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WO1996039391B1 - Styryl benzimidazole derivatives as inhibitors of smooth muscle cell proliferation - Google Patents

Styryl benzimidazole derivatives as inhibitors of smooth muscle cell proliferation

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Publication number
WO1996039391B1
WO1996039391B1 PCT/US1996/008375 US9608375W WO9639391B1 WO 1996039391 B1 WO1996039391 B1 WO 1996039391B1 US 9608375 W US9608375 W US 9608375W WO 9639391 B1 WO9639391 B1 WO 9639391B1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
compound
hydrogen
alkyl
pharmaceutically acceptable
Prior art date
Application number
PCT/US1996/008375
Other languages
French (fr)
Other versions
WO1996039391A1 (en
Filing date
Publication date
Priority claimed from US08/468,271 external-priority patent/US6444694B1/en
Application filed filed Critical
Priority to AT96916978T priority Critical patent/ATE205196T1/en
Priority to BR9609153A priority patent/BR9609153A/en
Priority to NZ309499A priority patent/NZ309499A/en
Priority to DE69615023T priority patent/DE69615023T2/en
Priority to EP96916978A priority patent/EP0830345B1/en
Priority to JP9500994A priority patent/JPH11506753A/en
Priority to DK96916978T priority patent/DK0830345T3/en
Priority to AU59684/96A priority patent/AU711965B2/en
Publication of WO1996039391A1 publication Critical patent/WO1996039391A1/en
Publication of WO1996039391B1 publication Critical patent/WO1996039391B1/en

Links

Abstract

Disclosed herein are compounds of formula (I) or (II), wherein R is phenyl or substituted phenyl; or R is furyl, pyridyl or quinolinyl; R1 and R2 are hydrogen, halogen, alkyl, alkoxy, nitro, carboxyl, alkoxycarbonyl or aryloxycarbonyl; R3 is hydrogen, alkyl, aryl or arylalkyl; R4 and R5 are hydrogen or alkyl; or a pharmaceutically acceptable salt thereof, which are useful as inhibitors of smooth muscle cell proliferation.

Claims

-28-
AMENDED CLAIMS
[received by the International Bureau on 27 November 1996 (27.11.96); original claims 1-27 replaced by amended claims 1-23 (6 pages)]
( 1 ) A compound of formula I or II:
Figure imgf000003_0001
wherein R is furyl, pyridyl, phenyl or phenyl substituted with alkoxy of 1 to 6 carbon atoms; Ri and R2 are hydrogen, alkoxy of 1 to 6 carbon atoms, nitro, carboxyl, alkoxycarbonyl of 2 to 7 carbon atoms or aryloxycarbonyl of 7 to 12 carbon atoms; R3 is hydrogen or benzyl substituted with alkoxycarbonyl of 2 to 6 carbon atoms; and R4 and R5 are hydrogen or methyl; provided that in formula I when Ri, R2 and R3 are hydrogen, R is not phenyl, 2- methoxyphenyl, 3-methoxyphenyl, 4- methoxyphenyl, 2,3-dimethoxyphenyl, 3,4,5- trimethoxyphenyl or 4-ethoxyphenyl, pyridyl, fur-2-yl or furan-3-yl, and provided that the compound of formula I is not 2-[2-(3,4-dimethoxyphenyl)-vinyl]-lH- benzoimidazole.
(2) A compound of formula I which is
Figure imgf000003_0002
wherein
Rl and R2 are hydrogen, halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, nitro, carboxyl, alkoxycarbonyl of 2 to 7 carbon atoms or aryloxycarbonyl of 7 to 12 carbon atoms; provided R1 and R2 is not nitro when the other is hydrogen, or a pharmaceutically acceptable salt thereof.
(3) A compound which is (E)-2-[2-(3,4-dimethoxyphenyl)-vinyl]-lH- benzoimidazole or a pharmaceutically acceptable salt thereof. (4) A compound which is 2-[2-(3,4-dimethoxyphenyl)-vinyl]-5-methoxy-lH- benzoimidazole or a pharmaceutically acceptable salt thereof.
(5) A compound which is { 2-[2-(3 .-dimetk axyphenyl)- vinyl]- lH-benzoimidazol-5- yl} -pheny 1-methanone or a pharmaceutically acceptable salt thereof.
(6) A compound which is 2-[2-(3,4-dimethoxyphenyl)-vinyl]-4,7-dimethoxy-5,6- dimethyl-lH-benzoimidazole or a pharmaceutically acceptable salt thereof.
(7) A compound which is (E)-2-[2-(3,4-dimethoxyphenyl)-vinyl]-lH- benzoimidazole-5-carboxylic acid methyl ester or a pharmaceutically acceptable salt thereof.
(8) A compound which is (E)-2-[2-(3,4-dimethoxyphenyl)-vinyl]-lH- benzoimidazole-5-carboxylic acid or a pharmaceutically acceptable salt thereof.
(9) A compound which is (E)-2-[2-(3,4-dimethoxyphenyl)-vinyl]-5-nitro-lH- benzoimidazole or a pharmaceutically acceptable salt thereof.
(10) A compound which is 4-{2-[2-(3,4-dimethoxyphenyl)-vinyl]-4,7-dimethoxy-5,6- dimethylbenzoimidazol-1 -ylmethyl} -benzoic acid methyl ester or a pharmaceutically acceptable salt thereof.
(11) A compound which is 2-[2-(3,4-dimethoxyphenyl)- vinyl] -5,6-dimethyl- 1H- benzoimidazol-4,7-dione or a pharmaceutically acceptable salt thereof.
(12) A compound which is (E)-5-nitro2-(2-pyridin-4-yl-vinyl)-lH-benzoimidazole or a pharmaceutically acceptable salt thereof.
(13) A compound which is (E)-2-(2-furan-3-yl-vinyl)-5-nitiO-lH-benzoimidazole or a pharmaceutically acceptable salt thereof.
(14) A compound of formula I or II:
Figure imgf000005_0001
wherein
R is phenyl or phenyl substituted with halogen, hydroxyl, alkoxy of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms, trifluoromethyl, or R is furyl, pyridyl or quinolinyl; Rl and R2 are hydrogen, halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, nitro, carboxyl, alkoxycarbonyl of 2 to 7 carbon atoms or aryloxycarbonyl of 7 to 12 carbon atoms; R3 is hydrogen, alkyl of 1 to 6 carbon atoms, aryl of 6 to 12 carbon atoms or arylalkyl of 7 to 12 carbon atoms optionally substituted with alkoxycarbonyl of 2 to 6 carbon atoms; R4 and R5 are hydrogen or alkyl of 1 to 6 carbon atoms; or a pharmaceutically acceptable salt thereof, provided that when R is substituted phenyl and one of R 1 or R2 is hydrogen, chlorine or nitro and the other is hydrogen, then R3 is not hydrogen, methyl or benzyl, and provided that when R3 is benzyl, R is not 2, 4-dichlorostyryl benzimidazole, and provided that when R is phenyl, Ri, R2 and R3 are not all hydrogen, and provided that when R\ or R2 is H, nitro or chloro and R3 is hydrogen, then R is not chloro-substituted phenyl, and provided that when one of Ri or R2 is bromo and R3 is hydrogen, then R is not phenyl; for use in the treatment of mammals.
(15) A compound as claimed in claim 14 for use in the treatment of diseases or conditions related to smooth muscle cell proliferation.
(16) A compound according to claim 15 wherein said smooth muscle cell proliferation manifests itself as restenosis following angioplasty.
(17) Use of a compound of formula I or II: -31
Figure imgf000006_0001
wherein
R is phenyl or phenyl substituted with halogen, hydroxyl, alkoxy of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms, trifluoromethyl, or R is furyl, pyridyl or quinolinyl; Rl and R2 are hydrogen, halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, nitro, carboxyl, alkoxycarbonyl of 2 to 7 carbon atoms or aryloxycarbonyl of 7 to 12 carbon atoms; R3 is hydrogen, alkyl of 1 to 6 carbon atoms, aryl of 6 to 12 carbon atoms or arylalkyl of 7 to 12 carbon atoms optionally substituted with alkoxycarbonyl of 2 to 6 carbon atoms; R4 and R5 are hydrogen or alkyl of 1 to 6 carbon atoms; or a pharmaceutically acceptable salt thereof, for the manufacture of a medicament for the prevention of smooth muscle cell proliferation in a mammal .
(18) Use of a compound according to claim 17 wherein said smooth muscle cell proliferation manifests itself as restenosis following angioplasty.
(19) A pharmaceutical composition comprising a compound of formula I or II according to any of claims 1 to 16 and a pharmaceutically acceptable carrier.
(20) A method for treatment of a mammal which comprises administering to that mammal, orally or parenterally, a compound of formula I or II:
Figure imgf000006_0002
wherein -32-
R is phenyl or phenyl substituted with halogen, hydroxyl, alkoxy of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms, trifluoromethyl, or R is furyl, pyridyl or quinolinyl; Rl and R2 are hydrogen, halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, nitro, carboxyl, a'-coxycarbonyl of 2 to 7 carbon atoms or aryloxycarbonyl of 7 to 12 carbon atoms; R3 is hydrogen, alkyl of 1 to 6 carbon atoms, aryl of 6 to 12 carbon atoms or arylalkyl of 7 to 12 carbon atoms optionally substituted with alkoxycarbonyl of 2 to 6 carbon atoms; R4 and R5 are hydrogen or alkyl of 1 to 6 carbon atoms; or a pharmaceutically acceptable salt thereof.
(21) A method according to claim 20 for preventing smooth muscle cell proliferation in mammals.
(22) A method according to claim 21 in which the smooth muscle cell proliferation manifests itself as restenosis following angioplasty.
(23) A process for the preparation of a compound of formula I or II:
Figure imgf000007_0001
wherein
R is phenyl or phenyl substituted with halogen, hydroxyl, alkoxy of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms, trifluoromethyl, or R is furyl, pyridyl or quinolinyl; Rl and R2 are hydrogen, halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, nitro, carboxyl, alkoxycarbonyl of 2 to 7 carbon atoms or aryloxycarbonyl of 7 to 12 carbon atoms; R3 is hydrogen, alkyl of 1 to 6 carbon atoms, aryl of 6 to 12 carbon atoms or arylalkyl of
7 to 12 carbon atoms optionally substituted with alkoxycarbonyl of 2 to 6 carbon atoms; R4 and R5 are hydrogen or alkyl of 1 to 6 carbon atoms; or a pharmaceutically acceptable salt thereof, which comprises: -33-
(a) reacting a nitrile of formula 1
R' .CN
1 with an alcohol and hydrogen chloride to form the compound of formula 2:
NH
R ',V^OMe - HCl
2
(b) reacting the compound of formula 2 with a compound of formula 3:
Figure imgf000008_0001
3 in the presence of an alcohol to form the compound of formula 4:
Figure imgf000008_0002
4
(c) reacting the compound of formula 4 with R3 -halide in the presence of an alkylating agent to form the compound of formula I:
(d) and optionally reacting 5:
Figure imgf000008_0003
5 with (NHU)2Ce(N)3)6 in the presence of acetic acid to form the compound of formula II:
Figure imgf000008_0004
PCT/US1996/008375 1995-06-06 1996-06-03 Styryl benzimidazole derivatives as inhibitors of smooth muscle cell proliferation WO1996039391A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AT96916978T ATE205196T1 (en) 1995-06-06 1996-06-03 STYRYLBENZIMIDAZOLE DERIVATIVES AS INHIBITORS OF SMOOTH MUSCLE CELL PROLIFERATION
BR9609153A BR9609153A (en) 1995-06-06 1996-06-03 Styrene-benzimidazole derivatives as inhibitors of smooth muscle cell proliferation
NZ309499A NZ309499A (en) 1995-06-06 1996-06-03 Styryl benzimidazole derivatives useful as inhibitors of smooth muscle cell proliferation
DE69615023T DE69615023T2 (en) 1995-06-06 1996-06-03 STYRYLBENE IMIDAZOLE DERIVATIVES AS INHIBITORS OF SMOOTH MUSCLE CELL PROPELLATION
EP96916978A EP0830345B1 (en) 1995-06-06 1996-06-03 Styryl benzimidazole derivatives as inhibitors of smooth muscle cell proliferation
JP9500994A JPH11506753A (en) 1995-06-06 1996-06-03 Styrylbenzimidazole derivatives as inhibitors of smooth muscle cell proliferation
DK96916978T DK0830345T3 (en) 1995-06-06 1996-06-03 Styryl benzimidazole derivatives as inhibitors of smooth muscle cell proliferation
AU59684/96A AU711965B2 (en) 1995-06-06 1996-06-03 Styryl benzimidazole derivatives as inhibitors of smooth muscle cell proliferation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/468,271 US6444694B1 (en) 1995-06-06 1995-06-06 Styryl benzimidazole derivatives
US08/468,271 1995-06-06

Publications (2)

Publication Number Publication Date
WO1996039391A1 WO1996039391A1 (en) 1996-12-12
WO1996039391B1 true WO1996039391B1 (en) 1997-01-09

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Country Status (19)

Country Link
US (1) US6444694B1 (en)
EP (1) EP0830345B1 (en)
JP (1) JPH11506753A (en)
KR (1) KR19990022266A (en)
CN (1) CN1192206A (en)
AR (1) AR002749A1 (en)
AT (1) ATE205196T1 (en)
AU (1) AU711965B2 (en)
BR (1) BR9609153A (en)
CA (1) CA2223585A1 (en)
DE (1) DE69615023T2 (en)
DK (1) DK0830345T3 (en)
ES (1) ES2162063T3 (en)
HU (2) HUP9900914A2 (en)
IL (1) IL118385A0 (en)
NZ (1) NZ309499A (en)
PT (1) PT830345E (en)
WO (1) WO1996039391A1 (en)
ZA (1) ZA964693B (en)

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US6448281B1 (en) 2000-07-06 2002-09-10 Boehringer Ingelheim (Canada) Ltd. Viral polymerase inhibitors
EP2335700A1 (en) 2001-07-25 2011-06-22 Boehringer Ingelheim (Canada) Ltd. Hepatitis C virus polymerase inhibitors with a heterobicylic structure
US7098231B2 (en) 2003-01-22 2006-08-29 Boehringer Ingelheim International Gmbh Viral polymerase inhibitors
US7223785B2 (en) 2003-01-22 2007-05-29 Boehringer Ingelheim International Gmbh Viral polymerase inhibitors
KR20120091276A (en) 2004-02-20 2012-08-17 베링거 인겔하임 인터내셔날 게엠베하 Viral polymerase inhibitors
EP1915378A4 (en) 2005-08-12 2009-07-22 Boehringer Ingelheim Int VIRAL POLYMERASE INHIBITORS
CA2656851C (en) 2006-07-05 2013-12-10 Fibrotech Therapeutics Pty Ltd Substituted cinnamoyl anthranilate compounds exhibiting anti-fibrotic activity
US9062076B2 (en) 2009-10-22 2015-06-23 Fibrotech Therapeutics Pty Ltd Fused ring analogues of anti-fibrotic agents
EP3577103A1 (en) 2017-02-03 2019-12-11 Certa Therapeutics Pty Ltd. Anti-fibrotic compounds
KR102853258B1 (en) * 2023-06-20 2025-09-01 이원다이애그노믹스(주) Novel compound, preparation method thereof and pharmaceutical composition for preventing and treating cancer as active ingredient

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US3575956A (en) * 1967-07-24 1971-04-20 Sterling Drug Inc 2-substituted-benz-x-azol-6-ylazo-aminonaphthalene compounds
DE1670908A1 (en) * 1967-08-16 1971-04-29 Hoechst Ag Novel benzimidazole compounds, processes for their preparation and their use as optical brightening agents
FR2104717A1 (en) * 1970-09-28 1972-04-21 Dynachim Sarl Organophosphorus pesticides stabilised with benzimidazole derivs - - for controlling insects and internal parasites of animals
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US5196446A (en) 1990-04-16 1993-03-23 Yissum Research Development Company Of The Hebrew University Of Jerusalem Certain indole compounds which inhibit EGF receptor tyrosine kinase
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