Phencyclidine derivatives, preparation method and...

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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C514S432000, C514S444000, C514S447000, C546S187000, C549S028000, C549S060000, C549S068000

Reexamination Certificate

active

06342511

ABSTRACT:

The [N-(1-phenylcyclohexyl)piperidine (or PCP), developed as an anesthesic agent then withdrawn due to its very significant psychotopic effect, is today no more than a pharmalogical tool, interesting at least through its derivatives or analogues. One of the derivatives, N-(1-(2-thienyl)cyclohexyl)piperidine (or TCP), is, in its tritiated form, a ligand often used as a label for the PCP receptor. In vitro and in vivo studies of the [
3
H]TCP bond to the PCP receptor has revealed the existence of a second type of bond corresponding to the said PCP sites of low affinity in comparison to the first said sites of high affinity (Brain Res., 378, 133-141(1986)).
The present invention relates to novel derivatives of phencyclidines with selective affinity for low affinity receptors, processes for their preparation, pharmaceutical compositions containing them and their use as protective agents for central or peripheral nervous system cells against acute or chronic degeneration or as an anticonvulsant.
Therefore the subject of the invention is the compounds of formula I characterized in that they correspond either to formula I
A
in which
Ar represents a carboxcylic or heterocyclic aryl radical, monocyclic with 5 or 6 members or constituted by condensed rings, and optionally substituted by one or more identical or different radicals chosen from halogen atoms, hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, alkylthio, haloalkyl, hydroxyalkyl radicals, having at most 6 carbon atoms; free esterified or salified carboxy; cyano; nitro; amino optionally substituted by one or two identical or different alkyl radicals containing at most 6 carbon atoms;
R
1
and R
2
identical or different represent a hydrogen atom or an alkyl radical having at most 6 carbon atoms optionally substituted by one or more identical or different radicals chosen from the hydroxyl, free esterified or salified carboxy, cyano, nitro radicals, or R
1
and R
2
form with the nitrogen atom to which they are linked a
 radical in which n represents an integer from 0 to 2 and R
3
and R′
3
identical or different represent a hydrogen atom, a halogen atom or a hydroxyl, free esterified or salified carboxy, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, alkylthio, haloalkyl, hydroxyalkyl radical having at most 6 carbon atoms;
R
4
has the same meaning as R
3
or R′
3
;
X, Y and Z are such that at least one represents a sulphur or oxygen atom and the others represent a methylene radical,
with the exception of the compounds in which R
3
, R′
3
and R4 each represents a hydrogen atom and
1) R
1
and R
2
form with the nitrogen atom to which they are linked a pyrrolidine radical, Ar represents a phenyl or 2-thienyl radical and one of X, Y and Z represents an oxygen atom,
2) R
1
and R
2
form with the nitrogen atom to which they are linked a piperidine radical, Ar represents a phenyl, thienyl and benzothienyl radical, Y represents a sulphur atom and X and Z each represent a methylene radical,
3) R
1
and R
2
form with the nitrogen atom to which they are linked a piperidine radical, Ar represents a phenyl, methoxyphenyl, benzothienyl or 2-thienyl radical, Y represents an oxygen atom and X and Z each represent a methylene radical,
4) R
1
and R
2
form with the nitrogen atom to which they are linked a piperidine radical, Ar represents a phenyl, methoxyphenyl or 2-thienyl radical, one of X or Z represents an oxygen atom, the other represents a methylene radical and Y represents a methylene radical,
5) R
1
and R
2
form with the nitrogen atom to which they are linked a piperidine radical, Ar represents a phenyl or 2-thienyl radical, one of X or Z represents a sulphur atom, the other represents a methylene radical and Y represents a methylene radical,
6) R
1
and R
2
form with the nitrogen atom to which they are linked a pyrrolidine radical, Ar represents a 2-thienyl radical, one of X or Z represents a sulphur atom, the other represents a methylene radical and Y represents a methylene radical,
7) R
1
and R
2
form with the nitrogen atom to which they are linked an ethylamino or pyrrolidine radical, Ar represents a phenyl radical, Y represents a sulphur atom and X and Z each represent a methylene radical,
or one of the following formulae:
—N-[1-(2-thienyl)-cyclohexan- 1-yl]-3-hydroxymethyl-piperidine,
—N-[1-(2-thienyl)-cyclohexan- 1-yl]-4-hydroxy-3-methyl piperidine,
—N-[1-(2-benzothiophenyl)-cyclohexan-1-yl]-4-hydroxy-3-methyl piperidine,
—N-ethyl-1-(2-thienyl)-cyclohexylamine or
—N-[1-(2-furyl)-cyclohexan-1-yl] piperidine,
said compounds of formula I being in all possible racemic, enantiomeric and diastereoisomeric isomer forms as well as the addition salts with mineral and organic acids or with mineral and organic bases of said compounds of formula I.
A more particular subject of the invention is the compounds of general formula IA as defined below in which
Ar represents an heterocyclic aryl radical, monocyclic with 5 members or constituted by two condensed rings, and optionally substituted by one or more identical or different alkyl or alkenyl radicals;
R
1
and R
2
, identical or different, represent a hydrogen atom or an alkyl radical having at most 6 carbon atoms or R
1
and R
2
form together with a nitrogen atom to which they are linked a
radical in which n is equal to 1 and R
3
and R′
3
, identical or different, represent a hydrogen atom or a hydroxyl. aklyl or hydroxyalkyl radical having at most 6 carbon atoms.
In the definitions indicated above, the expression halogen represents a fluorine, chlorine, bromine or iodine atom.
The expression alkyl having at most 6 carbon atoms represents a linear or branched alkyl radical such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl or isohexyl radical.
Among the alkenyl radicals. The linear or branched alkyl radicals such as vinyl, allyl, 1-propenyl, butenyl, pentynyl or hexynyl radicals can be mentioned.
Among the alkynyl radicals, the ethynyl, propargyl, butynyl, pentynyl or hexynyl radicals can be mentioned. The linear or branched alkoxy radical preferably designates the radicals in which the alkyl radical is as defined above. The methoxy, ethoxy, propoxy, isopropyloxy or butoxy radicals are preferred.
The alkylthio radical preferably designates the radicals in which the alkyl radical is as defined above such as for example methylthio or ethylthio.
The haloalkyl radical preferably designates the radicals in which the alkyl radical is as defined above and is substituted by one or more halogen atoms as defined above such as, for example, bromoethyl, trifluoromethyl, trifluoroethyl or also pentafluoroethyl.
The hydroxyalkyl radical preferably designates the radicals in which the alkyl radical is as defined above such as for example hvdroxymethyl or hydroxyethyl.
The aryl radical can be carbocyclic or heterocyclic. The heterocyclic aryl radical can contain one or more identical or different heteroatoms chosen from oxygen, nitrogen and sulphur atoms. As an example of a carbocyclic or heterocyclic aryl radical, the phenyl. naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyrrolyl, thiazolyl, diazolyl, oxadiazolyl, benzothienyl, benzofuryl, benzopyrrolyl, benzimidazolyl or indolyl radicals can be mentioned.
A more particular subject of the invention is the compounds of general formula I
A
as defined above in which
Ar represents the thienyl, furyl, benzothienyl, benzofuryl radical and optionally substituted by one or more methyl, ethyl, propyl or allyl radicals;
R
1
and R
2
identical or different represent a hydrogen atom or a methyl or ethyl radical, or
R
1
and R
2
form with the nitrogen atom to which they are linked a
radical in which n is equal to 1 and R
3
and R′
3
identical or different represent a hydrogen atom or a hydroxyl, hydroxymethyl, hydroxyethyl, methyl or ethyl radical.
More particularly, a subject of the invention is the compounds of formula I
A
described hereafter in the examples, in particular the compounds corresponding to the

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