4-amino-1-aryl-1,5-dihydropyrrol-2-ones and process for making

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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C514S231500, C514S252130, C514S317000, C514S422000, C540S602000, C544S141000, C544S372000, C546S208000, C548S550000

Reexamination Certificate

active

06500821

ABSTRACT:

FIELD OF THE INVENTION
The invention relates to 1,5-dihydropyrrol-2-ones which contain a secondary amine radical in the 4-position and an aryl radical in the 1-position, to a process for their preparation, and to a process for their use as medicaments, specifically for the treatment of epilepsies of various forms and for the treatment of states of anxiety and tension.
BACKGROUND
Unsubstituted 1-phenyl-1,5-dihydropyrrol-2-one was described in 1981 by a Japanese group [K. Tabei et al., Heterocycles 1981, 16, 795 ]. 1,5-dihydropyrrol-2-ones having aryl substituents in the 1-position and primary amines as substituents in the 4-position have been described by Lonza AG in German patent No. 2,214,488. No biological activity of the compounds described therein was mentioned or suggested.
Compounds which are alkoxy-substituted in the 4-position, such as, for example, 4-ethoxy-1-phenyl-1,5-dihydropyrrol-2-one, are known [T. Nishio et al., J. Chem. Soc. Perkin Trans. 1, 1992, 899]. Also for these compounds, no biological activity has been disclosed.
1,5-dihydropyrrol-2-ones having a secondary amine radical in the 4-position and an aryl radical in the 1-position have so far not been described.
Epilepsy is a behavioral change in the form of convulsions. The cause is short-term, extremely strong neuronal discharges of the brain. Altogether, about 5% of all people suffer an epileptic attack in their life; 1% suffer from epilepsy.
Fundamentally, two factors are to be considered for the genesis of convulsions, pathological discharges in groups of nerve cells and/or absent stimulus limitation which makes possible a spread of the pathological stimulation, i.e. there is an increased instability of the cell membrane potential with a tendency for spontaneous electrical discharges.
Only about 60-80% of patients currently become attack-free under medicinal treatment. Certain forms of epilepsy, however, can still not be treated adequately. In addition, undesired side effects, such as neurotoxicity and idiosyncrasy, can occur through the administration of anticonvulsants that are on the market.
Anxiety states and tension of differing etiology and intensity cannot be currently satisfactorily treated in all cases. Since approximately 1960, benzodiazepine derivatives have been employed as a matter of priority for the treatment of anxiety states and tension. Substances generally having such a profile have a calming and emotion-dampening action. In the short term, these medicaments can be of great help, but even in therapeutic doses side effects such as sedation, drowsiness and decreases responsiveness will occur.
There can be an adverse effect on mental processes due to sedation. In some cases, ataxia and coordination disorders can be observed, which affect performance.
On continuous use, these benzodiazepine compounds lead to habituation effects, i.e. the so-called tolerance. The efficacy of the preparation decreases and the dose has to be increased. A psychological dependence, and even a physiological dependence, can develop. Hence, complicated withdrawal phenomena will occur when withdrawal is attempted.
The most important representatives of the anxiolytics introduced onto the market are the active compounds diazepam, clonazepam and medazepam.
To achieve an anxiolytic action of diazepam, plasma concentrations of 300 to 400 ng/ml are necessary. The side effects mentioned, such as sedation and psychomotor disorders, which are manifested in daytime sedation, drowsiness and restricted attentiveness and responsiveness, also occur, however, at the same concentrations. On account of the long half-life of diazepam and clonazepam, severe “hang-over” effects occur, which are likewise associated with drowsiness, impairment of intellectual and motor capacities, and prolonged reaction time. The anxiolytic action of clonazepam is masked by the sedating or hypnotic action. High doses of medazepam are also associated with hypnotic, muscle-relaxing phenomena. All three medicaments potentiate the action of numerous centrally acting pharmaceuticals and of alcohol. In these cases, effects can occur which are barely noticeable after administration of the individual substances.
Until now, attempts to achieve a satisfactory therapeutic standard in the case of relatively long-lasting states of anxiety have been unsuccessful. A therapy-outlasting action of anxiolytic medicaments is presently also not adequately ensured.
DESCRIPTION OF THE INVENTION
It is an object of the present invention to provide compounds having favorable pharmacological properties, which can be employed as medicaments, in particular for the treatment of epilepsy.
It is a further object of the present invention to provide medicaments for the treatment of different states of anxiety and tension and which have a great therapeutic spectrum.
According to the present invention, these novel medicaments are 4-amino-1-aryl-1,5-dihydropyrrol-2-ones of Formula 1
where
X is hydrogen, halogen, a C
1-4
-alkyl, C
1-4
-alkoxy, trifluoromethyl or trifluoromethoxy, nitro, or amine residue;
Y is a secondary amine residue, such as, for example, a morpholine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, pyrrolidine, 4-methylpiperazine, azepam, diethylamino, bis(methoxyethyl)amine residue; and
m is a cardinal number between 1 and 3.
Examples of compounds of Formula 1 include:
1-(2-chlorophenyl)-4-morpholin-4-yl-1,5-dihydropyrrol-2-one;
1-(3-methylphenyl)-4-morpholin-4-yl-1,5-dihydropyrrol-2-one;
1-(4-fluorophenyl)-4-morpholin-4-yl-1,5-dihydropyrrol-2-one;
1-(4-chlorophenyl)-4-morpholin-4-yl-1,5-dihydropyrrol-2-one;
1-(4-bromophenyl)-4-morpholin-4-yl-1,5-dihydropyrrol-2-one;
1-(4-methylphenyl)-4-morpholin-4-yl-1,5-dihydropyrrol-2-one;
1-(4-methoxyphenyl)-4-morpholin-4-yl-1,5-dihydropyrrol-2-one;
4-morpholin-4-yl-1-(4-trifluoromethylphenyl)-1,5-dihydropyrrol-2-one;
4-morpholin-4-yl-1-(4-trifluoromethoxyphenyl)-1,5-dihydropyrrol-2-one;
1-(3-chloro-4-fluorophenyl)-4-morpholin-4-yl-1,5-dihydropyrrol-2-one;
4-morpholin-4-yl-1-(3,4, 5-trimethoxyphenyl)-1,5-dihydropyrrol-2-one;
1-(3-methylphenyl)-4-piperidin-1-yl-1,5-dihydropyrrol-2-one;
1-(4-fluorophenyl)-4-piperidin-1-yl-1,5-dihydropyrrol-2-one;
1-(4-chlorophenyl)-4-piperidin-1-yl-1,5-dihydropyrrol-2-one;
1-(4-methylphenyl)-4-piperidin-1-yl-1,5-dihydropyrrol-2-one;
1-(3-chloro-4-fluorophenyl)-4-piperidin-1-yl-1,5-dihydropyrrol-2-one;
1-(4-chlorophenyl)-4-pyrrolidin-1-yl-1,5-dihydropyrrol-2-one;
1-(4-chlorophenyl)-4-(4-methylpiperidin-1-yl)-1,5-dihydropyrrol-2-one;
1-(4-chlorophenyl)-4-(3-methylpiperidin-1-yl)-1,5-dihydropyrrol-2-one;
1-(4-chlorophenyl)-4-(2-methylpiperidin-1-yl)-1,5-dihydropyrrol-2-one,
1-(4-chlorophenyl)-4-(4-methylpiperazin-1-yl)-1,5-dihydropyrrol-2-one;
1-(4-chlorophenyl)-4-azepam-1-yl-1,5-dihydropyrrol-2-one;
1-(4-chlorophenyl)-4-(diethylamino)-1,5-dihydropyrrol-2-one;
1-(4-chlorophenyl)-4-(bis(methoxyethyl)amino)-1,5-dihydropyrrol-2-one; and
4-morpholin-4-yl-1-phenyl-1,5-dihydropyrrol-2-one.
Compounds of Formula 1 are prepared by the substitution of compounds of Formula 2 by the corresponding amines.
where
X is hydrogen, halogen, a C
1-4
-alkyl, C
1-4
-alkoxy, trifluoromethyl or trifluoromethoxy, nitro, or amine residue; and
m is a cardinal number between 1 and 3.
Compounds of Formula 2 are obtained by heating 4-(arylamino)-3-methoxybut-2-enoic esters in an organic solvent, preferably acetic acid, at boil for 1-6 hours.
4-(arylamino)-3-methoxybut-2-enoic esters can be obtained from 4-haloacetoacetic esters by known methods.
Alternatively, compounds of Formula 3 can be condensed with the corresponding amines.
where
X is hydrogen, halogen, a C
1-4
-alkyl, C
1-4
-alkoxy, trifluoromethyl or trifluoromethoxy, nitro, or amine residue; and
m is a cardinal number from 1 to 3.
Compounds of Formula 3 are synthesized by starting from known N-aryl-substituted glycine esters, analogously to the description by Mulholland, T. P. C.; Foster, R., Haydock, D. B.; J. Chem. Soc., Perkin Trans. 1 1972, 17, 2121-8.
The active compounds according to the present invention are suitable f

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