hydrogen,
unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkylcarbonyl or alkoxycarbonyl;
R
5
is alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl, or in the case where X is NR
a
, additionally is hydrogen.
The invention additionally relates to processes and intermediates for preparing these compounds, compositions containing them and their use for controlling animal pests or harmful fungi.
WO-A 93/15,046, discloses 2-[1,2,4-triazol-5-yloxymethylene]anilides for controlling animal pests and harmful fungi.
The object of the present invention are compounds having an improved action.
We have found that this object is achieved by the compounds I defined at the outset. In addition, we have found processes and intermediates for their preparation, mixtures containing them and methods of controlling animal pests and harmful fungi using the compounds I.
The compounds I are obtainable in various ways.
Those compounds I where R
4
is hydrogen and X is a direct bond or oxygen are obtained, for example, by converting a benzyl derivative of the formula II in the presence of a base using a 3-hydroxytriazole of the formula III to the corresponding 2-[1,2,4-triazol-3-yloxymethylene]nitrobenzene of the formula IV, then reducing IV to the N-hydroaniline of the formula Va and converting Va to I using a carbonyl compound of the formula VI.
L
1
in the formula II and L
2
in the formula VI are in each case a nucleophilically replaceable group, for example halogen (eg. chlorine, bromine or iodine) or an alkyl- or arylsulfonate (eg. methylsulfonate, trifluoromethylsulfonate, phenylsulfonate or 4-methylphenylsulfonate).
The etherification of the compounds II and III is customarily carried out at from 0° C. to 80° C., preferably from 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, others 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 dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidin-2-one and 1,2-dimethyltetrahydro-2(1 H)-pyrimidine, preferably methylene chloride, acetone, toluene, tert-butyl methyl ether and dimethylformamide. Mixtures of the solvents mentioned can also be used.
Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides (eg. lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide), alkali metal and alkaline earth metal oxides (eg. lithium oxide, sodium oxide, calcium oxide and magnesium oxide), alkali metal 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 and alkaline earth metal carbonates (eg. lithium carbonate and calcium carbonate) and also alkali metal hydrogen carbonates (eg. sodium hydrogen carbonate), organometallic compounds, in particular alkali metal alkyls (eg. such as methyllithium, butyllithium and phenyllithium), alkylmagnesium halides (eg. methylmagnesium chloride) and also alkali metal and alkaline earth metal alkoxides (eg. sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium), additionally organic bases, eg. tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, as well as bicyclic amines.
Sodium hydroxide, potassium carbonate and potassium tert-butoxide are particularly preferred.
The bases are in general used in an equimolar amount, in an excess or if appropriate as a 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 consisting of a solution of alkali metal alkaline earth metal hydroxides or carbonates in water and an organic phase (eg. aromatic and/or halogenated hydrocarbons). Suitable phase transfer catalysts in this case are, for example, ammonium halides and tetraflouroborates (eg. benzyltriethylammonium chloride, benzyltributylammonium bromide, tetrabutylammonium chloride, hexadecyltrimethylammonium bromide or tetrabutylammonium tetraflouroborate) and phosphonium halides (eg. tetrabutylphosphonium chloride and tetraphenylphosphonium bromide).
It may be advantageous for the reaction first to convert the 3-hydroxytriazole to the corresponding hydroxylate using the base and then to react it with the benzyl derivative.
The starting substances II required for preparing the compounds I are disclosed in EP-A 513 580 or can be prepared by the methods described there [Synthesis 1991, 181; Anal. Chim. Acta 185 (1986), 295; EP-A 336 567].
3-Hydroxytriazoles III are likewise discloses in the literature or can be prepared by the methods described there [Chem. Ber. 56 (1923), 1794; DE-A 21 50 169; DE-A 22 00 436; U.S. Pat. No. 4,433,148; J. Med. Chem. 33 (1990), 2772; Synthesis 1987, 986; DE-A 22 60 015; DE-A 24 17 970].
The nitro compounds IV are reduced to the corresponding N-hydroxyanilines IVa in a similar manner to methods known from the literature, for example using metals such as zinc [cf. Ann. Chem. 316 (1901), 278] or with hydrogen (cf. EP-A 085 890).
The N-hydroxyanilines Va are reacted with the carbonyl compounds VI under alkaline conditions, in particular at from −10° C. to 30° C. The preferred solvents are methylene chloride, toluene, tert-butyl methyl ether or ethyl acetate. The preferred bases are sodium hydrogen carbonate, potassium carbonate, sodium hydroxide or aqueous sodium hydroxide solution.
The compounds of the formula I where R
4
does denote hydrogen and X is a direct bond or oxygen are additionally obtained, for example, by first reducing a benzyl derivative of the formula IIa to the corresponding hydroxyaniline of the formula Vb, converting Vb to the corresponding anilide of the formula VII using a carbonyl compound of the formula VI, then converting VII to the amide of the formula IX using a compound VIII, then converting IX to the corresponding benzyl h

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