Process for the preparation of pesticides

Details Process for the preparation of pesticides Process for the preparation of pesticides

2000-09-26

2003-11-11

O'Sullivan, Peter (Department: 1621)

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

Organic compounds

Carboxylic acid esters

C556S419000, C558S391000, C564S156000, C564S164000, C564S165000

Reexamination Certificate

active

06646151

ABSTRACT:

The invention relates to a process for the preparation of compounds of the formula
and, where appropriate, their tautomers, in each case in the free form or salt form, in which either
X is CH or N, Y is OR
1
and Z is O, or
X is N, Y is NHR
8
and Z is O, S or S(═O);
R
1
is C
1
-C
4
alkyl;
R
2
is H, C
1
-C
4
alkyl, halogeno-C
1
-C
4
alkyl, C
3
-C
6
cycloalkyl or C
1
-C
4
alkoxymethyl;
R
3
and R
4
independently of one another are H, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, OH, CN, NO
2
, a (C
1
-C
4
alkyl)
3
—Si group, where the alkyl groups can be identical or different, halogen, (C
1
-C
4
alkyl)S(═O)
m
, (halogeno-C
1
-C
4
alkyl)S(═O)
m
, halogeno-C
1
-C
4
alkyl or halogeno-C
1
-C
4
alkoxy;
R
5
is C
1
-C
6
alkyl, halogeno-C
1
-C
6
alkyl, C
1
-C
6
alkoxy, halogeno-C
1
-C
6
alkoxy, C
1
-C
6
-alkylthio, halogen-C
1
-C
6
alkylthio, C
1
-C
6
alkylsulfinyl, halogeno-C
1
-C
6
-alkylsulfinyl, C
1
-C
6
alkyl-sulfonyl, halogeno-C
1
-C
6
alkylsulfonyl, C
1
-C
6
alkoxy-C
1
-C
6
alkyl, halogeno-C
1
-C
6
alkoxy-C
1
-C
6
alkyl, C
1
-C
6
alkylthio-C
1
-C
6
alkyl, halogeno-C
1
-C
6
alkylthio-C
1
-C
6
alkyl, C
1
-C
6
alky sulfinyl-C
1
-C
6
alkyl, halogeno-C
1
-C
6
-alkylsulfinyl-C
1
-C
6
alkyl, C
1
-C
6
-alkylsulfonyl-C
1
-C
6
alkyl, halogeno-C
1
-C
6
-alkylsulfonyl-C
1
-C
6
alkyl, C
1
-C
6
-alkylcarbonyl, halogeno-C
1
-C
6
-alkylcarbonyl, C
1
-C
6
-alkoxycarbonyl, halogeno-C
1
-C
6
-alkoxycarbonyl, C
1
-C
6
-alkyl-aminocarbonyl, C
1
-C
4
-alkoxyiminomethyl; di(C
1
-C
6
alkyl)-aminocarbonyl, where the alkyl groups can be identical or different; C
1
-C
6
-alkylaminothiocarbonyl; di(C
1
-C
6
alkyl)-aminothiocarbonyl, where the alkyl groups can be identical or different; C
1
-C
6
-alkyl-amino, di(C
1
-C
6
alkyl)-amino, where the alkyl groups can be identical or different; halogen, NO
2
, CN, SF
5
, thioamido, thiocyanatomethyl; an unsubstituted or mono- to tetrasubstituted C
1
-C
4
alkylenedioxy group, where the substituents are selected from the group consisting of C
1
-C
4
alkyl and halogen; or QR
6
, where, if n is greater than 1, the radicals R
5
can be identical or different;
R
6
is C
2
-C
6
alkenyl or C
2
-C6 alkynyl which are unsubstituted or substituted by 1 to 3 halogen atoms; (C
1
-C
4
alkyl)
3
Si, where the alkyl groups can be identical or different; CN; or an unsubstituted or mono- to pentasubstituted C
3
-C
6
cycloalkyl, aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen, C
1
-C
6
alkyl, halogeno-C
1
-C
6
alkyl, C
1
-C
6
alkoxy, halogeno-C
1
-C
6
alkoxy, phenoxy, naphthoxy and CN;
A either is a direct bond, C
1
-C
10
alkylene, —C(═O)—, —C(═S)— or halogeno-C
1
-C
10
alkylene and R
7
is a radical R
10
, or is C
1
-C
10
alkylene, —C(═O)—, —C(═S)— or halogeno-C
1
-C
10
alkylene and R
7
is OR
10
, N(R
10
)
2
, where the radicals R
10
can be identical or different, or —S(═O)
q
R
10;
R
8
is H or C
1
-C
4
alkyl;
R
9
is methyl, fluoromethyl or difluoromethyl;
R
10
is H; an unsubstituted or substituted C
1
-C
6
alkyl, C
2
-C
6
alkenyl or C
2
-C
6
alkynyl group, where the substituents are selected from the group consisting of halogen; (C
1
-C
4
alkyl)
3
Si, where the alkyl groups can be identical or different; C
3
-C
6
cyclo-alkyl, which is unsubstituted or substituted by halogen; C
1
-C
6
alkoxycarbonyl, which is unsubstituted or substituted by halogen; unsubstituted or substituted aryl, where the substituents are selected from the group consisting of halogen, halogeno-C
1
-C
4
alkyl and CN; a (C
1
-C
4
alkyl)
3
Si group, where the alkyl groups can be identical or different; C
3
-C
6
cycloalkyl, which is unsubstituted or substituted by halogen; C
1
-C
6
alkoxycarbonyl which is unsubstituted or substituted by halogen; or an unsubstituted or substituted aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen and halogeno-C
1
-C
4
alkyl;
Q is a direct bond, C
1
-C
8
alkylene, C
2
-C
6
alkenylene, C
2
-C
6
alkynylene, O, O(C
1
-C
6
alkylene), (C
1
-C
6
alkylene)O, S(═O)p, S(═O)
p
(C
1
-C
6
alkylene) or (C
1
-C
6
alkylene)S(═O)
p
;
m is 0, 1 or 2;
n is 0, 1, 2, 3, 4 or 5;
p is 0, 1 or 2; and
q is 0, 1 or 2,
and the C═N double bond marked with E has the E configuration,
which comprises
a1) reacting either a compound of the formula
 in which A, R
2
, R
5
, R
7
and n are as defined for formula I and the C═N double bond marked with E has the E configuration, or a tautomer thereof, in each case in the free form or in salt form, if appropriate in the presence of a base, with a compound of the formula
 which is known or can be prepared by methods known per se and
in which X, Y, Z, R
3
, R
4
and R
9
are as defined for formula I and X
1
is a leaving group, or a tautomer thereof, in each case in the free from or in salt form, or
a2) reacting a compound of the formula
 in which A, R
2
, R
5
, R
7
and n are as defined for formula I and the C═N double bond marked with E has the E configuration, or a tautomer thereof, in each case in the free form or in the salt form, if appropriate in the presence of a base, with a compound of the formula
 which is known or can be prepared by methods known per se and
in which X, Y, Z, R
3
, R
4
and R
9
are as defined for formula I, or a tautomer thereof, in each case in the free form or in salt form, or
b1) reacting a compound of the formula
 in which A, R
2
, R
5
and n are as defined for formula I and the C═N double bond marked with E has the E configuration, or a tautomer thereof, in each case in the free form or in salt form, if appropriate in the presence of a base, with a compound of the formula
R
7
—A—X
2
  (VII),
 which is known or can be prepared by methods known per se and
in which A and R
7
are as defined for formula I and X
2
is a leaving group, and either further reacting the compound thus obtainable, of the formula IV, for example according to method a1), or
b2) reacting it with hydroxylamine or a salt thereof, if appropriate in the presence of a base or acid catalyst, and further reacting the compound thus obtainable, of the formula II, for example according to method a1), or
c) reacting a compound of the formula
 which is known or can be prepared by methods known per se and
in which R
2
, R
5
and n are as defined for formula I, or a tautomer thereof, in each case in the free form or in salt form, if appropriate in the presence of a base, with a C
1
-C
6
alkyl nitrite, and further reacting the compound thus obtainable, of the formula VI, for example according to method b),
the E isomers of the compounds of the formulae II, IV and VI, or a tautomer thereof, in each case in the free form or in salt form, a process for their preparation and their use for the preparation of compounds of the formula I.
The compounds of the formula I are known pesticides. The processes known to date for their preparation give mixtures of E and Z isomers in respect of the C═N double bond marked with E in formula I of different composition, depending on the process. Since the biological properties of the E isomers are in each case found to be superior to those of the mixtures and of the Z isomers, there is a need to develop preparation processes for compounds of the formula I having the isomerically pure E configuration. This object is achieved by the preparation process according to the invention.
Unless defined differently, the general terms used above and below are defined as follows.
Carbon-containing groups and compounds in each case contain 1 up to and including 8, preferably 1 up to and including 6, in particular 1 up to and including 4, especially 1 or 2, carbon atoms.
Alkyl—as a group per se and as a structural element of other groups and compounds, such as of halogenoalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, halogenoalkoxycarbonyl, alkylaminocarbonyl, alkoxyiminomethyl, alkylaminothiocarbonyl and alkylamino—is, in each case taking into due consideration the number, included from case to case, o

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