Benzamidoxim derivatives, intermediate products and methods...

Details Benzamidoxim derivatives, intermediate products and methods... Benzamidoxim derivatives, intermediate products and methods...

2000-03-14

2002-07-16

Kumar, Shailendra (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C514S406000, C514S438000, C514S617000, C548S375100, C549S077000, C564S183000

Reexamination Certificate

active

06420605

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to novel benzamidoxime derivatives, to processes and intermediates for their preparation and to their use as fungicides.
BACKGROUND OF THE INVENTION
JP-A 02/006453 descibes fungicidally active benzamidoxime derivatives which, however, are not entirely satisfactory, in particular when low rates of application are used.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide novel benzamidoxime derivatives which have improved activity, in particular even at low rates of application.
We have found that this object is achieved by benzamidoxime derivatives of the formula I
where:
R
1
is difluoromethyl or trifluoromethyl
R
2
is hydrogen or fluorine
R
3
is C
1
-C
4
-alkyl which may be substituted by cyano, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy-C
1
-C
4
-alkyl, C
3
-C
6
-alkenyl, C
3
-C
6
-haloalkenyl, C
3
-C
6
-alkynyl, C
3
-C
8
-cycloalkyl-C
1
-C
4
-alkyl
R
4
is phenyl-C
1
-C
6
-alkyl which may carry one or more substitutents selected from the group consisting of halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy and 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 and C
1
-C
4
-haloalkoxy on the thienyl ring, 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 and C
1
-C
4
-haloalkoxy on the pyrazole ring.
In the definition of the substituents R
1
to R
4
, the terms indicated are a collective term for a group of compounds.
Halogen is in each case fluorine, bromine, chlorine 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 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, for example trichloromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-fluoropropyl, 3-fluoropropyl, 2-chloropropyl or 3-chloropropyl, in particular 2-fluoroethyl or 2-chloroethyl;
cyano-C
1
-C
4
-alkyl: for example cyanomethyl, 1-cyanoeth-1-yl, 2-cyanoeth-1-yl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanoprop-2-yl or 2-cyanoprop-2-yl, in particular cyanomethyl or 2-cyanoethyl;
C
1
-C
4
-alkoxy: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, in particular methoxy or ethoxy;
C
1
-C
4
-alkoxy-C
1
-C
4
-alkyl: C
1
-C
4
-alkyl which is substituted by C
1
-C
4
-alkoxy as mentioned above, i.e. for example methoxymethyl, ethoxymethyl, n-propoxymethyl, (1-methylethoxy)methyl, n-butoxymethyl, (1-methylpropoxy)methyl, (2-methylpropoxy)methyl, (1,1-dimethylethoxy)methyl, 2-(methoxy)ethyl or 2-(ethoxy)ethyl, in particular methoxymethyl or 2-methoxyethyl;
C
3
-C
6
-alkenyl: for example prop-2-en-1-yl, n-buten-4-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl or 2-buten-1-yl, in particular prop-2-en-1-yl;
C
3
-C
6
-haloalkenyl: C
3
-C
6
-alkenyl as mentioned above which is partially or fully substituted by fluorine, chlorine and/or bromine, for example 2-chloroallyl, 3-chloroallyl, 2,3-dichloroallyl or 3,3-dichloroallyl, in particular 2-chloroallyl;
C
3
-C
6
-alkynyl: for example prop-1-yn-1-yl, prop-2-yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl or n-but-2-yn-1-yl, in particular prop-2-yn-1-yl;
C
3
-C
8
-cycloalkyl-C
1
-C
4
-alkyl: for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, (cyclopropyl)ethyl, 1-(cyclobutyl )ethyl, 1-(cyclopentyl)ethyl, 1-(cyclohexyl)ethyl, 1-(cycloheptyl)ethyl, 1-(cyclooctyl)ethyl, 2-(cyclopropyl)ethyl or 2-(cyclobutyl)ethyl, in particular cyclopentylmethyl;
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, in particular benzyl or 2-phenylethyl;
thienyl-C
1
-C
4
-alkyl: for example 2-thienylmethyl, 3-thienylmethyl or 2-thienylethyl;
pyrazolyl-C
1
-C
4
-alkyl: for example 1-pyrazolylmethyl, 2-pyrazolylmethyl, 3-pyrazolylmethyl or 2-pyrazolylethyl.
Compounds in which the substituent R
1
is difluoromethyl, the substituent R
3
is cyclopropylmethyl and the substituent R
4
is benzyl which carries one to three substituents selected from the group mentioned above 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.
Compounds of the formula I where R
1
to R
4
have the meanings listed in Table 1 below are particularly preferred.
TABLE 1
M.p.
No.
R
1
R
2
R
3
R
4
° C.
I.1
CHF
2
H
C
2
H
5
C
6
H
5
—CH
2
oil
I.2
CHF
2
H
C
2
H
5
4-CH
3
O—C
6
H
4
—CH
2
oil
I.3
CHF
2
H
CH
2
—CH═CH
2
C
6
H
5
—CH
2
oil
I.4
CHF
2
H
CH
2
—C≡CH
C
6
H
5
—CH
2
oil
I.1
CHF
2
H
C
2
H
5
C
6
H
5
—CH
2
oil
I.2
CHF
2
H
C
2
H
5
4-CH
3
O—C
6
H
4
—CH
2
oil
I.3
CHF
2
H
CH
2
—CH═CH
2
C
6
H
5
—CH
2
oil
I.4
CHF
2
H
CH
2
—C≡CH
C
6
H
5
—CH
2
oil
I.5
CHF
2
H
CH
2
—C≡CH
4-CH
3
O—C
6
H
4
—CH
2
oil
I.6
CHF
2
H
cPr
C
6
H
5
—CH
2
I.7
CF
3
H
cPr
C
6
H
5
—CH
2
I.8
CHF
2
H
cPr
4-F—C
6
H
4
—CH
2
75-
77
I.9
CHF
2
H
cPr
4-Cl—C
6
H
4
—CH
2
81-
83
I.10
CHF
2
H
cPr
4-CH
3
O—C
6
H
4
—CH
2
57-
59
I.11
CHF
2
H
cPr
4-CF
3
—C
6
H
4
—CH
2
I.12
CHF
2
H
cPr
2-Thienylmethyl
oil
I.13
CHF
2
H
cPr
3-Thienylmethyl
oil
I.14
CHF
2
H
cPr
Pyrazolyl-1-methyl
I.15
CHF
2
H
cPr
4-CH
3
—C
6
H
4
—CH
2
I.16
CHF
2
5-F
CH
2
—CH═CH
2
C
6
H
5
—CH
2
I.17
CHF
2
5-F
CH
2
—CH═CH
2
4-CH
3
—C
6
H
4
—CH
2
I.18
CHF
2
5-F
CH
2
—C≡CH
C
6
H
5
—CH
2
I.19
CHF
2
5-F
CH
2
—C≡CH
4-CH
3
O—C
6
H
4
—CH
2
I.20
CHF
2
5-F
cPr
C
6
H
5
—CH
2
62-
65
I.21
CHF
2
5-F
cPr
4-F—C
6
H
4
—CH
2
64-
67
I.22
CHF
2
5-F
cPr
4-Cl—C
6
H
4
—CH
2
72-
75
I.23
CHF
2
5-F
cPr
4-CH
3
—C
6
H
4
—CH
2
74-
76
I.24
CHF
2
5-F
cPr
4-CH
3
O—C
6
H
4
—CH
2
79-
81
I.25
CHF
2
5-F
cPr
4-CF
3
—C
6
H
4
—CH
2
I.26
CF
3
5-F
cPr
C
6
H
5
—CH
2
I.27
CHF
2
4-F
cPr
C
6
H
5
—CH
2
I.28
CHF
2
4-F
cPr
4-CH
3
O—C
6
H
4
—CH
2
I.29
CHF
2
H
cPr
4-CH
3
—C
6
H
4
—CH
2
69-
71
I.30
CHF
2
H
CH
2
—C≡CH
4-F—C
6
H
4
—CH
2
74-
76
I.31
CHF
2
H
C
2
H
5
4-F—C
6
H
4
—CH
2
oil
I.32
CHF
2
H
CH
2
—CH═CH
2
4-F—C
6
H
4
—CH
2
oil
I.33
CHF
2
H
CH
2
—CH═CH
2
4-CH
3
O—C
6
H
4
—CH
2
oil
I.34
CHF
2
H
CH
2
—CH(CH
3
)
2
C
6
H
5
—CH
2
65-
67
I.35
CHF
2
H
CH
2
—C(CH
3
)═CH
2
C
6
H
5
—CH
2
oil
In the above table, cPr is cyclopropylmethyl
The benzamidoxime derivatives according to the invention of the formula I are obtained by the process according to the invention by means of ether cleavage of fluorinated benzonitriles of the formula II, reaction of the resulting benzonitriles III with haloalkanes CH
m
F
n
Hal (m has the value 0 or 1, n the value 2 or 3), such as CHF
2
Cl or CF
3
I, in an alkaline medium (preferably in the presence of an alkali metal hydroxide) to give benzonitriles IV and subsequent reaction of IV with hydroxylamine or salts thereof in aqueous solution, preferably in water or water/alkanol mixtures, in the presence or absence of a base, to give the benzamidoximes of the formula V, which are then subsequently alkylated in a manner known per se to give the precursors VI.
The benzamidoximes VI can then be acylated in a manner known per se with the suitable acyl halides, preferably the suitable 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.
R
1
in the above equation is a group CH
m
F
n
, where m is 0 or 1 and n is 2 or 3.
The intermediates of the formula III where R
2
is fluorine and the intermediates of the formulae IV, V and VI, all of whi

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