Aryl aniline &bgr;2 adrenergic receptor agonists

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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C546S157000, C546S229000, C546S312000, C564S086000, C564S336000, C548S193000, C544S128000, C544S158000, C544S297000, C514S235200, C514S237800, C514S275000, C514S331000, C514S352000, C514S370000, C514S649000

Reexamination Certificate

active

06670376

ABSTRACT:

FIELD OF THE INVENTION
The invention is directed to novel &bgr;
2
adrenergic receptor agonists. The invention is also directed to pharmaceutical compositions comprising such compounds, methods of using such compounds to treat diseases associated with &bgr;
2
adrenergic receptor activity, and processes and intermediates useful for preparing such compounds.
BACKGROUND OF THE INVENTION
&bgr;
2
adrenergic receptor agonists are recognized as effective drugs for the treatment of pulmonary diseases such as asthma and chronic obstructive pulmonary disease (including chronic bronchitis and emphysema). &bgr;
2
adrenergic receptor agonists are also useful for treating pre-term labor, and are potentially useful for treating neurological disorders and cardiac disorders. In spite of the success that has been achieved with certain &bgr;
2
adrenergic receptor agonists, current agents possess less than desirable potency, selectivity, speed of onset, and/or duration of action. Thus, there is a need for additional &bgr;
2
adrenergic receptor agonists having improved properties. Preferred agents may possess, among other properties, improved duration of action, potency, selectivity, and/or onset.
SUMMARY OF THE INVENTION
The invention provides novel compounds that possess &bgr;
2
adrenergic receptor agonist activity. Accordingly, this invention provides compounds of formula (I):
wherein:
each of R
1
-R
5
is independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, and R
a
;
or R
1
and R
2
, R
2
and R
3
, R
3
and R
4
, or R
4
and R
5
are joined together to form a group selected from the group consisting of —C(R
d
)═C(R
d
)C(═O)NR
d
—, —CR
d
R
d
—CR
d
R
d
—C(═O)NR
d
—, —NR
d
C(═O)C(R
d
)═C(R
d
)—, —NR
d
C(═O)CR
d
R
d
—CR
d
R
d
—, —NR
d
C(═O)S—, —SC(═O)NR
d
—, —(CR
d
R
d
)
p
—, —S(CR
d
R
d
)
q
—, —(CR
d
R
d
)
q
S—, —S(CR
d
R
d
)
r
O—, —O(CR
d
R
d
)
r
S—, and —NHC(R
j
)═C(R
k
)—;
R
6
is hydrogen, alkyl, or alkoxy;
R
7
is hydrogen or alkyl;
R
8
is hydrogen or alkyl; or R
8
together with R
9
is —CH
2
— or —CH
2
CH
2
—;
R
9
is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, and R
a
, or R
9
together with R
8
is —CH
2
— or —CH
2
CH
2
—;
R
10
is hydrogen or alkyl;
each R
11
, R
12
, and R
13
is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, —NO
2
, halo, —NR
d
R
e
, —C(═O)R
d
, —CO
2
R
d
, —OC(═O)R
d
, —CN, —C(═O)NR
d
R
e
, —NR
d
C(═O)R
e
, —OC(═O)NR
d
R
e
, —NR
d
C(═O)OR
e
, —NR
d
C(═O)NR
d
R
e
, —OR
d
, —S(O)
m
R
d
, —NR
d
—NR
d
—C(═O)R
d
, —NR
d
N═CR
d
R
d
, —N(NR
d
R
e
)R
d
, and —S(O)
2
NR
d
R
e
;
or R
11
and R
12
together with the atoms to which they are attached form a fused benzo ring, which benzo ring can optionally be substituted with 1, 2, 3, or 4 R
c
;
or R
11
and R
12
together with the atoms to which they are attached form a heterocyclic ring;
wherein for R
1
-R
6
, R
9
, and R
11
-R
13
, each alkyl, alkenyl, and alkynyl is optionally substituted with R
m
, or with one or more (e.g. 1, 2, 3, or 4) substituents independently selected from R
b
; for R
1
-R
6
, R
9
, and R
11
-R
13
each aryl and heteroaryl is optionally substituted with 1, 2, 3, or 4 substituents independently selected from R
c
, and for R
1
-R
6
, R
9
, and R
11
-R
13
each cycloalkyl and heterocyclic ring is optionally substituted with 1, 2, 3, or 4 substituents independently selected from R
b
and R
c
;
each R
a
is independently —OR
d
, —NO
2
, halo, —S(O)
m
R
d
, —S(O)
2
OR
d
, —S(O)
m
NR
d
R
e
, —NR
d
R
e
, —O(CR
f
R
g
)
n
NR
d
R
e
, —C(═O)R
d
, —CO
2
R
d
, —CO
2
(CR
f
R
g
)
n
—CONR
d
R
e
, —OC(═O)R
d
, —CN, —C(═O)NR
d
R
e
, —NR
d
C(═O)R
e
, —OC(═O)NR
d
R
e
, —NR
d
C(═O)OR
e
, —NR
d
C(═O)NR
d
R
e
, —CR
d
(═N—OR
e
), —CF
3
, or —OCF
3
;
each R
b
is independently R
a
, oxo, or ═N—OR
e
;
each R
c
is independently R
a
, alkyl, alkenyl, or alkynyl; wherein each alkyl, alkenyl and alkynyl is optionally substituted with 1, 2, 3, or 4 substituents independently selected from R
b
;
each R
d
and R
e
is independently hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, or heterocyclyl; wherein each alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl and heterocyclyl is optionally substituted with one or more (e.g. 1, 2, 3, or 4) substituents independently selected from R
h
; or R
d
and R
e
together with the atoms to which they are attached form a heterocyclic ring having from 5 to 7 ring atoms, wherein the heterocyclic ring optionally contains 1 or 2 additional heteroatoms independently selected from oxygen, sulfur and nitrogen;
each R
f
and R
g
is independently hydrogen, alkyl, aryl, heteroaryl, cycloalkyl, or heterocyclyl; wherein each alkyl, aryl, heteroaryl, cycloalkyl and heterocyclyl is optionally substituted with 1, 2, 3, or 4 substituents independently selected from R
h
; or R
f
and R
g
together with the carbon atom to which they are attached form a ring having from 5 to 7 ring atoms, wherein the ring optionally contains 1 or 2 heteroatoms independently selected from oxygen, sulfur and nitrogen;
each R
h
is independently halo, C
1-8
alkyl, C
1-8
alkoxy, —S—C
1-8
alkyl, aryl, (aryl)-C
1-6
alkyl, (aryl)-C
1-8
alkoxy, heteroaryl, (heteroaryl)-C
1-6
alkyl, (heteroaryl)-C
1-8
alkoxy, hydroxy, amino, —NHC
1-6
alkyl, —N(C
1-6
alkyl)
2
, —OC(═O)C
1-6
alkyl, —C(═O)C
1-6
alkyl, —C(═O)OC
1-6
alkyl, —NHC(═O)C
1-6
alkyl, —C(═O)NHC
1-6
alkyl, carboxy, nitro, —CN, or —CF
3
;
R
j
and R
k
together with the carbon atoms to which they are attached form a phenyl ring that is optionally substituted with 1, 2, 3, or 4 R
c
;
each R
m
is independently aryl, heteroaryl, cycloalkyl or heterocyclyl; wherein each aryl or heteroaryl is optionally substituted with 1, 2, 3, or 4 substituents selected from the group consisting of R
c
, and wherein each cycloalkyl and heterocyclyl is optionally substituted with 1, 2, 3, or 4 substituents selected from R
b
;
m is 0, 1, or 2;
n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;
p is 3, 4, or 5;
q is 2, 3, or 4;
r is 1, 2, or 3;
w is 0, 1, 2, 3, or 4;
or a pharmaceutically-acceptable salt or solvate or stereoisomer thereof.
The invention also provides compounds of formula (II):
wherein:
R
4
is —CH
2
OH or —NHCHO and R
5
is hydrogen; or R
4
and R
5
taken together are —NHC(═O)CH═CH—;
R
11
is phenyl or heteroaryl, wherein each phenyl is optionally substituted with 1 or 2 substituents selected from halo, —OR
d
, —CN, —NO
2
, —SO
2
R
d
, —C(═O)R
d
, —C(═O)NR
d
R
e
, and C
1-3
alkyl, wherein C
1-3
alkyl is optionally substituted with 1 or 2 substituents selected from carboxy, hydroxy, and amino, and each R
d
and R
e
is independently hydrogen or C
1-3
alkyl; and wherein each heteroaryl is optionally substituted with 1 or 2 C
1-3
alkyl substituents; and
R
12
is hydrogen or —OC
1-6
alkyl;
or a pharmaceutically-acceptable salt or solvate or stereoisomer thereof.
The invention also provides a pharmaceutical composition comprising a compound of the invention and a pharmaceutically-acceptable carrier.
The invention also provides a method of treating a disease or condition associated with &bgr;
2
adrenergic receptor activity (e.g. a pulmonary disease, such as asthma or chronic obstructive pulmonary disease, pre-term labor, a neurological disorder, a cardiac disorder, or inflammation) in a mammal, comprising administering to the mammal, a therapeutically effective amount of a compound of the invention.
The invention also provides a method of treating a disease or condition associated with &bgr;
2
adrenergic receptor activity (e.g. a pulmonary disease, such as asthma or chronic obstructive pulmonary disease, pre-term labor, a neurological disorder, a cardiac disorder, or inflammation) in a mammal, comprising administering to the mammal, a therapeutically effective amou

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