Azetidine derivatives, their preparation and medicaments...

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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C514S210190, C514S210200, C514S210210, C544S060000, C544S111000, C546S139000, C546S150000, C546S165000, C546S172000, C546S268100, C548S179000, C548S203000, C548S217000, C548S465000, C548S950000, C549S058000, C549S059000, C549S407000, C549S462000, C549S471000

Reexamination Certificate

active

06518264

ABSTRACT:

The present invention relates to azetidine derivatives of formula:
their optical isomers, their salts, their preparation and medicaments containing them.
In formula (I),
R represents a chain
R
1
represents a methyl or ethyl radical,
R
2
represents either an aromatic chosen from phenyl, naphthyl or indenyl, these aromatics being nonsubstituted or substituted with one or more halogens, alkyl, alkoxy, —CO—alk, hydroxyl, —COOR
5
, formyl, trifluoromethyl, trifluoromethylsulfanyl, trifluoromethoxy, nitro, —NR
6
R
7
, —CO—NH—NR
6
R
7
, —N(alk)COOR
8
, cyano, —CONHR
9
, —CO—NR
16
R
17
, alkylsulfanyl, hydroxyalkyl, —O—alk-NR
12
R
13
or alkylthioalkyl or a heteroaromatic chosen from the benzofuryl, benzothiazolyl, benzothienyl, benzoxazolyl, chromanyl, 2,3-dihydrobenzofuryl, 2,3-dihydrobenzothienyl, indolinyl, isochromanyl, isoquinolyl, pyridyl, quinolyl, 1,2,3,4-tetrahydroisoquinolyl, 1,2,3,4-tetrahydroquinolyl, thiazolyl, or thienyl rings, it being possible for these heteroaromatics to be nonsubstituted or substituted with a halogen, alkyl, alkoxy, —COOR
5
, trifluoromethyl, trifluoromethylsulfanyl, trifluoromethoxy, nitro, —NR
6
R
7
, —CO—NH—NR
6
R
7
, cyano, —CONHR
9
, alkylsulfanyl, hydroxyalkyl or alkylthioalkyl,
R
3
and R
4
, which are identical or different, represent either an aromatic chosen from phenyl, naphthyl or indenyl, these aromatics being nonsubstituted or substituted with one or more halogens, alkyl, alkoxy, formyl, hydroxyl, trifluoromethyl, trifluoromethoxy, —CO-alk, cyano, —COOR
5
, —CONR
10
R
11
, —CO—NH—NR
6
R
7
, alkylsulfanyl, hydroxyalkyl, -alk-NR
6
R
7
or alkylthioalkyl; or a heteroaromatic chosen from benzofuryl, benzothiazolyl, benzothienyl, benzoxazolyl, chromanyl, 2,3-dihydrobenzofuryl, 2,3-dihydrobenzothienyl, furyl, isochromanyl, isoquinolyl, pyrrolyl, quinolyl, 1,2,3,4-tetrahydroisoquinolyl, thiazolyl or thienyl rings, it being possible for these heteroaromatics to be nonsubstituted or substituted with a halogen, alkyl, alkoxy, hydroxyl, trifluoromethyl, trifluoromethoxy, cyano, —COOR
5
, —CO—NH—NR
6
R
7
, —CONR
10
R
11
, -alk-NR
6
R
7
, alkylsulfanyl, hydroxyalkyl or alkylthioalkyl;
R
5
is an alkyl or phenyl radical which is optionally substituted with one or more halogen atoms,
R
6
and R
7
, which are identical or different, represent a hydrogen atom or an alkyl, —COOalk, cycloalkyl, alkylcycloalkyl, -alk-O-alk or hydroxyalkyl radical or alternatively R
6
and R
7
together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated or unsaturated mono- or bicyclic heterocycle optionally containing another heteroatom chosen from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl, —COalk, —COOalk, —CO—NHalk, —CS—NHalk, —CO-alk-NR
14
R
15
, oxo, hydroxyalkyl, -alk-O-alk or —CO—NH
2
radicals,
R
8
represents an alkyl radical,
R
9
represents a hydrogen atom or an alkyl radical or an alkyl radical substituted with a dialkylamino, phenyl, cycloalkyl (optionally substituted with —COOalk) or a 3- to 10-membered saturated or unsaturated mono- or bicyclic heterocycle optionally containing one or more heteroatoms chosen from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl radicals,
R
10
and R
11
, which are identical or different, represent a hydrogen atom or an alkyl radical or alternatively R
10
and R
11
together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle optionally containing another heteroatom chosen from oxygen, sulfur and nitrogen and being optionally substituted with an alkyl radical,
R
12
and R
13
, which are identical or different, represent hydrogen atom or an alkyl or cycloalkyl radical or alternatively R
12
and R
13
together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle optionally containing another heteroatom chosen from oxygen, sulfur and nitrogen and being optionally substituted with an alkyl, —COalk, —COOalk, —CO—NHalk, —CS—NHalk or —CO-alk-NR
14
R
15
radical or a 3- to 10-membered saturated mono- or bicyclic heterocycle containing a heteroatom chosen from oxygen, sulfur and nitrogen,
R
14
and R
15
, which are identical or different, represent a hydrogen atom or an alkyl or —COOalk radical,
R
16
and R
17
together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle optionally containing another heteroatom chosen from oxygen, sulfur and nitrogen,
R′ represents a hydrogen atom or a —CO-alk radical, alk represents an alkyl or alkylene radical.
In the preceding definitions and in those which follow, unless otherwise stated, the alkyl and alkylene radicals and portions and the alkoxy radicals and portions are in the form of a straight or branched chain and contain 1 to 6 carbon atoms.
Among the alkyl radicals, there may be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl and hexyl radicals. Among the alkoxy radicals, there may be mentioned methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy and pentyloxy radicals.
The term halogen comprises chlorine, fluorine, bromine and iodine.
When R
2
and/or R
3
and/or R
4
represent independently a substituted phenyl, the latter is preferably mono-, di- or trisubstituted.
When R
6
and R
7
together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated or unsaturated mono- or bicyclic heterocycle, the latter is preferably an azetidinyl, pyrrolidinyl, piperazinyl, piperidyl, morpholinyl, imidazolyl, thiomorpholinyl or furyl ring, these rings being optionally substituted with an alkyl, hydroxyalkyl, -alk-O-alk, —CONH
2
, —COalk, —COOalk, oxo, —CSNHalk, —CONHalk or —CO-alk-NR
14
R
15
radical and, in particular, with a methyl, ethyl, propyl, isobutyl, acetyl, N,N-dimethylaminomethylcarbonyl, methyloxycarbonyl, methylcarbamoyl, methylthiocarbamoyl, N-methylaminomethylcarbonyl, N-methyl-N-tertbutoxycarbonylaminomethylcarbonyl, oxo, —CSNHCH
3
or —CONHCH
3
radical.
When R
10
and R
11
together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle, the latter is preferably an azetidinyl, pyrrolidinyl, piperazinyl, piperidyl, morpholinyl or thiomorpholinyl ring, these rings being optionally substituted with an alkyl.
When R
12
and R
13
form together with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle, the latter is preferably an azetidinyl, pyrrolidinyl, piperazinyl, piperidyl, morpholinyl or thiomorpholinyl ring, these rings being optionally substituted with an alkyl, —COalk, —COOalk, —CO—NHalk, —CS—NHalk or —CO-alk-NR
14
R
15
radical or a 3- to 10-membered saturated mono- or bicyclic heterocycle containing a heteroatom chosen from oxygen, sulfur and nitrogen, and, in particular, with a thiomorpholinyl radical.
When R
16
and R
17
together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle, the latter is preferably a piperidyl ring.
When R
9
represents an alkyl radical substituted with a 3- to 10-membered saturated or unsaturated mono- or bicyclic heterocycle optionally containing one or more heteroatoms chosen from oxygen, sulfur and nitrogen, the latter is preferably a pyrrolidinyl, tetrahydrofuryl, morpholinyl or pyrrolyl ring, these rings being optionally substituted with one or more alkyl radicals.
The compounds of formula (I) may be provided in the form of enantiomers and diastereoisomers. These optical isomers and mixtures thereof form part of the invention.
The compounds of formula (I) for which R represents a chain of formula (A) may be prepared by dehydration of a corresponding compound of formula (Ia)
in which R
1
, R
2
, R
3
and R
4
have the same meanings as in formula (I) and R″ represents a hydroxyl, methanesulfonyloxy or acetyloxy radical.
This dehydration is carried out by a

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