Retinoic acid mimetic anlides

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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C514S383000, C514S400000, C514S407000, C514S427000, C548S253000, C548S267600, C548S338500, C548S375100, C548S561000

Reexamination Certificate

active

06319939

ABSTRACT:

The present invention concerns anilides, their N-oxides and addition salts; it further relates to processes for their preparation, compositions comprising them. The compounds of the present invention are potent inhibitors of the retinoic acid metabolism, and hence, their use as a medicine is also described.
EP-A-0,260,744, published on Mar. 23, 1988, discloses (1H-imidazol-1-ylmethyl) substituted benzimidazoles as inhibitors of the androgen formation from C
21
-steroids, as inhibitors of the biosynthesis of thromboxane A
2
, and also having the capability to increase the excretion of ureic acid. EP-A-0,371,559, published on Jun. 6, 1990, discloses said benzimidazoles and analogous benzotriazoles as potent suppressers of the plasma elimination of endogenously or exogenously administered retinoic acid.
Retinoic acid (RA) is a key molecule in the regulation of growth and differentiation of epithelial tissues. However, RA is very rapidly metabolized by a series of enzymatic reactions, which results in its deactivation. Inhibition of RA-metabolism leads to enhanced RA levels in plasma and tissue. Therefore, compounds with such an inhibitory action, also called retinoic mimetic activity, have therapeutic and/or preventive potential in the field of dermatology and oncology.
The present invention is concerned with compounds of formula
the N-oxides, the pharmaceutically acceptable addition salts and the stereochemically isomeric forms thereof, wherein:
X represents O, S or NR
3
;
R
1
represents hydrogen, hydroxy, C
1-6
alkyl or aryl;
R
2
represents hydrogen; C
1-12
alkyl; C
3-7
cycloalkyl; C
2-8
alkenyl; aryl; Het
1
; or C
1-12
alkyl substituted with one or two substituents selected from C
3-7
cycloalkyl, hydroxy, C
1-4
alkyloxy, cyano, amino, mono- and di(C
1-4
alkyl)amino, mono- or di(arylC
1-4
alkyl)amino, di(arylC
1-4
alkyl)aminocarbonyloxy, (C
1-4
alkyl) (arylC
1-4
alkyl)amino, mono- and di(aryl)amino, (C
1-4
alkyl)(di(C
1-4
alkyl)-aminoC
1-4
alkyl)amino, pyrrolidinyl, piperidinyl, piperazinyl optionally substituted with C
1-4
alkyl, morpholinyl, perhydro-azepinyl, carboxyl, C
1-4
alkyloxycarbonyl, aminocarbonyl, mono- and di(C
1-4
alkyl)aminocarbonyl, aryl, aryloxy and arylthio; or
R
1
and R
2
taken together may form a bivalent radical of formula —R
1
—R
2
— wherein —R
1
—R
2
— represents —(CH
2
)
n
— wherein n is 2, 3, 4, 5 or 6;
R
3
represents hydrogen, C
1-6
alkyl, aryl, Het
1
or C
1-6
alkyl substituted with aryl or Het
1
;
R
4
represents hydrogen; hydroxy; mercapto; C
1-6
alkyloxy; C
1-6
alkylthio; aryloxy; arylthio; Het
1
-oxy; Het
1
-thio; C
1-12
alkyl optionally substituted with one, two or three substituents each independently selected from halo, hydroxy, mercapto, C
1-6
alkyloxy, C
1-6
alkylthio, aryloxy, arylthio, Het
1
-oxy, Het
1
-thio, C
3-7
cycloalkyl optionally substituted with hydroxycarbonylC
1-6
alkyl, carboxyl, C
1-6
alkyloxy-carbonyl, arylC
1-6
alkyloxy, arylC
1-6
alkylthio, aryl, Het
1
; C
2-8
alkenyl optionally substituted with one, two or three substituents selected from halo, C
3-7
cycloalkyl, aryl, Het
1
; C
2-8
alkynyl optionally substituted with halo, C
3-7
cycloalkyl, aryl; C
3-7
cycloalkyl optionally substituted with C
1-6
alkyl or aryl; C
5-7
cycloalkenyl optionally substituted with C
1-6
alkyl or aryl; aryl; Het
1
; or
—Alk—NR
3
R
5
  (i) or
—NR
3
R
5
  (ii)
 wherein Alk represents C
1-6
alkanediyl; and
R
5
represents hydrogen, C
1-6
alkyl, aryl, Het
1
, (aryl or Het
1
)C
1-6
alkyl, (aryl or Het
1
)carbonyl or (aryl or Het
1
)C
1-6
alkyloxycarbonyl;
aryl represents indanyl, indenyl, naphtyl, 5,6,7,8-tetrahydro-2-naphtalenyl, phenyl; said indanyl, indenyl, naphtyl or phenyl may be substituted with one, two, three, four or five substituents each independently selected from hydroxy, halo, nitro, cyano, amino, azido, mono- or di(C
1-6
alkyl)amino, C
1-6
alkylcarbonylamino, C
1-6
alkyl, polyhaloC
1-6
alkyl, hydroxyC
1-6
alkyl, phenyl, phenyloxy, phenylC
1 6
alkyloxy, pyridinylC
1-6
alkyloxy, C
1-6
alkyloxy, formyl, carboxyl and C
1-6
alkylcarbonyl; or two adjacent carbon atoms on said phenyl may be substituted by a single bivalent radical having the formula C
1-12
alkanediyl or polyhaloC
1-12
alkanediyl;
Het represents an unsaturated heterocycle selected from pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl and pyridinyl; each of said unsaturated heterocycles may optionally be substituted with amino, mercapto, C
1-6
alkyl, C
1-6
alkylthio or aryl; and
Het
1
represents a monocyclic heterocycle selected from pyrrolidinyl, pyrrolyl, pyrazolyl, imidazolyl, 1,3,4-triazolyl, 1,2,4-triazolyl, tetrahydrofuranyl, furanyl, thiolanyl, thienyl, dioxolanyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, isoxazolidinyl, oxazolidinyl, isothiazolidinyl, thiazolidinyl, piperidinyl, pyridinyl, piperazinyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, tetrahydropyranyl, pyranyl, morpholinyl and dioxanyl; each of said monocyclic heterocycles may be optionally substituted with one or two substituents each independently selected from C
1-4
alkyl, hydroxy, amino, halo, aryl, arylcarbonyl or C
1-4
alkyloxycarbonyl; or a bicyclic heterocycle selected from indolinyl, indolyl, indazolyl, benzimidazolyl, benzotriazolyl, benzofuranyl, benzothienyl, 2H-1-benzopyranyl, 3,4-dihydro-2H-1-benzopyranyl, benzthiazolyl, isoquinolinyl, quinolinyl, 3,4-dihydroquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, chromanyl, 1,4-benzodioxinyl, 1,4-benzoxathianyl, benzodioxanyl and benzodioxolanyl; each of said bicyclic heterocycles may be substituted with one or two substituents each independently selected from C
1-4
alkyl, hydroxy, amino, halo, aryl, arylcarbonyl or C
1-4
alkyloxycarbonyl.
As used in the foregoing definitions and hereinafter, halo is generic to fluoro, chloro, bromo and iodo; C
3-7
cycloalkyl is generic to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; C
5-7
cycloalkenyl is generic to cyclopentenyl, cyclohexenyl and cycloheptenyl; C
2-8
alkenyl defines straight and branch chained hydro-carbon radicals containing one double bond and having from 2 to 8 carbon atoms such as, for example, ethenyl, 1-propenyl, 2-butenyl, 2-pentenyl, 3-pentenyl, 3-methyl-2-butenyl, 3-hexenyl, 3-heptenyl, 2-octenyl and the like; C
1-4
alkyl defines straight and branched chain saturated hydrocarbon radicals having from 1 to 4 carbon atoms such as, for example, methyl, ethyl, propyl, butyl, 1-methylethyl, 2-methylpropyl, 2,2-dimethylethyl and the like; C
1-6
alkyl is meant to include C
1-4
alkyl and the higher homologues thereof having 5 or 6 carbon atoms such as, for example, pentyl, 2-methylbutyl, hexyl, 2-methylpentyl and the like; C
1-12
alkyl is meant to include C
1-6
alkyl and the higher homologues thereof having from 7 to 12 carbon atoms such as, for example, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2-methylhexyl, 3-ethyloctyl and the like; C
1-12
alkanediyl defines bivalent straight and branched chain saturated hydrocarbon radicals having from 1 to 12 carbon atoms such as, for example, 1,1-methanediyl, 1,2-ethanediyl, 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,2-propanediyl, 2,3-butanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,11-undecanediyl, 1,12-dodecanediyl, 1,1,4,4-tetra-methylbutane-1,4-diyl and the like; polyhaloC
1-6
alkyl is defined as polyhalosubstituted C
1-6
alkyl, in particular C
1-6
alkyl substituted with 1 to 6 halogen atoms, more in particular difluoro- or trifluoromethyl; polyhaloC
1-12
alkanediyl is defined as polyhalo-substituted C
1-12
alkanediyl, in particular C
1-12
alkanediyl substituted with 1 to 12 halogen atoms; triazolyl is meant to include 1,2,4-triazolyl and 1,3,4-triazolyl; tetrazolyl is meant to include 1H-tetrazolyl and 2H-tetrazolyl; benzodioxanyl is meant to include 2,3-dihydro-1,4-benzodioxinyl.
The unsaturated heteroaryl group represented by Het may be attached to the remainder of the molecule of formula (I) through any ring carbon or heteroatom as appropriate. Thus, for example, when the heteroaryl group is imidaz

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