Bis-aryl or heteroaryl indoles

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

Reexamination Certificate

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C548S312100, C548S311100

Reexamination Certificate

active

06337342

ABSTRACT:

This application is a 371 of PCT/SE98/02300 filed Dec. 14, 1998.
The present invention relates to novel compounds which are protein kinase C inhibitors, methods for their preparation, intermediates therefor and pharmaceutical compositions comprising them.
Protein kinase C (PKC) is a family of phospholipid-dependent serine/threonine-specific protein kinases which play an important role in cellular growth control, regulation and differentiation.
Since the activation of PKC has been implicated in several human disease processes, including various forms of cancer, different forms of inflammatory and/or immunological disorders as well as some neurological disorders, inhibition of PKC could be of therapeutic value in treating these conditions.
Several classes of compounds have been identified as PKC inhibitors, e.g. isoquinoline sulphonamides, sphingosine and related sphingolipids, indolocarbazoles and bisindolylmaleimides.
EP 0 328 026 describes the use of certain bisindolylmaleimides, a class of compounds related to the indolocarbazoles, in medicaments for the treatment of various conditions.
Baskakow et al.; SU 389096; 1973 describes 1,5 subsituted diphenyl imidazolones although these are not suggested to be of any therapeutic potential.
Although PKC inhibitors are described in the prior art, there is a need for specific anti-inflammatory and immunosuppressive compounds which are suitable for oral administration, and for inhalation.
The present invention provides kinase inhibitors which are particularly PKC inhibitors, methods for their preparation and intermediates used for their preparation.
The present invention also provides the use of the compounds of the present invention for the treatment of inflammatory, immunological, bronchopulmonary, cardiovascular, oncological or CNS-degenerative disorders.
Also provided by the present invention are pharmaceutical compositions comprising a compound according to the present invention, as active ingredient, together with a pharmaceutically acceptable adjuvant, diluent or carrier.
The present invention provides compounds of formula (I)
wherein:
Ar is an optionally substituted aromatic or heteroaromatic group,
R1 is H, C
1-6
alkyl, fluoro substituted C
1-6
alkyl, phenyl, benzyl, carboC
1-6
alkoxy, carbamoyl, or methyl(N—C
1-6
alkylcarbamoyl),
R2 is H, C
1-6
alkyl, aminoC
1-6
alkyl, hydroxyC
1-6
alkyl, (mono- or di- C
1-6
alkyl)aminoC
1-6
alkyl, (aminoC
1-3
alkylphenyl)C
1-3
alkyl, or amidinothio C
1-6
alkyl,
R3 is H or C
1-6
alkoxy,
R4 is H or together with R2, forms an annulated ring which may be substituted by hydroxyC
1-3
alkyl or amidinothio C
1-3
alkyl, or aminoC
1-3
alkyl,
and pharmaceutically acceptable salts thereof.
For compounds of formula (I), the following independent preferences apply:
Ar is an optionally substituted bicyclic aromatic or an optionally substituted bicyclic heteroaromatic group,
R1 is H or methyl; or if a fluoro substituted C
1-6
alkyl, is preferably CF
3
, when R4 is H, R2 is H, methyl, aminopropyl, hydroxypropyl or amidinothiopropyl, when R2 and R4 together form an annulated ring, they together comprise 4 or 5 carbons,
R3 is H or methoxy.
In more preferred embodiments of formula (I), Ar comprises a single heteroatom selected from N, O and S.
In yet more preferred embodiments of formula (I), Ar is selected from benzothiophene, naphthyl, phenoxyphenyl, or an optionally substituted indolyl which if substituted is preferably substituted with aminobutyl, aminomethyl benzyl, ethoxy carbamate, or 2,2,2-trichloroethylcarbamate.
Preferred compounds according to the present invention include:
5-[1-(3-Aminopropyl)-3-indolyl]-1-(3-indolyl)-1,3-dihydroimidazol-2-one,
5-[1-(3-Aminopropyl)-3-indolyl]-1-(3-benzo[b]thoiphenyl-1,3-dihydroimidazol-2-one,
5-[1-(3-Aminopropyl)-3-indolyl]-1-(1-naphthyl)-1,3-dihydroimidazol-2-one,
5-[1-{3-(Aminomethyl)benzyl}-3-indolyl]-1-(3-indolyl)-1,3-dihydroimidazol-2-one,
5-[1-(3-Aminopropyl)-3-indolyl]-1-(3-indolyl)-4-methyl-1,3-dihydroimidazol-2-one,
5-[1-(3-Amidinothiopropyl)-3-indolyl]-1-(3-indolyl)-1,3-dihydroimidazol-2-one,
5-{1-[3-(N,N-Dimethylamino)propyl]-3-indolyl}-1-(3-indolyl)-1,3-dihydroimidazol-2-one; and
5-[1-(3-Aminopropyl)-3-indolyl]-1-(3-indolyl)-4-phenyl-1,3-dihydroimidazol-2-one;
and salts thereof.
Salts of the compounds of formula (I) according to the invention are preferably pharmaceutically acceptable salts. Other salts may however be useful in the preparation of the compounds or in the preparation of pharmaceutically acceptable salts.
Pharmaceutically acceptable salts of compounds of the present invention are preferably those well known in the art as being suitable and are preferably acid addition salts and more preferably acetate salts or trifluoroacetate salts.
Compounds of formula (I) may be synthesised in the following ways:
(A) Compounds of formula (I) may be synthesised by converting a compound of formula (I) to a pharmaceutically acceptable salt thereof, or vice versa; or converting a pharmaceutically acceptable salt of a compound of formula (I) into a different pharmaceutically acceptable salt.
(B) Compounds of formula (I) may be synthesised by intramolecular condensation of a compound of formula (III):
in which Ar, R1, R2, R3 and R4 are as defined for formula (I).
The condensation may be performed under acidic conditions (preferably acetic acid or scandium(III) trifluoromethanesufonate) at elevated temperatures (preferably 110° C.).
Compounds of formula (I) in which Ar carries functional groups which might be sensitive to or interfere with the reaction conditions in process (B), can be prepared by intramolecular condensation of a corresponding compound of formula (III), but in which the functional groups on Ar are suitably protected, followed by subsequent deprotection.
Functional groups that might be sensitive for or interfere with the reaction conditions in process (B), as well as suitable protecting groups and deprotecting methods, are evident to those skilled in the art.
Compounds of formula (I), in which at least one of R
2
or Ar carries an amino, or hydroxy group; and pharmaceutically acceptable salts thereof, may be prepared by deprotecting a compound of formula (II) corresponding to formula (I) but in which at least one of R
2
or Ar carries a protected amino or hydroxy group.
In the processes described above, the protecting groups and conditions for deprotection are well known to those skilled in the art. Suitable protecting groups for amino groups are e.g phthaloyl groups and the deprotecting agent may be methylamine in e.g. water. The deprotecting step may be carried out in a suitable solvent, e.g tetrahydrofuran at about 10-30° C., e.g for about 5 hours. The hydroxy groups may be protected as their corresponding acetoxy groups and the deprotecting agent may be methylamine in e.g. water. The deprotecting step may be carried out in a suitable solvent, e.g tetrahydrofuran at about 10-30° C., e.g for about 16 hours.
The starting materials for the above processes (A) and (B) may be made by the methods described herein and particularly by those methods set out in the Examples or by methods analogous thereto. Other conventional methods for making the starting materials will be evident to those skilled in the art.
Compounds of formula (III) in which R2 is not H may be synthesised by alkylation with an optionally substituted alkylating agent, of compounds of formula (IV). The alkylating agent may be an alkyl halide, or an alkyl halide carrying a dialkyl amino group, or an alkylating agent carrying a protected amino or hydroxy group.
in which Ar, R1, R3 and R4 are as defined for formula (I).
Compounds of formula (III), in which R2 is not H, and Ar, R1, R3 and R4 are as defined in formula (I), may also be prepared by reaction of the appropriate isocyanate with a relevant alpha-ketoamine carrying R2, and in which R2 is not H, by standard techniques.
Compounds of formula (IV) may be prepared by reaction of the appropriate isocyanate with a relevant

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