Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2000-03-14
2002-07-09
Kumar, Shailendra (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C514S617000, C564S124000, C564S184000
Reexamination Certificate
active
06417398
ABSTRACT:
TECHNICAL FIELD
The present invention relates to novel benzamidoxime derivatives, to processes and intermediates for their preparation, and to their use as fungicides.
BACKGROUND ART
JP-A 02/006453 describes fungicidally active benzamidoxime derivatives which, however, are not entirely satisfactory, in particular when low rates of application are used.
It is an object of the present invention to provide novel benzamidoxime derivatives which have an improved activity, in particular even at low rates of application.
SUMMARY OF THE INVENTION
Surprisingly we have found that this object is achieved by benzamidoxime derivatives of the formula I
wherein
R
1
is hydrogen or fluorine
R
2
is phenyl-C
1
-C
6
-alkyl which may carry one or more substituents selected from the group consisting of halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy on the phenyl ring, or
is thienyl-C
1
-C
4
-alkyl, which may carry one or more substituents selected from the group consisting of halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy, or
is pyrazolyl-C
1
-C
4
-alkyl, which may carry one or more substituents selected from the group consisting of halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy.
In the definition of the substituents R
1
and R
2
, the terms indicated are collective terms for a group of compounds.
Halogen is in each case fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine.
Other meanings are, for example:
C
1
-C
4
-alkyl: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl, in particular methyl or ethyl;
C
1
-C
4
-haloalkyl: a C
1
-C
4
-alkyl radical as mentioned above, which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e. for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-tri-chloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoro-propyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloro-propyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoro-methyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl, in particular trifluoromethyl;
C
1
-C
4
-alkoxy: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethyl-ethoxy, in particular methoxy or ethoxy;
C
1
-C
4
-haloalkoxy: a C
1
-C
4
-alkoxy radical as mentioned above, which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e. for example chloro-methoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoro-ethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromo-ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, in particular difluoromethoxy;
phenyl-C
1
-C
6
-alkyl: for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-(phenylmethyl)eth-1-yl, 1-(phenyl-methyl)-1-(methyl)eth-1-yl or 1-(phenylmethyl)prop-1-yl, in particular benzyl or 2-phenylethyl;
thienyl-C
1
-C
4
-alkyl: for example 2-thienylmethyl, 3-thienyl-methyl, 2-thienylethyl, 2-thienylprop-1-yl or 3-thienylprop-1-yl;
pyrazoly1-C
1
-C
4
-alkyl: for example 1-pyrazolylmethyl, 2-pyrazolylmethyl, 3-pyrazolylmethyl, 2-pyrazolylethyl, 2-pyrazolylprop-1-yl or 3-pyrazolylprop-1-yl,
Compounds in which the substituent R
2
is benzyl which carries one to three substituents selected from the abovementioned group on the phenyl ring, in particular one to three substituents selected from the group consisting of fluorine, chlorine, methyl, methoxy or trifluoromethyl, have generally proved especially effective. Particularly preferred substituents R
2
are 4-fluorobenzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl, 4-trifluoro-methylbenzyl and 4-difluoromethoxybenzyl.
Compounds of the formula I in which R
1
and R
2
have the meanings listed in Table 1 below are particularly preferred.
TABLE 1
No.
R
1
R
2
m.p. (° C.)
I.1
H
4-CH
3
—C
6
H
4
—CH
2
86-88
I.2
H
4-F—C
6
H
4
—CH
2
79-81
I.3
H
4-Cl—C
6
H
4
—CH
2
105-107
I.4
H
4-CH
3
O—C
6
H
4
—CH
2
73-76
I.5
H
4-CF
3
—C
6
H
4
—CH
2
I.6
5-F
4-CH
3
—C
6
H
4
—CH
2
87-90
I.7
5-F
4-F—C
6
H
4
—CH
2
71-74
I.8
5-F
4-Cl—C
6
H
4
—CH
2
85-87
I.9
5-F
4-CH
3
O—C
6
H
4
—CH
2
90-92
I.10
5-F
4-CF
3
—C
6
H
4
—CH
2
I.11
H
2-thienylmethyl
87-89
I.12
H
3-thienylmethyl
I.13
5-F
2-thienylmethyl
90-93
I.14
5-F
3-thienylmethyl
I.15
5-F
3-CH
3
—C
6
H
4
—CH
2
72-75
I.16
5-F
2-F—C
6
H
4
—CH
2
73-76
I.17
5-F
4-CH
2
OF—C
6
H
4
—CH
2
oil
The benzamidoxime derivatives of the formula I according to the invention are obtained by the process according to the invention by means of the reaction of benzonitriles of the formula II with hydroxylamine or salts thereof in aqueous solution, preferably in (water or water/alkanol mixtures, if appropriate in the presence of a base, to give the benzamidbximes of the formula III which are subsequently reacted in a manner known per se in the presence of a base with cyclopropylmethyl halide to give the compounds of the formula IV.
The benzamidoximes IV can then be acylated in a manner known per se with the appropriate acyl halides, preferably the appropriate acyl chlorides, by heating in inert solvents (preferably at from 20 to 100° C.).
Particularly suitable inert solvents are hydrocarbons or ethers, especially preferably aromatic hydrocarbons, such as toluene or xylene, to mention but two examples.
The intermediates of the formula III listed in the reaction scheme above in which R
1
is fluorine, and the intermediates of the formula IV are novel. Preferred compounds are those in which R
1
and R
2
have the meanings mentioned for the compounds I.
The compounds I are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically, and they can therefore also be employed as foliar- and soil-acting fungicides.
Normally, the plants are sprayed or dusted with the active ingredients, or the seeds of the plants are treated with the active ingredients.
The formulations are prepared in a known manner, eg. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Auxiliaries which are suitable are essentially: solvents such as aromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (eg. mineral oil fractions), alcohols (eg. methanol, butanol), ketones (eg. cyclohexanone), amines (eg. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (eg. kaolins, clays, talc, chalk) and ground synthetic minerals (eg. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite w
Ammermann Eberhard
Eicken Karl
Lorenz Gisela
Rheinheimer Joachim
Strathmann Siegfried
Keil & Weinkauf
Kumar Shailendra
LandOfFree
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