Tetrahydronaphthyridinyl-carboxamides having anti-convulsant...

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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C514S278000, C546S018000, C546S122000, C546S081000

Reexamination Certificate

active

06762192

ABSTRACT:

This invention relates to novel compounds, to processes for preparing them, and to their use as therapeutic agents.
WO97/48683 (SmithKline Beecham) discloses that benzamide compounds of formula (A) below possess anti-convulsant activity and are therefore believed to be useful in the treatment and/or prevention of anxiety, mania, and related depression disorders.
where n and p are independently integers from 1 to 4 and (n+p) is from 2 to 5;
R
1
is C
1-6
alkylO—;
R
2
is hydrogen, halogen, CN, N
3
, trifluoromethyldiazirinyl, CF
3
, CF
3
O—, CF
3
S—, CF
3
CO—, C
1-6
alkyl, C
3-6
cycloalkyl, C
3-6
cycloalkyl-C
1-4
alkyl-, C
1-6
alkylO—, C
1-6
alkylCO—, C
3-6
cycloalkylCO—, C
3-6
cycloalkyl-C
1-4
alkylCO—, phenyl, phenoxy, benzyloxy, benzoyl, phenyl-C
1-4
alkyl-, C
1-6
alkylS—, C
1-6
alkylSO
2
—, (C
1-4
alkyl), NSO
2
— or (C
1-4
alkyl)NHSO
2
—;
R
3
is hydrogen, halogen, NO
2
, CN, N
3
, trifluoromethyldiazirinyl, C
1-6
alkylO—, C
1-6
alkylS—, C
1-6
alkyl, C
3-6
cycloalkyl, C
3-6
cycloalkyl-C
1-4
alkyl-, C
1-6
alkenyl, C
1-6
alkynyl, CF
3
CO—, C
1-6
alkylCO—, C
3-6
cycloalkylCO—, C
3-6
cycloalkyl-C
1-4
alkylCO—, phenyl, phenoxy, benzyloxy, benzoyl, phenyl-C
1-4
alkyl-, or —NR
5
R
6
where R
5
is hydrogen or C
1-4
alkyl, and R
6
is hydrogen, C
1-4
alkyl, —CHO, —CO
2
C
1-4
alkyl or —COC
1-4
alkyl;
R
4
is hydrogen, C
1-6
alkyl, C
1-6
alkenyl, or C
1-6
alkynyl.
It has now been surprisingly found that tetrahydronaphthyridinyl-carboxamide compounds of formula (I) below possess anti-convulsant activity and are therefore believed to be useful in the treatment and/or prevention of anxiety, mania, depression, panic disorders and/or aggression, disorders associated with a subarachnoid haemorrhage or neural shock, the effects associated with withdrawal from substances of abuse such as cocaine, nicotine, alcohol and benzodiazepines, disorders treatable and/or preventable with anti-convulsive agents, such as epilepsy including post-traumatic epilepsy, Parkinson's disease, psychosis, migraine, cerebral ischaemia. Alzheimer's disease and other degenerative diseases such as Huntingdon's chorea, schizophrenia, obsessive compulsive disorders (OCD), neurological deficits associated with AIDS, sleep disorders (including circadian rhythm disorders, insomnia & narcolepsy), tics (e.g. Giles de la Tourette's syndrome), traumatic brain injury, tinnitus, neuralgia, especially trigeminal neuralgia, neuropathic pain, dental pain, cancer pain, inappropriate neuronal activity resulting in neurodysthesias in diseases such as diabetes, multiple sclerosis (MS) and motor neurone disease, ataxias, muscular rigidity (spasticity), temporomandibular joint dysfunction, and amyotrophic lateral sclerosis (ALS).
Accordingly, the present invention provides a compound of formula (I):
where R
1
is hydrogen, C
1-6
alkyl (optionally substituted by hydroxy or C
1-4
alkoxy), phenyl-C
1-4
alkyl-, C
1-6
alkenyl, or C
1-6
alkynyl;
R
2
is hydrogen or up to three substituents selected from halogen, NO
2
, CN, N
3
, CF
3
O—, CF
3
S—, CF
3
SO
2
—, CF
3
CO—, C
1-6
alkyl, C
1-6
alkenyl, C
1-6
alkynyl, C
1-6
perfluoroalkyl, C
3-6
cycloalkyl, C
3-6
cycloalkyl-C
4
alkyl-, C
1-6
alkylO—, C
1-6
alkylCO—, C
3-6
cycloalkylO—, C
3-6
cycloalkylCO—, C
3-6
cycloalkyl-C
1-4
alkylO—, C
3-6
cycloalkyl-C
1-4
alkylCO—, phenyl, phenoxy, benzyloxy, benzoyl, phenyl-C
1-4
alkyl-, C
1-6
alkylS—, C
1-6
alkylSO
2
—) (C
1-4
alkyl)
2
NSO
2
—, (C
1-4
alkyl)NHSO
2
—, (C
1-4
alkyl)
2
NCO—, (C
1-4
alkyl)NHCO— or CONH;
or —NR
5
R
6
where R) is hydrogen or C
1-4
alkyl, and
R
6
is hydrogen, C
1-4
alkyl, formyl, —COC
1-4
alkyl or —COC
1-4
alkyl;
or two R
2
groups together form a carbocyclic ring that is saturated or unsaturated, optionally interrupted by O or NH;
R
3
groups and R
4
groups are each independently hydrogen or C
1-6
alkyl and/or the two R
3
groups and/or the two R
4
groups together form a C
3-6
spiroalkyl group, provided that at least one R
3
or R
4
group is not hydrogen; and
X is selected from hydrogen, halogen, cyano, alkyl and alkoxy.
The compounds of this invention are tetrahydronaphthyridinyl-carboxamides, especially (tetrahydronaphthyridin-3-yl)carboxamides. The carboxamide moiety is typically a benzamide, but when two R
2
groups form a carbocyclic ring, this is typically a 5-7 membered ring, and the carboxamide moiety may be a naphthalene carboxamide or an indane carboxamide, or when interrupted by O or NH may be a benzofuran carboxamide or an indole carboxamide.
In the formula (I), alkyl groups, including alkyl groups that are part of other moieties, such as alkoxy or acyl, may be straight chain or branched. Phenyl groups, including phenyl groups that are part of other moieties, in R
2
may optionally be substituted with one or more independently selected halogen or C
1-6
alkyl. C
1-6
alkoxy or C
1-6
alkylcarbonyl.
Suitable C
3-6
cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Suitable halo substituents include fluoro, chloro, iodo and bromo.
It should be appreciated that compounds of the present invention possess chiral centres and as such may exist in different enantiomeric forms, the present invention extends to each enantiomeric form and mixtures thereof including diastereoisomers and racemates.
Preferably, the two R
3
groups are the same, and the two R
4
groups are the same; typically either both R
3
groups are gem-dialkyl or spiro-alkyl, preferably gem-dialkyl, and both R
4
groups are hydrogen, or vice versa.
Accordingly one suitable group of compounds is of formula (IA):
A further suitable group is of formula (IB):
where R
1
, R
2
, R
3
, R
4
, X are as defined above.
A suitable group of compounds of formula (I) have
R
1
as hydrogen, methyl, ethyl, propyl, benzyl, hydroxyethyl, methoxyethyl,
R
2
as hydrogen or one or more of methyl, ethyl, n-butyl, iso-propyl, t-butyl, phenyl, methoxy, ethoxy, iso-propoxy, cyclopropylmethoxy, n-butoxy, phenoxy, benzyloxy, amino, acetylamino, nitro, azido, cyano, bromo, chloro, fluoro, iodo, acetyl, propionyl, pivaloyl, n-butyroyl, iso-butyroyl, benzoyl, iodobenzoyl, trifluoromethyl, perfluoroethyl, trifluoromethoxy, trifluoroacetyl, methanesulfonyl, n-propylsulfonyl, isopropylsulfonyl, dimethylsulfamoyl,
R
3
one or both is hydrogen or methyl,
R
4
one or both is hydrogen or methyl.
A preferred group of compounds of formula (I) have
R
1
as hydrogen, methyl,
R
2
as hydrogen or one or more of methyl, ethyl, i-propyl, t-butyl, methoxy, ethoxy, i-propoxy, bromo, chloro, cyano, trifluoromethyl,
R
3
both methyl,
R
4
both hydrogen.
Examples of compounds of formula (I) are:
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)benzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-3-cyano-4-iso-propylbenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-4-methoxy-3-trifluoromethylbenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-3-bromo-4-ethylbenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-3-bromo-4-ethoxybenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-3-chloro-4-iso-propyloxybenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl [1,6]naphthyridin-3-yl)-3-bromo-4-iso-propyloxybenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-3-acetyl-4-iso-propyloxybenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-4-ethoxy-3-trifluoromethylbenzamide;
N-(8,8-dimethyl-5,6,7,8-tetrahydro[1,6]naphthyridin-3-yl)-4-methoxy-3-trifluoromethylbenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-3-bromo-4-methoxybenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-3-chloro-4-methoxybenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-3-cyano-4-methoxybenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]naphthyridin-3-yl)-3-cyano-4-ethylbenzamide;
N-(5,6,7,8-tetrahydro-6,8,8-trimethyl[1,6]napht

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