Tetrahydropyran derivatives and their use as therapeutic agents

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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C514S459000, C514S422000, C514S397000, C514S359000, C514S326000, C514S231500, C549S416000, C549S417000, C549S419000, C544S149000, C548S266200, C548S311100, C548S255000, C548S517000, C546S207000

Reexamination Certificate

active

06458830

ABSTRACT:

CROSS REFERENCE TO RELATED APPLICATIONS
This application is a U.S. National Phase application under 35 U.S.C. § 371 of PCT Application No. PCT/GB00/00974, filed Mar. 16, 2000, which claims priority under 35 U.S.C. § 119 from GB Application No. 9906480.0, filed Mar. 19, 1999 and GB Application No. 9924616.7 filed Oct. 18, 1999.
This invention relates to a class of tetrahydropyran compounds which are useful as tachykinin antagonists. More particularly, the compounds of the invention are useful as neurokinin 1(NK-1) receptor antagonists.
The present invention provides compounds of the formula (I):
wherein
R
1
is hydrogen, halogen, C
1-6
alkyl, C
1-6
alkoxy, fluoroC
1-6
alkyl, fluoroC
1-6
alkoxy, C
3-7
cycloalkyl, C
3-7
cycloalkylC
1-4
alkyl, NO
2
, CN, SR
a
, SOR
a
, SO
2
R
a
, CO
2
R
a
, CONR
a
R
b
, C
2-6
alkenyl, C
2-6
alkynyl or C
1-4
alkyl substituted by C
1-4
alkoxy, wherein R
a
and R
b
each independently represent hydrogen or C
1-4
alkyl;
R
2
is hydrogen, halogen, C
1-6
alkyl, fluoroC
1-6
alkyl or C
1-6
alkoxy substituted by C
1-4
alkoxy;
R
3
is hydrogen, halogen or fluoroC
1-6
alkyl;
R
4
is hydrogen, halogen, C
1-6
alkyl, C
1-6
alkoxy, fluoroC
1-6
alkyl, fluoroC
1-6
alkoxy, hydroxy, NO
2
, CN, SR
a
, SOR
a
, SO
2
R
a
, CO
2
R
a
, CONR
a
R
b
, C
2-6
alkenyl, C
2-6
alkynyl or C
1-4
alkyl substituted by C
1-4
alkoxy, wherein R
a
and R
b
are as previously defined;
R
5
is hydrogen, halogen, C
1-6
alkyl, fluoroC
1-6
alkyl or C
1-6
alkoxy substituted by C
1-4
alkoxy;
R
6
represents hydrogen or a C
1-4
alkyl group optionally substituted by a hydroxy group;
R
7
represents halogen, hydroxy, C
2-4
alkenyl, C
2-4
alkynyl, N
3
, —NR
11
R
12
, —NR
a
COR
b
, —OSO
2
R
a
, —(CH
2
)
p
NR
a
(CH
2
)
q
COOR
b
, COR
a
, COOR
a
, —N═C═O, or a five membered or six membered nitrogen-containing heteroaromatic ring optionally containing 1, 2 or 3 additional heteroatoms selected from N, O and S which heteroaromatic ring is optionally substituted at any substitutable position by a substituent selected from ═O, ═S, halogen, hydroxy, —SH, COR
a
, CO
2
R
a
, —ZNR
11
R
12
, C
1-4
alkyl, hydroxyC
1-4
alkyl, fluoroC
1-4
alkyl, chloroC
1-4
alkyl, C
1-4
alkoxy, fluoroC
1-4
alkoxy or C
1-4
alkoxy substituted by a C
1-4
alkoxy or hydroxyl group, and wherein said C
2-4
alkenyl and C
2-4
alkynyl groups are optionally substituted by a substituent selected from halogen, hydroxy, N
3
, —NR
11
R
12
, —NR
a
COR
b
, —OSO
2
R
a
, —(CH
2
)
p
NR
a
(CH
2
)
q
COOR
b
, COR
a
or COOR
a
;
R
8
represents hydrogen, C
1-6
alkyl, fluoroC
1-6
alkyl, hydroxy, C
1-6
alkoxy or hydroxyC
1-6
alkyl;
R
9
and R
10
each independently represent hydrogen, halogen, C
1-6
alkyl, CH
2
OR
c
, oxo, CO
2
R
a
or CONR
a
R
b
where R
a
and R
b
are as previously defined and R
c
represents hydrogen, C
1-6
alkyl or phenyl;
R
11
is hydrogen, C
1-4
alkyl, C
3-7
cycloalkyl, C
3-7
cycloalkylC
1-4
alkyl, C
2-4
alkyl substituted by a C
1-4
alkoxy or hydroxyl group, or R
11
is a five membered or six membered nitrogen-containing heteroaromatic ring as previously defined;
R
12
is hydrogen or C
1-4
alkyl, C
3-7
cycloalkyl, C
3-7
cycloalkylC
1-4
alkyl, or C
2-4
alkyl substituted by a C
1-4
alkoxy or hydroxyl group;
or R
11
, R
12
and the nitrogen atom to which they are attached form a heteroaliphatic ring of 4 to 7 ring atoms, optionally substituted by one or two groups selected from hydroxy, COR
e
, CO
2
R
e
, C
1-4
alkyl optionally substituted by a C
1-4
alkoxy or hydroxyl group, or C
1-4
alkoxy optionally substituted by a C
1-4
alkoxy or hydroxyl group, or a five membered or six membered nitrogen-containing heteroaromatic ring as previously defined, or said heteroaliphatic ring is substituted by a spiro-fused lactone ring, and said heteroaliphatic ring optionally containing a double bond, which heteroaliphatic ring may optionally contain an oxygen or sulphur ring atom, a group S(O) or S(O)
2
or a second nitrogen atom which will be part of a NH or NR
d
moiety, where R
d
is C
1-4
alkyl optionally substituted by hydroxy or C
1-4
alkoxy, and where R
e
is hydrogen, C
1-4
alkyl or benzyl;
or R
11
, R
12
and the nitrogen atom to which they are attached form a non-aromatic azabicyclic ring system of 6 to 12 ring atoms;
or R
11
, R
12
and the nitrogen atom to which they are attached form a heteroaliphatic ring of 4 to 7 ring atoms to which is fused a benzene ring or a five membered or six membered nitrogen-containing heteroaromatic ring ring optionally containing 1, 2 or 3 additional heteroatoms selected from N, O and S;
Z represents a bond, C
1-6
alkylene or C
3-6
cycloalkylene;
n is zero, 1 or 2;
p is 1 or 2; and
q is 1 or 2;
and pharmaceutically acceptable salts thereof.
A preferred class of compounds of formula (I) is that wherein:
R
7
represents halogen, hydroxy, C
2-4
alkenyl, N
3
, —NR
11
R
12
, —NR
a
COR
b
, —OSO
2
R
a
, —(CH
2
)
p
NR
a
(CH
2
)
q
COOR
b
, COR
a
, COOR
a
, or a five membered or six membered nitrogen-containing heteroaromatic ring optionally containing 1, 2 or 3 additional heteroatoms selected from N, O and S which heteroaromatic ring is optionally substituted at any substitutable position by a substituent selected from ═O, ═S, halogen, hydroxy, —SH, COR
a
, CO
2
R
a
, —ZNR
11
R
12
, C
1-4
alkyl, hydroxyC
1-4
alkyl, fluoroC
1-4
alkyl, C
1-4
alkoxy, fluoroC
1-4
alkoxy or C
1-4
alkoxy substituted by a C
1-4
alkoxy or hydroxyl group.
Another preferred class of compounds of formula (I) is that wherein:
R
7
represents halogen, hydroxy, C
2-4
alkenyl, N
3
, —NR
11
R
12
, —NR
a
COR
b
, —OSO
2
R
a
, —(CH
2
)
p
NR
a
(CH
2
)
q
COOR
b
or a five membered or six membered nitrogen-containing heteroaromatic ring optionally containing 1, 2 or 3 additional heteroatoms selected from N, O and S which heteroaromatic ring is optionally substituted at any substitutable position by a substituent selected from ═O, ═S, halogen, hydroxy, —SH, COR
a
, CO
2
R
a
, —ZNR
11
R
12
, C
1-4
alkyl, hydroxyC
1-4
alkyl, fluoroC
1-4
alkyl, C
1-4
alkoxy, fluoroC
1-4
alkoxy or C
1-4
alkoxy substituted by a C
1-4
alkoxy or hydroxyl group;
R
11
is hydrogen or C
1-4
alkyl, C
3-7
cycloalkyl, C
3-7
cycloalkylC
1-4
alkyl, or C
2-4
alkyl substituted by a C
1-4
alkoxy or hydroxyl group;
R
12
is hydrogen or C
1-4
alkyl, C
3-7
cycloalkyl, C
3-7
cycloalkylC
1-4
alkyl, or C
2-4
alkyl substituted by a C
1-4
alkoxy or hydroxyl group;
or R
11
, R
12
and the nitrogen atom to which they are attached form a heteroaliphatic ring of 4 to 7 ring atoms, optionally substituted by one or two groups selected from hydroxy, COR
a
, CO
2
R
a
or C
1-4
alkoxy optionally substituted by a C
1-4
alkoxy or hydroxyl group, and said ring optionally containing a double bond, which ring may optionally contain an oxygen or sulphur ring atom, a group S(O) or S(O)
2
or a second nitrogen atom which will be part of a NH or NR
d
moiety where R
d
is C
1-4
alkyl optionally substituted by hydroxy or C
1-4
alkoxy;
or R
11
, R
12
and the nitrogen atom to which they are attached form a non-aromatic azabicyclic ring system of 6 to 12 ring atoms;
or a pharmaceutically acceptable salt thereof.
A further preferred class of compounds of formula (I) is that wherein R
1
is hydrogen, C
1-4
alkyl, C
1-4
alkoxy, halogen or CF
3
.
Another preferred class of compounds of formula (I) is that wherein R
2
is hydrogen, C
1-4
alkyl, C
1-4
alkoxy, halogen or CF
3
.
Also preferred is the class of compounds of formula (I) wherein R
3
is hydrogen, fluorine, chlorine or CF
3
.
A particularly preferred class of compounds of formula (I) is that wherein R
1
is fluorine, chlorine or CF
3
.
Another particularly preferred class of compounds of formula (I) is that wherein R
2
is hydrogen, fluorine, chlorine or CF
3
.
Also particularly preferred is the class of compounds of formula (I) wherein R
3
is hydrogen, fluorine, chlorine or CF
3
.
Preferably R
1
and R
2
are in the 3 and 5 positions of the phenyl ring.
More preferably R
1
is 3-fluoro or 3-CF
3
.
More preferably R
2
is 5-fluoro or 5-CF
3
.
More preferably R
3
is hydrogen.
Most preferably R
1
is 3-F or 3-CF
3
, R
2
is

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