Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-04-20
2002-10-22
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C562S496000, C562S840000
Reexamination Certificate
active
06469196
ABSTRACT:
The invention relates to new phenyl-substituted cyclic ketoenols, a plurality of processes and intermediates for their preparation and their use as pesticides and herbicides.
It has already been disclosed that certain phenyl-substituted cyclic ketoenols are effective as insecticides, acaricides and/or herbicides.
Pharmaceutical properties of 3-acyl-pyrrolidine-2,4-diones have previously been described (S. Suzuki et al. Chem. Pharm. Bull. 15 1120 (1967)). Furthermore, N-phenylpyrrolidine-2,4-diones have been synthesized by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem. 1985, 1095). A biological activity of these compounds has not been described.
EP-A-0 262 399 and GB-A-2 266 888 disclose compounds (3-aryl-pyrrolidine-2,4-diones) of similar structure, of which, however, no herbicidal, insecticidal or acaricidal action has been disclosed. Unsubstituted, bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-355 599 and EP-A-415 211) and substituted monocyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442 077) with herbicidal, insecticidal or acaricidal action are known.
Polycyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives (EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613 884, DE 4 440 594, EP-A-613 885, WO 94/01 997 and WO 95/01 358) are furthermore known.
It is known that certain substituted &Dgr;
3
-dihydrofuran-2-one derivatives have herbicidal properties (cf. DE-A4 014 420). The synthesis of the tetronic acid derivatives used as starting compounds (e.g. 3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-&Dgr;
3
-dihydrofuran-2-one) is likewise described in DE-A4 014 420. Compounds of similar structure without details of an insecticidal and/or acaricidal activity are known from the publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76. Furthermore, 3-aryl-&Dgr;
3
-dihydrofuranone derivatives having herbicidal, acaricidal and insecticidal properties are disclosed in EP-A-528 156, but the action described there is not always adequate. 3-Aryl-4-hydroxy-&Dgr;
3
-dihydrofuranone derivatives are disclosed in EP-A-647 637. Thiotetronic acids are disclosed in WO 95/26345.
The literature further discloses certain 3H-pyrazol-3-one derivatives, for example 1,2-diethyl-1,2-dihydro-5-hydroxy-4-phenyl-3H-pyrazol-3-one or {[5-oxo-1,2-di-phenyl-4-(p-sulphophenyl)-3-pyrazolin-3-yl]-oxy}[lacuna] disodium salt or p-(3-hydroxy-5-oxo-1,2-diphenyl-3-pyrazolin-4-yl)-benzenesulphonic acid (cf. J. Heterocycl. Chem., 25(5), 1301-1305, 1988 or J. Heterocycl. Chem., 25(5), 1307-1310, 1988 or Zh. Obshch. Khim., 34(7), 2397-2402, 1964). A biological action of these compounds, however, is not described.
It is furthermore known that the trisodium salt of 4,4′,4″-(5-hydroxy-3-oxo-1H-pyrazole-1,2,4(3H)-triyl)-tris-benzenesulphonic acid has pharmacological properties (cf. Farmakol. Toksikol. (Moscow), 38(2), 180-186, 1976). Its use in plant protection, however, is not known.
In addition, EP-A-508 126 and WO 92/16 510 describe 4-arylpyrazolidine-3,5-dione derivatives having herbicidal, acaricidal and insecticidal properties.
Certain phenyl-pyrone derivatives unsubstituted in the phenyl ring have already been disclosed (cf. A. M. Chirazi, T. Kappe and E. Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K. Heidenbluth, Chem. Ber. 91, 2849), a possible utility for these compounds as pesticides not being indicated. Phenyl-pyrone derivatives substituted in the phenyl ring and having herbicidal, acaricidal and insecticidal properties are described in EP-A-588 137.
Certain 5-phenyl-1,3-thiazine derivatives unsubstituted in the phenyl ring have already been described (cf. E. Ziegler and E. Steiner, Monatsh. 95 147 (1964), R. Ketcham T. Kappe and E. Ziegler, J. Heterocycl. Chem. 10, 223 (1973)), a possible application as pesticides not being indicated for these compounds. 5-Phenyl-1,3-thiazine derivatives substituted in the phenyl ring and having herbicidal, acaricidal and insecticidal action are described in WO 94/14 785.
The activity and spectrum of action of these compounds, however, is not always completely satisfactory, in particular at low application rates and concentrations.
New compounds of the formula (I)
have now been found,
in which
X represents alkyl,
Y represents halogen or alkyl and
Z represents halogen or alkyl,
with the proviso that one of the radicals Y and Z always represents halogen and the other alkyl,
Het represents one of the groups
in which
A represents hydrogen or alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or alkylthioalkyl, each of which is optionally substituted by halogen or cycloalkyl or heterocyclyl, each of which is saturated or unsaturated and optionally substituted, or aryl, arylalkyl or hetaryl, each of which is optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, cyano or nitro,
B represents hydrogen, alkyl or alkoxyalkyl, or A and B, together with the carbon atom to which they are bonded, represent a saturated or unsaturated, optionally substituted carbocycle or heterocycle,
D represents hydrogen or an optionally substituted radical of the series alkyl, alkenyl, alkinyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl, saturated or unsaturated heterocyclyl, arylalkyl, aryl, hetarylalkyl or hetaryl, or
A and D, together with the atoms to which they are bonded, represent a saturated or unsaturated and optionally substituted carbocycle or heterocycle,
G, in the case in which Het represents one of the radicals (1), (2), (3), (5) or (6), represents hydrogen (a) or, in the case in which Het represents one of the radicals (1), (2), (3), (4), (5) or (6), represents one of the groups
in which
E represents a metal ion equivalent or an ammoniumn 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, or cycloalkyl or heterocyclyl, each of which is optionally substituted by halogen, alkyl or alkoxy, or phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, each of which is optionally substituted,
R
2
represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, each of which is optionally substituted by halogen, or cycloalkyl, phenyl or benzyl, each of which is optionally substituted,
R
3
, R
4
and R
5
independently of one another represent alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio, each of which is optionally substituted by halogen, or phenyl, phenoxy or phenylthio, each of which is optionally substituted,
R
6
and R
7
independently of one another represent hydrogen, or alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, each of which is optionally substituted by halogen, or phenyl or benzyl, each of which is optionally substituted, or, together with the N atom to which they are bonded, form an optionally substituted cyclic system optionally containing oxygen or sulphur.
The compounds of the formula (I) can also be present, depending on the nature of the substituents, as geometric and/or optical isomers or isomer mixtures of differing composition which, if appropriate, can be separated in a customary manner. Both the pure isomers and the isomer mixtures, their preparation and use, and compositions containing these are a subject of the present invention. In the following, for the sake of simplicity, however, compounds of the formula (I) are always referred to, although both the pure compounds and, if appropriate, mixtures of different proportions of isomeric compounds are intended.
Including the meanings (1) to (6) of the group Het, the following principle structures (I-1) to (I-6) result:
in which
A, B, D, G, X, Y and Z have the meanings given above.
Including the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principle structures (I-1-a) to (I-1-g) result if Het represents the group (1)
in which
A, B, D, E, L, M, X, Y, Z, R
1
, R
2
,
Andersch Wolfram
Bretschneider Thomas
Dahmen Peter
Dollinger Markus
Erdelen Christoph
Bayer Aktiengesellschaft
Norris & McLaughlin & Marcus
Raymond Richard L.
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