Methylen-oxindole derivatives compositions and tyrosine kinase i

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...

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548455, 514421, C07D40106, A61K 3140

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active

054099498

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to new 3-methylene-2-oxindole derivatives, to a process for their preparation, to pharmaceutical compositions containing them and to their use as therapeutic agents.
The present invention provides compounds having the following general formula (I) ##STR3## wherein
R is a group ##STR4## in which R.sub.4 is hydrogen, hydroxy, C.sub.1 -C.sub.6 alkoxy, C.sub.2 -C.sub.6 alkanoyloxy, carboxy, nitro or NHR.sub.7, wherein R.sub.7 is hydrogen or C.sub.1 -C.sub.6 alkyl; nitro or --NHR.sub.7 in which R.sub.7 is as defined above; and the pharmaceutically acceptable salts thereof; and wherein, when, at the same time, R.sub.2 is hydrogen, C.sub.1 -C.sub.6 alkyl, halogen or cyano and R.sub.3 is hydrogen, R.sub.1 and n being as defined above, then at least one of R.sub.4, R.sub.5 and R.sub.6 is other than hydrogen. In the compounds of the present invention each of the substituents R, --OR.sub.1 and R.sub.2 may be independently on either of the benzene or pyrrole moiety of the condensed indole ring system.
The invention includes within its scope all the possible isomers, stereoisomers, in particular Z and E isomers and their mixtures, and the metabolites and the metabolic precursors or bio-precursors (otherwise known as pro-drugs) of the compounds of formula (I).
The substituent R is preferably linked to position 2 or 3 of the indole ring, in particular to position 3.
When n is 2, each of the --OR.sub.1 groups may be the same or different.
A substituent --OR.sub.1 is preferably linked to position 4, 5, 6 or 7, in particular to position 5 or 7.
The substituent R.sub.2 is preferably on the benzene ring moiety, in particular linked to position 5.
Of course only one of the substituents R, --OR.sub.1 and R.sub.2 can be linked to the same position in the indole ring system. The substituent R.sub.4 is preferably linked to position 4 or 5, in particular to position 5.
When R.sub.4 is carboxyl, nitro or --NHR.sub.7, in which R.sub.7 is as defined above, the R.sub.2 substituent preferably has not the same meanings. Vice versa, when R.sub.2 is carboxyl, nitro or --NHR.sub.7, in which R.sub.7 is as defined above, the R.sub.4 substituent preferably is other than carboxy, nitro or --NHR.sub.7.
The alkyl groups, and the alkyl moiety in the alkanoyl groups, may be branched or straight alkyl chain. A C.sub.1 -C.sub.6 alkyl group is preferably a C.sub.1 -C.sub.4 alkyl group, e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl, in particular methyl or ethyl. A C.sub.2 -C.sub.6 alkanoyl group is preferably a C.sub.2 -C.sub.4 alkanoyl group, in particular acetyl, propionyl or butyryl. A halogen is, preferably, chlorine, bromine or fluorine, in particular bromine.
Pharmaceutically acceptable salts of the compounds of the invention include acid addition salts, with inorganic, e.g. nitric, hydrochloric, hydrobromic, sulphuric, perchloric and phosphoric acids, or organic, e.g. acetic, propionic, glycolic, lactic, oxalic, malonic, malic, maleic, tartaric, citric, benzoic, cinnamic, mandelic and salicylic acids, and salts with inorganic, e.g. alkali metal, especially sodium or potassium, bases or alkaline-earth metal, especially calcium or magnesium bases, or with organic bases, e.g. alkylamines, preferably triethyl-amine.
As stated above the present invention also includes within its scope pharmaceutically acceptable bio-precursors (otherwise known as pro-drugs) of the compounds of formula (I), i.e. compounds which have a different formula to formula (I) above but which nevertheless upon administration to a human being are converted directly or indirectly in vivo into a compound of formula (I). Preferred compounds of the invention are the compounds of formula (I), wherein R.sub.5 and R.sub.6 are hydrogen;
More preferred compounds of the invention are the compounds of formula (I) in which
R is as defined above, R.sub.4 is hydroxy, amino or carboxy; and R.sub.5 and R.sub.6 are hydrogen; n is 0 or 1; R.sub.1 is hydrogen; R.sub.2 is hydrogen, amino or carboxy; R.sub.3 is hydrogen; and the pharmaceutically

REFERENCES:
patent: 4642309 (1987-02-01), Michel et al.
Patent Abstracts of Japan, 19 Sep. 1991, & JP, A, 3 213 847.
Canadian J. Chem. vol. 46, No. 13, 1 Jul. 1968, pp. 2189-2194; R. Hodges, et al.: `Chemical and biological properties of some oxinodolidyl-3-methines`.
Chem. Ber. vol. 102, No. 4, 1969, pp. 1347-1356; H. Von Dobeneck et al.: `alpha.beta'-Diindolylmethane und-methene. Der Urorosein-Chromophor`.
Yakugaku Zasshi, vol. 97, No. 9, 1977, pp. 1033-1039; G. Kobayashi et al.: "Anti-tumor Activity of Indole Derivatives".

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