Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
2000-06-26
2001-10-30
Raymond, Richard L. (Department: 1624)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C514S272000, C544S296000, C544S298000, C544S316000, C544S330000
Reexamination Certificate
active
06310071
ABSTRACT:
The present invention relates to 2-(O-[pyrimidin-4-yl]methyleneoxy)phenylacetic acid derivatives of the general formula I
and the salts and N-oxides thereof where the radicals R
1
to R
4
and Q have the following meanings:
R
1
is hydrogen or C
l
-C
4
-alkyl;
R
2
is halogen, C
1
-C
2
-alkyl or C
1
-C
2
-haloalkyl;
R
3
is hydrogen; amino; hydroxyl; mercapto; halogen; C
1
-C
8
-alkyl, it being possible for the alkyl radicals to have attached to them a phenyl group which, in turn, can have attached to it one or, independently of one another, two of the following substituents: halogen, cyano, nitro, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl and C
1
-C
4
-alkoxy; C
1
-C
8
-haloalkyl; C
1
-C
8
-alkoxy-C
1
-C
4
-alkyl; C
1
-C
8
-alkoxy; C
1
-C
8
-monoalkylamino; di-C
1
-C
8
-alkylamino; C
1
-C
8
-alkylthio; C
1
-C
8
-alkylsulfoxyl; C
1
-C
8
-alkylsulfonyl; C
3
-C
8
-cycloalkyl; tri-C
1
-C
8
-alkylsilyloxy or the following, unsubstituted or substituted in the aromatic ring: phenyl, phenoxy, phenoxymethyl, benzyloxy or hetaryl;
R
4
is hydrogen; cyano; halogen; C
1
-C
4
-alkyl; C
1
-C
4
-haloalkyl or C
1
-C
4
-alkoxy;
Q is
C(═NOCH
3
)—CONHCH
3
,
C(═NOCH
3
)—COOCH
3
or
N(OCH
3
)—COOCH
3
.
In addition, the invention relates to compositions comprising the compounds I and to their use for controlling harmful fungi and animal pests.
Fungicidally and/or insecticidally and acaricidally active methyl &agr;-[2-(heteroaryloxymethylene)phenyl]-&agr;-methoxyiminoacetamides have been disclosed (EP-A 398 629; EP-A 477 631; JP-A 04/182 461; German Patent Application File Ref. No. 1 95 26 661.7).
Furthermore, fungicidally and/or insecticidally and acaricidally active methyl &agr;-[2-(heteroaryloxymethylene)phenyl]-&agr;-methoxyiminoacetates have been disclosed (cf. EP-A 254 426, EP-A 363 818, EP-A 407 873).
In addition, fungicidally and/or insecticidally and acaricidally active methyl N-[2-(heteraryloxymethylene)phenyl]-N-methoxycarbamates have been disclosed (cf. WO-A 93/15046).
The activity of the compounds described in the abovementioned publications is as yet unsatisfactory.
It is an object of the invention to provide novel compounds which have improved properties in the control of harmful fungi and animal pests.
We have found that this object is achieved by the compounds I defined at the outset, by compositions comprising them and by their use for controlling harmful fungi and animal pests.
The compounds I are prepared by methods similar to those described in the literature mentioned at the outset.
When synthesizing the compounds I, it is generally irrelevant whether the group Q or the 2-(O-[pyrimidin-4-yl]-methyleneoxy) group is synthesized first.
For example, the compounds I are obtained by reacting a pyrimidin-4-ol of the formula II with a benzyl derivative of the formula III in a manner known per se in an inert organic solvent in the presence of a base.
In formula III, X is a nucleophilically exchangeable leaving group such as halogen (eg. chlorine, bromine or iodine), alkylsulfonyl (eg. methylsulfonyl or trifluoromethylsulfonyl) or arylsulfonyl (eg. [phenylsulfonyl or 4-methylphenylsulfonyl).
The reaction is normally carried out at from 0 to 80, preferably from 20 to 60° C.
Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, duisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, ketones such as acetone and methyl ethyl ketone, and also dimethyl sulfoxide, dimethyl formamide, dimethylacetamide, 1,3-dimethylimidazolidin-2-one and 1,3-dimethyltetrahydro-2(1H)-pyrimidinone. Especially preferred are methylene chloride, acetone and dimethylformamide.
Mixtures of these can also be used.
Suitable bases are, generally, inorganic compounds with basic character such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as potassium carbonate and calcium carbonate, and alkali metal hydrogen carbonates such as potassium hydrogen carbonate and calcium hydrogen carbonate and alkali metal hydrogen carbonates such as sodium hydrogen carbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride, and alkali metal and alkaline earth metal alkoxides such as sodium methoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium.
Furthermore suitable as bases are organic bases, for example tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, and bicyclic amines.
Especially preferred are sodium hydroxide, sodium hydride, potassium carbonate and potassium tert-butoxide.
The bases are generally used in equimolar amounts or in an excess or else, if desired, as the solvent.
It may be advantageous for the reaction to add a catalytic amount of a crown ether, for example 18-crown-6 or 15-crown-5.
The reaction can also be carried out in two-phase systems composed of, for example, a solution of alkali metal or alkaline earth metal hydroxides or alkali metal or alkaline earth metal carbonates in water and an organic phase, for example halogenated hydrocarbons. Phase-transfer catalysts which can be added are ammonium halides and ammonium tetrafluoroborates, eg. benzyltriethylammonium chloride, benzyltributylammonium bromide, tetrabutylammonium chloride, hexadecyltrimethylammonium bromide or tetrabutylammonium tetrafluoroborate, and phosphonium halides such as tetrabutylphosphonium chloride or tetraphenylphosphonium bromide.
It may be advantageous for the reaction first to treat the compounds II with base and to react the resulting salt with the compounds III.
The compounds II can be obtained by subjecting &bgr;-ketoesters VI to a condensation reaction with amidines, guanidines, ureas or thioureas VII by methods similar to known processes [cf. J. Chem. Soc. (1946), page 5].
R in formula VI is mainly a C
1
-C
4
-alkyl group, in particular methyl or ethyl.
The reaction is normally carried out at from 0 to 120, preferably 20 from 20 to 80,° C. and in particular at the boiling point of the solvent. Solvents which are normally used are alcohols, in particular methanol or ethanol.
The compounds VII can also be employed in the form of their salts, in particular as the hydrohalides (eg. hydrochloride or hydrobromide). If salts are used, it is expedient to carry out the reaction in the presence of a base (eg. alkaline earth metal or alkali metal alkoxides, or alkaline earth metal or alkali metal hydroxides, eg. sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide and calcium hydroxide).
The starting compounds of type II and their syntheses are generally known, in particular from the following publications:
Justus Liebigs Ann. Chem. 758, (1972), pages 125, 127, 130;
Chem. Pharm. Bull. 22, (1974), pages 1239, 1240, 1245-1247;
J. Amer. Chem. Soc. 79 (1957) page 2230;
Bull. Soc. Chim. Fr. (1965), pages 2301-2306;
Bull. Soc. Chim. Fr. (1963), page 673;
BE-A 645062;
Recl. Trav. Chim. Pays-Bas 87, 10, (1968), page 1089;
Chem. Pharm. Bull. 36, 5, (1988), pages 1669-1675;
Tetrahedron 25, (1969), pages 5989, 5992;
J. Org. Chem. 35, (1970), pages 3786, 3790, 3791;
Z. Chem., GE 25, 9, (1985), pages 328-329;
J.
Ammermann Eberhard
Bayer Herbert
Grammenos Wassilios
Grote Thomas
Harries Volker
Balasubramanian Venkataraman
BASF - Aktiengesellschaft
Keil & Weinkauf
Raymond Richard L.
LandOfFree
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