Benzopyran and related LTB antagonists

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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514255, 514256, 514307, 514309, 514312, 514314, 514337, 514432, 514444, 514269, 514274, 544298, 544316, 544319, 544405, 544333, 546139, 546141, 546152, 546153, 546256, 5462684, 5462804, 5462811, 5462834, 5462841, 5462844, 5462744, 5462777, 5462791, 5462811, C07D31122, A61K 3135

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055524354

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BRIEF SUMMARY
This invention relates to novel benzopyran and other benzo-fused leukotriene B.sub.4 (LTB.sub.4) antagonists, to pharmaceutical compositions containing such compounds, and to a method of using such compounds as LTB.sub.4 antagonists.
The compounds of this invention inhibit the action of LTB.sub.4 and are therefore useful in the treatment of LTB.sub.4 induced illnesses such as inflammatory disorders including rheumatoid arthritis, osteoarthritis, inflammatory bowel disease, psoriasis and other skin disorders such as eczema, erythma, pruritis and acne, stroke and other forms of reperfusion injury, graft rejection, autoimmune diseases, asthma and other conditions where marked neutrophil infiltration occurs.
LTB.sub.4 antagonists are disclosed in European patent publications 276 064 and 292 977 which refer to diphenylethers, benzophenones, and other compounds containing two phenyl groups, and 7-(3-alkoxy-4-alkanoyl-phenoxy)alkoxy benzopyran derivatives, respectively.
According to the invention, it was found that the following compounds of formula I have LTB.sub.4 antagonistic properties: ##STR2## wherein A is O, CH.sub.2, S, NH, or N(C.sub.1 -C.sub.6 alkyl); n is 0, 1 or 2;
R.sup.1 is a substituent at position b or c of the formula ##STR3##
R.sup.2, R.sup.8, R.sup.9 and R.sup.10 are hydrogen or each independently are one or any two of the following: fluoro, chloro, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.4 perfluoroalkyl, C.sub.1 -C.sub.4 perfluoroalkoxy, C.sub.1 -C.sub.6 alkylthio, C.sub.1 -C.sub.6 alkylsulfinyl, or C.sub.1 -C.sub.6 alkylsulfonyl; R.sup.3 is --(CH.sub.2).sub.q CHR.sup.11 R.sup.12, --(CH.sub.2).sub.q R.sup.12, --O(CH.sub.2).sub.p CHR.sup.11 R.sup.12, or --(CH.sub.2).sub.p R.sup.12, wherein p is 0, 1 or 2 and q is 0, 1, 2, or 3; R.sup.4 is carboxy, tetrazolyl or R.sup.13 SO.sub.2 NHCO; R.sup.11 is hydrogen, C.sub.1 -C.sub.6 alkyl or R.sup.8 -substituted phenyl wherein R.sup.8 is as defined above; R.sup.12 and R.sup.13 are hydrogen or each independently are C.sub.1 -C.sub.6 alkyl or C.sub.3 -C.sub.8 cycloalkyl; or phenyl, thienyl, pyridyl, furyl, naphthyl, quinolyl, isoquinolyl, pyrimidinyl, or pyrazinyl, each of which is optionally substituted by phenyl, R.sup.9, or R.sup.9 -substituted phenyl wherein R.sup.9 is as defined above; and the salts and esters of those compounds of formula I containing a carboxy group, wherein the esters contain ester groups selected from the group consisting of C.sub.1 -C.sub.6 alkyl, phenyl(C.sub.1 -C.sub.6) alkyl, C.sub.3 -C.sub.7 cycloalkyl, and phenyl and benzyl substituted by fluoro, chloro, C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy.
Preferred compounds of the invention are those of formula I wherein A is oxygen, those wherein n is 1, those wherein R.sup.1 is a substituent at position c, those wherein R.sup.2 is hydrogen or monofluoro, and those wherein R.sup.3 is benzyl, 4-fluorobenzyl, 4-phenylbenzyl, 4-(4-fluorophenyl)benzyl, phenethyl or phenoxy, preferably benzyl or 4-phenylbenzyl.
More specific compounds of the formula I are those wherein A is oxygen, n is 1, and R.sup.1 is a substituent at position c, and those wherein A is oxygen, n is 1, R.sup.1 is a at position c and is 2-carboxyphenyl, 3-carboxyphenyl, 2-carboxy-3-fluorophenyl, 2-carboxy-4-fluorophenyl, 2-carboxy-5-fluorophenyl, 2-carboxy-6-fluorophenyl, 2-carboxy-5-trifluoromethylphenyl, 2-tetrazolyl-5-fluorophenyl, 2-carboxy-5-chlorophenyl, or 2-carboxy-5-methoxyphenyl, R.sup.2 is hydrogen or monofluoro and R.sup.3 is benzyl, 4-fluorobenzyl, 4-phenylbenzyl, 4-(4-fluorophenyl)benzyl, phenethyl or phenoxy,
Specific compounds are those wherein A is oxygen, n is 1, R.sup.2 is hydrogen, R.sup.3 is benzyl, 4-fluorobenzyl, 4-phenylbenzyl, 4-(4-fluorophenyl)benzyl, phenethyl or phenoxy, and R.sup.1 is at position c and is 2-carboxyphenyl, 3-carboxyphenyl, 2-carboxy-3-fluorophenyl, 2-carboxy-4-fluorophenyl, 2-carboxy-5-fluorophenyl, 2-carboxy-6-fluorophenyl,2-carboxy-5-trifluoromethylphenyl,2-tetrazolyl-5- fluorophenyl,2-carboxy-5-chlorophenyl or 2-carboxy-5-methoxyphenyl, an

REFERENCES:
patent: 4238501 (1980-12-01), Kabbe et al.
patent: 4565882 (1986-01-01), Miyano et al.
Djuric et al., J. of Medicinal Chemistry, 32, 1145-7 (Jun. 1989).

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