Plant protecting and regulating compositions – Plant growth regulating compositions – Organic active compound containing
Patent
1997-02-03
1999-01-26
Richter, Johann
Plant protecting and regulating compositions
Plant growth regulating compositions
Organic active compound containing
548210, A01N 4380, C07D27506
Patent
active
058638644
DESCRIPTION:
BRIEF SUMMARY
This application is a 371 of PCT/EP95/03022 filed Jul. 29, 1995.
The present invention relates to the preparation of saccharincarboxylic acids and saccharincarboxylic acid esters of the formula I ##STR4## where the substituents have the following meanings: L and M are hydrogen, alkyl, alkoxy, alkylthio, chlorine, cyano, alkylsulfonyl, nitro or trifluoromethyl;
The invention further relates to selected saccharin derivatives Ia which have herbicidal activity and serve as intermediates for the preparation of saccharin derivatives in which the OR radical is replaced by other groups. These secondary products are the subject of parallel German applications.
The invention furthermore relates to a method of controlling undesired plant growth using the compounds Ia'.
According to the prior art, eg. DE-A 36 07 343, saccharin derivatives containing a carboxyl substituent in the phenyl ring are obtained via the following reaction sequence: ##STR5## Thus the carboxyl function is introduced into the intermediate by oxidation of a methyl group, oxidative ring closure taking place simultaneously (see also German Reichspatent (DRP) 671 788 from 1936). This method is disadvantageous in that in the presence of a plurality of oxidizable functional groups selective oxidation is not guaranteed. In addition, the number of stages in the entire process is very high, which is inevitably associated with a decrease in yield.
U.S. Pat. No. 5,034,534 describes the preparation of saccharin derivatives by carbonylation of chlorinated aromatic sulfonamides in the presence of complexes of palladium and at least one alkylphosphine ligand. Nothing can be inferred about introduction of the carboxyl function into the phenyl ring of the saccharin structure from this document.
It is an object of the present invention to enable access to saccharin derivatives of the formula I having a carboxyl function in the phenyl ring, in which drastic oxidative methods, such as the use of potassium permanganate, are to be avoided.
We have found that this object is achieved by a process for preparing saccharin derivatives of the formula I, which comprises reacting corresponding bromo- or iodo-substituted saccharin derivatives of the formula II ##STR6## where L, M and Z have the abovementioned meanings, or if Z.noteq.H, compounds of the formula III ##STR7## in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and of a base with carbon monoxide and water or a C.sub.1 -C.sub.6 -alcohol under elevated pressure.
Alkyl radicals in formula I in particular are low-molecular weight alkyl radicals, eg. having 1 to 6 carbon atoms. The same applies for the alkoxy or alkylthio radicals and alkylsulfonyl radicals. Cycloalkyl is eg. C.sub.3 -C.sub.8 -cycloalkyl such as cyclopentyl, cyclohexyl or cyclopropyl. Aryl is eg. phenyl which may carry inert substituents. Aralkyl is eg. phenyl-C.sub.1 -C.sub.4 -alkyl which may carry inert substituents, such as benzyl or phenethyl. ##STR8##
The transition metal-catalyzed conversion of haloaromatics to the corresponding carbonyl or carboxyl compounds by means of carbonylation reagents is known per se, eg. from U.S. Pat. No. 2,640,071; U.S. Pat. No. 3,988,358; U.S. Pat. No. 4,845,273; Urata et al. in J. Org. Chem. 56 (1991), 4320ff; Pri-Bar, Buchman in J. Org. Chem. 53 (1988), 624ff; U.S. Pat. No. 4,990,657, GB-A 2,261,662 and M. Foa et al., J. Organometallic Chem. 285 (1985), 293ff.
The applicability of this method in the case of the specific starting substances II and III is surprising, however. In particular, the success of the process according to the invention had not been expected on the basis of the functional groups present in the starting substances. In addition, it had not been expected that the starting substance III could be converted directly to the carboxylated saccharin derivative I with elimination of the primary amine ZNH.sub.2 via the route according to the invention.
The catalysts nickel, cobalt, rhodium and in particular palladium can be present in metallic form or in the form of customa
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Gerber Matthias
Plath Peter
Rang Harald
Walter Helmut
Westphalen Karl-Otto
BASF - Aktiengesellschaft
Lutz Laura R. C.
Richter Johann
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