Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
2000-03-21
2003-07-08
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...
C514S462000, C514S438000, C548S408000, C549S062000, C549S284000, C504S284000
Reexamination Certificate
active
06589976
ABSTRACT:
The invention relates to novel spirocyclic phenylketoenols, to a plurality of processes and intermediates for their preparation and to their use as pesticides and herbicides.
It is already known that certain phenyl-substituted cyclic ketoenols are active as insecticides, acaricides and/or herbicides, for example 1H-arylpyrrolidine-dione derivatives (EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, DE-44 40 594, WO 94/01 997, WO 95/01 358, WO 95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO 97/01 535 and WO 97/02 243).
Furthermore, it is known that certain substituted &Dgr;
3
-dihydrofuran-2-one derivatives have herbicidal properties (cf. DE-A-4 014 420). The synthesis of the tetronic acid derivatives employed as starting materials (such as, for example, 3-(2-methylphenyl)-4-hydroxy-5-(4-fluorophenyl)-&Dgr;
3
-dihydrofuran-(2)-one) is also described in DE-A-4 014 420. Compounds of a similar structure are known from the publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76, without any insecticidal and/or acaricidal activity having been mentioned. Furthermore, 3-aryl-&Dgr;
3
-dihydrofuranone derivatives having herbicidal, acaricidal and insecticidal properties are known from EP-A-528 156, EP-A 0 647 637, WO 95/26345, WO 96/20 196, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243 and WO 97/36 868.
However, the efficacy and the spectrum of action of these compounds is, in particular at low application rates and concentrations, not always entirely satisfactory. Furthermore, the crop plant safety of these compounds is not always sufficient.
This invention, accordingly, provides novel compounds of the formula (I)
in which,
X represents halogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, halogenoalkyl, halogenoalkenyl, halogenoalkoxy, halogenoalkenyloxy, nitro, cyano or represents phenyl, phenoxy, phenylthio, benzyloxy or benzylthio, each of which is optionally substituted,
Y represents hydrogen, halogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, halogenoalkyl, halogenoalkenyl, halogenoalkoxy, halogenoalkenyloxy, nitro or cyano,
Z represents halogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, alkoxy, alkenyloxy, halogenoalkoxy, halogenoalkenyloxy, nitro or cyano,
n represents 0, 1, 2 or 3,
Het represents one of the groups
in which
G represents hydrogen (a) or represents one of the groups
in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R
1
represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl, each of which is optionally substituted by halogen, represents cycloalkyl which is optionally substituted by halogen, alkyl or alkoxy and which may be interrupted by one or more hetero atoms, or represents phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, each of which may optionally be substituted,
R
2
represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, each of which may optionally be substituted by halogen, or represents cycloalkyl, phenyl or benzyl, each of which may optionally be substituted,
R
3
, R
4
and R
5
independently of one another each represent alkyl, alkoxyl, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio, each of which may optionally be substituted by halogen, or represents phenyl, benzyl, phenoxy or phenylthio, each of which may optionally be substituted,
R
6
and R
7
independently of one another represent hydrogen, represent alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl, each of which may be substituted by halogen, represent phenyl which may optionally be substituted, represent benzyl which may optionally be substituted, or together with the N atom to which they are attached represents an optionally hydrogen- or sulphur-containing ring,
Q represents
R
9
represents hydrogen, represents alkyl, cycloalkyl, phenyl, benzyl or hetaryl, each of which may optionally be substituted, or represents CO—R
1′
; CO
2
—R
2′
; SO
2
—R
1′
; CONH
2
; CONHR
11
or
R
10
represents hydrogen or alkyl,
R
11
represents alkyl or alkenyl,
R
12
represents alkyl or alkenyl,
m represents 0, 1 or 2,
R
1
′ independently of R
1
has the meanings given above for R
1
and
R
2
′ independently of R
2
has the meanings given above for R
2
.
Depending inter alia on the nature of the substituents, the compounds of the formula (I) can be present as geometric and/or optical isomers or isomer mixtures of varying composition, which can be separated, if appropriate, in a customary manner. The present invention provides both the pure isomers and the isomer mixtures, their preparation and use and compositions comprising them. For simplicity, however, reference is always made below to compounds of the formula (I), although this means both the pure compounds and, where appropriate, also mixtures with different contents of isomeric compounds.
Incorporating the meanings (1) to (3) of the group Het, the following main structures (I-1) to (I-3) result:
in which
Q, G, X, Y, Z, n and m are each as defined above.
Incorporating the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following main structures (I-1-a) to (I-1-g), result if Het represents the group (I)
in which
E, L, M, Q, X, Y, Z, n, m, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
7
are each as defined above.
Incorporating the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following main structures (I-2-a) to (I-2-g), result if Het represents the group (2)
in which
E, L, M, Q, X, Y, Z, n, m, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
7
are each as defined above.
Incorporating the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following main structures (I-3-a) to (I-3-g), result if Het represents the group (3)
in which
E, L, M, Q, X, Y, Z, n, m, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
7
are each as defined above.
Furthermore, it has been found that the novel compounds of the formula (I) are obtained by one of the processes described below:
(A) Substituted 3-phenylpyrrolidine-2,4-diones or enols thereof of the formula (I-1-a)
in which
Q, X, Y, Z, m and n are each as defined above,
are obtained when
N-acylamino acid esters of the formula (II)
in which
Q, X, Y, Z, m and n are each as defined above,
and
R
8
represents alkyl (preferably C
1
-C
6
-alkyl),
are intramolecularly condensed in the presence of a diluent and in the presence of a base.
(B) Furthermore, it has been found that substituted 3-phenyl-4-hydroxy-&Dgr;
3
-dihydrofuranone derivatives of the formula (I-2-a)
in which
Q, X, Y, Z, m and n are each as defined above,
are obtained when
carboxylic esters of the formula (III)
in which
Q, X, Y, Z, m, n and R
8
are each as defined above,
are intramolecularly condensed in the presence of a diluent and in the presence of a base.
(C) Furthermore, it has been found that substituted 3-phenyl-4-hydroxy-&Dgr;
3
-dihydrothiophenone derivatives of the formula (I-3-a)
in which
Q, X, Y, Z, m and n are each as defined above,
are obtained when
&bgr;-ketocarboxylic esters of the formula (IV)
in which
Q, X, Y, Z, m, n and R
8
are each as defined above and
W represents hydrogen, halogen, alkyl (preferably C
1
-C
6
-alkyl) or alkoxy (preferably C
1
-C
8
-alkoxy),
are intramolecularly cyclized in the presence of a diluent and in the presence of an acid.
Furthermore, it has been found that the compounds of the formulae (I-1-b) to (I-3-b), depicted above in which
(D) Q, X, Y, Z, m, n and R
1
are each as defined above are obtained when compounds of the formulae (I-1-a) to (I-3-a) depicted above in which Q, X, Y, Z, m and n are each as defined above are in each case reacted
&agr;) with acyl chlorides of the formula (V)
in which
R
1
is as defined above and
Hal represents halogen (in particular chlorine or bromine)
or
&bgr;) with carboxylic anhydrides of the formula (VI)
R
1
—CO—O—CO—R
1
(VI)
in which
R
1
is
Bretschneider Thomas
Dollinger Markus
Erdelen Christoph
Fischer Reiner
Turberg Andreas
Balasubramanian Venkataraman
Bayer Aktiengesellschaft
Gil Joseph C.
Harmuth Raymond J.
Henderson Richard E. L.
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