Monoesters of carboxymethylene anthranilic acids and process for

Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters

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C07C22956

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059731893

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BRIEF SUMMARY
The invention relates to monoesters of carboxymethylene-anthranilic acids and a process for their preparation.
Such monoesters of carboxymethylene-anthranilic acid are not yet described in the literature. Such compounds are valuable starting substances for novel synthesis variants for the preparation of aldose reductase inhibitors--as can be seen from the German patent application (file reference: 195 32 052.2) filed on the same day as the present German patent application (file reference 195 32 053.0)--and render novel classes of compounds, such as, for example, diesters of carboxymethyleneanthranilic acids with various ester radicals, accessible for the first time.
The quite simple and short synthesis route, which starts from 2,4-dichlorobenzoic acid and leads to the quinazolinediones of the formula (A) used as starting substances for the preparation of aldose reductase inhibitors, is represented in simplified form in the following equation: ##STR2##
The abovementioned quinazolinedione (formula (A)) is an ester of 1,2,3,4-tetrahydro-2,4-dioxoquinazolin-1-ylacetic acid, which, according to EP 218 999, can be used as a starting material for the preparation of aldose reductase inhibitors.
To extend the possibilities of the synthesis of aldose reductase inhibitors and to render novel compounds accessible, there was therefore a need to provide such compounds.
This object was achieved by compounds of the formula (I) ##STR3## in which R is straight-chain or branched (C.sub.1 -C.sub.20)-alkyl, phenyl or CH.sub.2 -phenyl, where the alkyl group or phenyl group can also be substituted by halogen, (C.sub.1 -C.sub.4)-alkyl or (C.sub.1 -C.sub.4)-alkoxy, and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently of one another are hydrogen, halogen, OH, NO.sub.2, (C.sub.1 -C.sub.6)alkoxy, (C.sub.1 -C.sub.6)alkyl or halogen-substituted (C.sub.1 -C.sub.6)alkyl.
Important compounds of the formula (I) among these are those in which R is straight-chain or branched (C.sub.1 -C.sub.12)-alkyl, phenyl or CH.sub.2 -phenyl, in particular (C.sub.1 -C.sub.6)-alkyl, preferably methyl or ethyl, and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are hydrogen, fluorine, chlorine, (C.sub.1 -C.sub.4)alkoxy, (C.sub.1 -C.sub.4)alkyl or chlorine- or fluorine-substituted (C.sub.1 -C.sub.4)alkyl, in particular hydrogen, fluorine, chlorine, methyl or ethyl.
The compounds in which two, and in particular three, of the radicals R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are hydrogen are of great importance here.
Compounds which are also of importance are those of the formula (II) ##STR4## in which R is a straight-chain or branched (C.sub.1 -C.sub.20)-alkyl, phenyl or CH.sub.2 -phenyl, where the alkyl group or phenyl group can be substituted by halogen, (C.sub.1 -C.sub.4)-alkyl or (C.sub.1 -C.sub.4)-alkoxy, and in particular the alkyl group can be substituted by halogen or (C.sub.1 -C.sub.4)-alkoxy and in particular the phenyl group can be substituted by (C.sub.1 -C.sub.4)-alkyl or (C.sub.1 -C.sub.4)-alkoxy.
In the compounds of the formula (II), R is, in particular, a straight-chain or branched (C.sub.1 -C.sub.12)-alkyl, phenyl or CH.sub.2 -phenyl, preferably a straight-chain or branched (C.sub.1 -C.sub.6)-alkyl or phenyl. For completeness, it should be mentioned here that the compounds of the formula (II) are monoesters of N-carboxymethylene-4-chloroanthranilic acid.
N-Carboethoxymethylene-4-chloroanthranilic acid and N-carbomethoxymethylene-4-chloroanthranilic acid, N-carboisopropoxymethylene-4-chloroanthranilic acid, N-carbopropoxymethylene-4-chloroanthranilic acid, N-carbobutoxy-methylene-4-chloroanthranilic acid, N-carbohexoxymethylene4-chloroanthranilic acid and N-carbobenzoxymethylene-4-chloroanthranilic acid are of particular interest.
The invention furthermore relates to a process for the preparation of the compounds of the formula (I), which comprises reacting an N-carboxymethylene-anthranilic acid with alcohols ROH in the presence of a catalyst and, if appropriate, of a solvent.
The N-carboxymethyleneanthranilic acid employed in the preparation of the c

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Organic Chemistry 4th ed., Pine, Hendrickson, Cram and Hammond, McGraw-Hill 1980, p. 314, 1980.

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