Azoline derivatives

Details Azoline derivatives Azoline derivatives

2000-05-03

2002-07-02

Stockton, Laura L. (Department: 1626)

Plant protecting and regulating compositions

Plant growth regulating compositions

Organic active compound containing

C504S270000, C548S146000, C548S239000

Reexamination Certificate

active

06413912

ABSTRACT:

The object of the invention is a compound of formula
wherein X and Y are, independently of one another, fluorine or chlorine, and Z is O or S;
and where appropriate their possible tautomers, in each case either in free form or in the form of a salt; a method for the preparation and application of these compounds, their salts and their tautomers; pesticides whose active ingredient is selected from these compounds and their tautomers; and a method for the preparation and application of these compositions, intermediates, in free form or in the form of a salt, for the preparation of these compounds, where appropriate tautomers, in free form or in the form of a salt.
In the literature, certain oxazoline derivatives are proposed as insecticidally active substances in pesticides. The biological properties of these known compounds, however, are not fully satisfactory in the field of pest control, which is why there is a need to produce further compounds with pesticidal properties, especially for the control of insects; this problem is solved according to the invention with the development of the present compounds of formula (I).
The compounds of formula (I) may be present partly in the form of tautomeric derivatives. Accordingly, any reference to compounds of formula (I) hereinbefore and hereinafter is understood to include also their corresponding tautomers, even if the latter are not specifically mentioned in each case.
The compounds of formula (I) and where appropriate their tautomers can form salts, for example acid addition salts. These are formed for example with strong inorganic acids, typically mineral acids, e.g. sulfuric acid, a phosphoric acid or a halogen acid, or with strong organic carbonic acids, typically C
1
-C
4
alkanecarbonic acids substituted where appropriate for example by halogen, e.g. acetic acid, such as dicarbonic acids that are unsaturated where necessary, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, typically hydroxycarbonic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, typically C
1
-C
4
alkane or arylsulfonic acids substituted where appropriate for example by halogen, e.g. methanesulfonic or p-toluenesulfonic acid. In a broader sense, compounds of formula (I) with at least one acid group can form salts with bases. Suitable salts with bases are for example metal salts, typically alkali or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl, diethyl, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine. Furthermore, where appropriate corresponding internal salts may also be formed. The free form is preferred. Among the salts of compounds of formula (I), the agrochemically beneficial salts are preferred. Hereinbefore and hereinafter, the free compounds of formula (I) and their salts are understood where appropriate to include also by analogy the corresponding salts or free compounds of formula (I). The same applies for tautomeric derivatives of compounds of formula (I) and salts thereof.
Compounds of formula (I), wherein X and Y are fluorine, are preferred. Likewise preferred are compounds of formula (I), wherein Z is O.
The individual compounds of this claim according to the invention are preferably
(1) 2-(2,6-Dichlorophenyl)-4-(4′-trifluoromethylbiphenyl-4yl)-4,5-dihydro-oxazole; or
(2) 2-(2,6-Chloro,6-fluorophenyl)-4-(4′-trifluoromethylbiphenyl-4-yl)-4,5-dihydro-oxazole; or
(3) 2-(2,6-Difluorophenyl)-4-(4′-trifluoromethylbiphenyl-4-yl)-4,5-dihydro-oxazole.
A further object of the invention is a method for preparing the compounds of formula (I) and where appropriate their tautomers, in each case in free form or in the form of a salt, comprising
a) the reaction of a compound of formula
which is known or can be prepared according to known methods, and wherein X and Y are as defined for formula (l) and Q is bromine or iodine, with a compound of formula
which is known; and
b) where appropriate, for preparing a compound of formula (I), wherein Z is S, the reaction of the resulting compound of formula (I), wherein Z is O, with Lawesson's reagent [2,4-bis(methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide] or with phosphorus pentasulfide;
and in each case, if so desired, the conversion of a compound of formula (I) obtainable according to the method or by other means, or a tautomer thereof, present in free form or in the form of a salt, into a different compound of formula (I) or a tautomer thereof, the separation of a mixture of isomers obtainable according to the method and isolation of the desired isomer and/or the conversion of a free compound of formula (I) obtainable according to the method, or a tautomer thereof, into a salt, or a salt obtainable according to the method from a compound of formula (I), or a tautomer thereof, into the free compound of formula (I), or a tautomer thereof, or into a different salt.
The statement made hereinabove with regard to tautomers and salts of formula (I) apply by analogy in respect of the tautomers and salts of starting materials mentioned hereinbefore and hereinafter.
The reactions described hereinbefore and hereinafter are carried out in a known manner, e.g. in the absence or usually in the presence of a suitable solvent or diluent or a mixture thereof, proceeding as required under conditions of cooling, of ambient temperature, or of heating, e.g. in a temperature range of about −80° C. to the boiling temperature of the reaction medium, preferably about 0° C. to about +150° C., and where appropriate in a closed vessel, under pressure, in an inert gas atmosphere, and/or under non-aqueous conditions. Especially advantageous reaction conditions are described in the Examples.
The starting materials listed hereinbefore and hereinafter for the preparation of compounds of formula (I) and where appropriate the tautomers thereof, either in free form or in the form of a salt, are known or can be prepared according to known methods, e.g. as described hereinafter.
Variant a):
Suitable catalysts are in particular transition metal catalysts, especially iron, palladium, ruthenium, rhodium, nickel, zinc, or platinum catalysts. Particularly suitable are iron(I), nickel(0) and palladium(0) catalysts, especially Pd(PPh
3
)
4
.
Suitable bases for facilitating the reaction are e.g. alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, cycloalkylamines (N-alkylated where appropriate and unsaturated where appropriate), basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples are: sodium hydroxide, hydride, amide, methanolate, acetate, and carbonate, potassium tert-butanolate, hydroxide, carbonate, hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU). Alkali and alkaline earth carbonates are preferred, especially potassium carbonate.
The reaction partners can be reacted with one another as they are, i.e. without the addition of a solvent or diluent, e.g. in the melt. In most cases, however, the addition of an inert solvent or diluent, or a mixture thereof, is of advantage. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, typically benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl

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