Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Ester doai
Reexamination Certificate
1999-07-28
2001-05-01
Richter, Johann (Department: 1621)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Ester doai
C514S539000, C514S619000, C560S035000, C564S163000
Reexamination Certificate
active
06225349
ABSTRACT:
TECHNICAL FIELD
The present invention relates to hydroximic acid halides of the formula I
where the substituents have the following meanings:
X is NOCH
3
, CHOCH
3
or CHCH
3
;
Y is O or NH;
R
1
is halogen;
R
2
is C
2
-C
6
-alkyl, C
2
-C
6
-alkenyl and C
2
-C
6
-alkynyl, it being possible for these groups to be partially or fully halogenated and/or to have attached to them one or two of the following radicals: cyano, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy and phenyl, it being possible for the phenyl, in turn, to be partially or fully halogenated and/or to have attached to it one to three of the following groups: cyano, nitro, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy and C
1
-C
4
-haloalkoxy;
methyl which is partially or fully halogenated and/or has attached to it one of the following radicals: cyano, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy;
C
5
-C
6
-cycloalkyl which can be partially or fully halogenated and/or can have attached to it one to three C
1
-C
4
-alkyl groups;
aryl or arylmethylene which can be partially or fully halogenated in the aryl moiety and/or can have attached to it one to three of the following radicals: cyano, nitro, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy and C
1
-C
4
-haloalkoxy;
R
3
is C
1
-C
6
-alkyl, C
1
-C
3
-alkoxy-C
1
-C
6
-alkyl, C
3
-C
6
-cycloalkyl-C
1
-C
6
-alkyl, C
3
-C
6
-alkenyl and C
3
-C
6
-alkynyl, it being possible for these groups to be partially or fully halogenated and it being possible for the cycloalkyl groups additionally to have attached to them one to three C
1
-C
4
-alkyl radicals,
and to the salts thereof.
Furthermore the invention relates to processes for the preparation of the compounds I, to compositions comprising them and to their use for controlling animal pests and harmful fungi.
BACKGROUND ART
Phenylacetic acid derivatives which act against animal pests and harmful fungi and whose general structure embraces the structure of the present compounds are known from the literature (WO-A 95/21,153; WO-A 95/21,154). Moreover, WO-A 95/18,789 describes compounds of similar structures which are active against animal pests and harmful fungi.
Against this background, it was an object of the present invention to provide compounds which have improved properties regarding their action.
We have found that this object is achieved by the compounds I defined at the outset. Moreover, there have been found processes and intermediates for their preparation, compositions comprising them, and their use against animal pests and harmful fungi.
The present compounds I differ from the compounds known from WO-A 95/21,153 and WO-A 95/21,154 by the particular combination of the groups R
1
to R
3
. In particular, it has been found that compounds of the known structural type have an improved activity when a halogen is bonded in the position of the radical R
1
and a sterically demanding group which increases the lipophilicity of the compound is bonded in the position of the radical R
2
, and when the position of the radical R
3
is not taken up by hydrogen.
DISCLOSURE OF INVENTION
In general, the compounds I can be obtained by the processes described in the literature cited at the outset.
The compounds I are especially advantageously obtained by first converting a carboxylic ester IIa with hydroxylamine to give the corresponding hydroxamic acid IIc, subsequently reacting IIc with a benzyl compound IIIa to give the corresponding hydroxamic ester IV and converting IV with a halogenating agent [HAL] to give I.
R
x
in formula IIa is the radical of a customary leaving group. Customary leaving groups for the purposes of the present reaction are to be understood as meaning especially the following groups: C
1
-C
4
-alkyl (especially methyl or ethyl) or phenyl.
L in formula IIIa is a nucleofugic leaving group. For the purposes of the present reaction, this is to be understood as meaning especially the following: halogen, alkyl sulfonate or aryl sulfonate, especially chlorine, bromine, iodine, mesylate, tosylate and triflate.
The reaction of the carboxylic ester IIa with hydroxylamine is normally carried out at from −20° C. to 50° C., preferably 0° C. to 20° C., in an inert organic solvent, preferably in the presence of a base (cf. literature: Houben-Weyl, 4th Edition, Vol. E5, p. 1141 et seq.).
Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, 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, nitrites such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, especially preferably alcohols such as methanol and ethanol. Mixtures of these may also be used.
Bases which are generally suitable are inorganic compounds such as alkali metal hydroxides and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal oxides and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal carbonates and alkaline earth metal carbonates such as lithium carbonate and calcium carbonate, and also alkali metal alkoxides and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, and 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. The following are especially preferred: alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and also alkali metal alkoxides such as sodium methoxide and sodium ethoxide.
In general, the bases are used in equimolar amounts or in an excess.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advantageous for the yield to employ an excess of hydroxylamine based on IIa.
The carboxylic esters IIa required for the preparation of the compounds I which are not already known from the literature [DE-A 28 08 317; DE-A 22 65 234; J. Chem. Soc. PT 1 (1975), 2340 et seq.; Chem. Ber. 16 (1883), 2987 et seq.; J. Org. Chem. 37 (1972), 139] can be prepared in accordance with the literature cited.
The reaction of the hydroxamic acid IIc with the benzyl compound IIIa is normally carried out at from 0° C. to 130° C., preferably 10° C. to 60° C., in an inert organic solvent in the presence of a base [cf. literature: Liebigs Ann. Chem. 1992, 997 et seq.; Synth. Commun. 19, (1989), 339 et seq.].
Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, 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, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, especially preferably tetrahydrofuran, acetonitrile and dimethylformamide. Mixtures of these may also be used.
Bases which are generally suitable are inorganic compounds such as alkali metal hydroxides and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal oxides and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal hydrides and alkaline earth metal hydrides such as lit
Ammermann Eberhard
Bayer Herbert
Gotz Roland
Grammenos Wassilios
Grote Thomas
BASF - Aktiengesellschaft
Davis Brian J.
Keil & Weinkauf
Richter Johann
LandOfFree
Hydroximic acid halogenides, method for the production and... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Hydroximic acid halogenides, method for the production and..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Hydroximic acid halogenides, method for the production and... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2453870