Bicyclic heterocycles, pharmaceutical compositions...

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

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Details

C514S255030, C514S266100, C514S266400, C514S312000, C544S107000, C544S253000, C544S363000

Reexamination Certificate

active

06653305

ABSTRACT:

The present invention relates to bicyclic heterocycles of general formula
the tautomers, the stereoisomers, and the salts thereof, particularly the physiologically acceptable salts thereof with inorganic or organic acids or bases which have valuable pharmacological properties, particularly an inhibitory effect on signal transduction mediated by tyrosine kinases, the use thereof for treating diseases, particularly tumoral diseases, diseases of the lungs and respiratory tract, and the preparation thereof.
In the above general formula I
R
a
denotes a benzyl or 1-phenylethyl group or a phenyl group substituted by the groups R
1
and R
2
, where
R
1
denotes a hydrogen, fluorine, chlorine, or bromine atom, or a methyl, trifluoromethyl, cyano, or ethynyl group, and
R
2
denotes a hydrogen or fluorine atom,
R
b
denotes an R
3
O—CO—CH
2
—N—CH
2
—CH
2
—OH group optionally substituted at the methylene groups by 1 or 2 methyl or ethyl groups, where
R
3
represents a hydrogen atom or a C
1-4
-alkyl group,
a 2-oxomorpholin-4-yl group which may be substituted by 1 or 2 methyl or ethyl groups, or a N-[(1,3-dioxolan-2-yl)methyl]methylamino group,
R
c
denotes a hydrogen atom, a methoxy, ethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, tetrahydrofuran-3-yloxy, tetrahydropyran-3-yloxy, tetrahydropyran-4-yloxy, tetrahydrofuranylmethoxy, or tetrahydropyranylmethoxy group, and
n denotes an integer from the range from 1 to 3 with the proviso that the following compounds:
4-[(3-bromophenyl)amino]-6-({4-[N-(1,3-dioxolan-2-ylmethyl)-N-methylamino]-1-oxo-2-buten-1-yl}amino)-7-methoxyquinazoline;
4-[(3-bromophenyl)amino]-6-{[4-(2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-methoxyquinazoline;
4-[(3-bromophenyl)amino]-6-[(4-{N-[(tert-butyloxycarbonyl)methyl]-N-(2-hydroxyethyl)amino}-1-oxo-2-buten-1-yl)amino]-7-methoxyquinazoline;
4-[(3-bromophenyl)amino]-6-({4-[N-(carboxymethyl)-N-(2-hydroxyethyl)amino]-1-oxo-2-buten-1-yl}amino)-7-methoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-[(4-{N-[(ethoxycarbonyl)methyl]-N-(2-hydroxyethyl)amino}-1-oxo-2-buten-1-yl)amino]-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-[(4-{N-[(ethoxycarbonyl)methyl]-N-(2-hydroxy-2-methylpropyl)amino}-1-oxo-2-buten-1-yl)amino]-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(2,2-dimethyl-6-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(5,5-dimethyl-2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(5-methyl-2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline;
(R)-4-[(3-chloro-4-fluorophenyl)amino]-6-[(4-{N-[1-(ethoxycarbonyl)ethyl]-N-(2-hydroxyethyl)amino}-1-oxo-2-buten-1-yl)amino]-7-cyclopropylmethoxyquinazoline; and
(R)-4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(3-methyl-2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline
are excluded.
Preferred compounds of the above general formula I are those wherein
R
a
denotes a benzyl or 1-phenylethyl group or a phenyl group substituted by the groups R
1
and R
2
, where
R
1
denotes a hydrogen, fluorine, chlorine, or bromine atom, a methyl, trifluoromethyl, cyano, or ethynyl group, and
R
2
denotes a hydrogen or fluorine atom,
R
b
denotes an R
3
O—CO—CH
2
—N—CH
2
—CH
2
—OH group optionally substituted at the methylene groups by 1 or 2 methyl or ethyl groups, where
R
3
represents a hydrogen atom or a C
1-4
-alkyl group,
a 2-oxomorpholin-4-yl group which may be substituted by 1 or 2 methyl or ethyl groups, or an N-[(1,3-dioxolan-2-yl)methyl]methylamino group,
R
c
denotes a hydrogen atom, a methoxy, ethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, tetrahydrofuran-3-yloxy, tetrahydropyran-3-yloxy, tetrahydropyran-4-yloxy, tetrahydrofuranylmethoxy, or tetrahydropyranylmethoxy group, and
n denotes an integer from the range from 1 to 3 with the proviso that the following compounds:
4-[(3-bromophenyl)amino]-6-({4-[N-(1,3-dioxolan-2-ylmethyl)-N-methylamino]-1-oxo-2-buten-1-yl}amino)-7-methoxyquinazoline;
4-[(3-bromophenyl)amino]-6-{[4-(2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-methoxyquinazoline;
4-[(3-bromophenyl)amino]-6-[(4-{N-[(tert-butyloxycarbonyl)methyl]-N-(2-hydroxyethyl)amino}-1-oxo-2-buten-1-yl)amino]-7-methoxyquinazoline;
4-[(3-bromophenyl)amino]-6-({4-[N-(carboxymethyl)-N-(2-hydroxyethyl)amino]-1-oxo-2-buten-1-yl}amino)-7-methoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-[(4-{N-[(ethoxycarbonyl)methyl]-N-(2-hydroxyethyl)amino}-1-oxo-2-buten-1-yl)amino]-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-[(4-{N-[(ethoxycarbonyl)methyl]-N-(2-hydroxy-2-methylpropyl)amino}-1-oxo-2-buten-1-yl)amino]-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(2,2-dimethyl-6-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(5,5-dimethyl-2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(5-methyl-2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline;
(R)-4-[(3-chloro-4-fluorophenyl)amino]-6-[(4-{N-[1-(ethoxycarbonyl)ethyl]-N-(2-hydroxyethyl)amino}-1-oxo-2-buten-1-yl)amino]-7-cyclopropylmethoxyquinazoline;
(R)-4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(3-methyl-2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline;
4-[(3-chloro-4-fluorophenyl)amino]-6-[(4-[N-(1,3-dioxolan-2-ylmethyl)-N-methylamino]-1-oxo-2-buten-1-yl)amino]-7-cyclopropylmethoxyquinazoline;
4-(3-chloro-4-fluorophenyl)amino]-6-{[4-(3-methyl-2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline; and
4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(6-methyl-2-oxomorpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxyquinazoline,
are excluded, the tautomers, the stereoisomers, and the salts thereof.
Particularly preferred compounds of the above general formula I are those wherein
R
a
denotes a benzyl or 1-phenylethyl group or a phenyl group substituted by the groups R
1
and R
2
, where
R
1
denotes a fluorine, chlorine, or bromine atom, or a methyl or ethynyl group, and R
2
denotes a hydrogen or fluorine atom,
R
b
denotes an R
3
O—CO—CH
2
—N—CH
2
—CH
2
—OH group substituted at the methylene groups by 1 or 2 methyl or ethyl groups, where
R
3
represents a C
1-4
-alkyl group,
a 2-oxomorpholin-4-yl group which is substituted by 1 or 2 methyl or ethyl groups,
R
c
denotes a hydrogen atom, a methoxy, ethoxy, 2-methoxyethoxy, cyclobutyloxy, cyclopentyloxy, cyclopropylmethoxy, cyclobutylmethoxy, tetrahydrofuran-3-yloxy, tetrahydropyran-4-yloxy, tetrahydrofuranylmethox

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