20,21-dinor-eburnamenines

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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Details

C546S051000

Reexamination Certificate

active

06534515

ABSTRACT:

It is an object of the invention to provide the novel 20,21-dinor-eburnamenines of formula I and their non-toxic, pharmaceutically acceptable salts and a novel process and novel intermediates for their preparation.
It is another object of the invention to provide novel pharmaceutical compositions and methods.
These and other objects and advantages of the invention will become obvious from the following detailed description.
THE INVENTION
The novel compounds of the invention are a compound selected from the group consistiny of all possible isomers or racemates of a compound of the formula
wherein X
1
, X
2
and X
3
are individually selected from the group consisting of hydrogen, halogen, unsubstituted or substituted alkyl of 1 to 18 carbon atoms, unsubstituted or substituted alkenyl and alkynyl of 2 to 18 carton atoms, unsubstituted or substituted alkoxy of 1 to 7 carbon atoms, —OH, —CF
3
, —NO
2
, —NH
2
, mono and dialkylamino of 1 to 5 alkyl carbon atoms and unsubstituted or substituted phenyl,
R is selected from the group consisting of unsubstituted or substituted alkyl of 1 to 7 carbon atoms, unsubstituted or substituted alkenyl and alkynyl of 2 to 7 carbon atoms, unsubstituted or substituted phenyl and carboxy optionally salified or esterified, R
1
is
one of R
8
and R
9
is selected from the group consisting of hydrogen, unsubstituted or substituted alkyl of 1 to 6 carbon atoms, unsubstituted or substituted alkenyl and alkynyl of 2 to 6 carbon atoms, unsubstituted or substituted phenyl, esterified carboxy, —CN, and acyl of 2 to 6 carbon atoms and the other and R
10
are selected from the group consisting of hydrogen, unsubstituted or substituted alkyl of 1 to 6 carbon atoms, unsubstituted or substituted alkenyl and alkynyl of 2 to 6 carbon atoms and unsubstituted or substituted phenyl and its non-toxic, pharmaceutically acceptable salts with acids or bases.
In the compounds of formula I, the 3-hydrogen and the 16-hydrogen can each leave the alpha or beta configuration which determines if the compounds will be the cis or trans diastereoisomeric form.
In the compounds of formula I, halogen may be bromine or iodine but is preferably chlorine or fluorine. Examples of alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert.-butyl and n-penityl and examples of alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy, tert.-butoxy. Examples of monoalkyl and dialkylaminio of 1 to 5 alkyl carbon atoms include methylamino, dimethylamino, ethylamino, diethylamino and isopropyl amino.
Examples of alkenyl and alkynyl include vinyl, allyl, 1-propenyl butenyl, pentenyl, ethynyl, propargyl, butynyl and pentynyl. Examples of acyl of 1 to 6 carbon atoms include formyl, acetyl, propionyl, butytyl, benzoyl, valeryl, hexanoyl, acryloyl, crotonoyl and carbamoyl. Examples of esterified carboxy are lower alkoxycarbonyls such as methoxycarbonyl, ethoxycarbonyl or benzyloxycarbonyl.
Examples of suitable acids to form the non-toxic, pharmaceutically acceptable acid addition salts are inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, phosphoric acid, and organic acids such as propioniic acid, acetic acid, formic acid, bezizoic acid, maleic acid, fumaric acid, succinic acid, tartaric acid, citric acid, oxalic, acid, glyoxylic acid, aspartic acid, ascorbic acid, alkylmonosulfonic acids such as metlanesulfonic acid, ethanesulfonic acid and propanesulfoniic acid alkyldisulfonic acids such as methanedisulfonic acid, &agr;,&bgr;-ethane-disulfonic acid, arylmonosulfonic acids such as benzenesulfonic acid and aryldisulfonic acids.
When R is carboxy, it can be salified by a base to form a salt of sodium, potassium, lithium, calcium, magnesium or ammonium or salts with organic bases such as methylamine, propylamine, trimethylamine, diethliylamine, triethylamine, N,N-dimethylethanolamine, tris (hydroxy-methyl) aminomethane, ethanolamine, pyridine, picoline, dicyclohexylamine, morpholine, benzylamine, procaine, lysine, argininie, histidine and N-methylglucamine.
The alkyl, alkenyl or alkynyl can be substituted with at least one member of the group consisting of hydroxy, aryl such as phenyl or naphthyl; arylalkyl such as benzyl or phenethyl; cycloalkyl, cyclo-pentyl or cyclohexyl; alkoxy such as methoxy, ethoxy, propoxy or isopropoxy, methoxymethyl or 1-ethoxyethyl; aryloxy such as phenoxy; (aralkoxy such as benzyloxy; mercapto; alkylthio such as methylthio or ethylthio; anylthio; aralkylthio; amino such as 2-amineoethyl; substituted amino such as methylamino, ethylamino or dimethylamino; halogen i.e., chloro or bromo, such as 2-bromoethyl; nitro; azido; carbamoyl; substituted carbamoyl such as a lower N-monoalkyl carbamoyl group like N-methylcarbamoyl, N-ethylcarbamoyl, a lower N,N-dialkyl carbamoyl such as N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl; an N-(lower hydroxyalkyl) carbamoyl such as N-(hydroxymethyl) carbamoyl, N-(hydroxyethyl) carbamoyl, a lower carbamoylalkyl such as carbamoylmethyl, carbamoylethyl; carboxy; esterified carboxy such as methoxycarbonyl or ethoxycarbonyl; formyl; acyl such as acetyl, propionyl or benzoyl; acyloxy such as acetoxy or propionyloxy; cyano; phthlalimido; acylamido such as acetamido or benzamido; alkoxycarbonylamino such as methoxycarbonylamino or ethoxycarbonylamino; or (arylalkyl)-oxycarbonylamino such as benzyloxycarbonylamino.
A The aryl and aralkyl can be unsubstituted or substituted with at least one member of the group consisting of hydroxy; halogen; alkyl such as methyl, ethyl, isopropyl or tert-butyl; alkoxy such as methoxy, ethoxy or isopropoxy; alkylthio such as methylthio or ethylthio; nitro; amino; substituted amino such as monoalkylamino and dialkylamino such as methylamino, ethylamino or dimethylamino.
When X
1
, X
2
or X
3
are substituted alkyl or alkoxy, this is preferably substituted by at least one hydroxy, free or esterified carboxy such as methoxycarbonyl or ethoxycarbonyl, and the alkyl may be substituted by a liner or branched alkoxy of 1 to 5 carbon atoms like methoxy, ethoxy or isopropoxy.
Among the preferred compounds of formula I are those wherein X
1
, X
2
and X
3
are hydrogen, those wherein the alkyl, alkoxy, alkenyl and alkynyl are substituted with at least one member of the group consisting of —OH, halogen, alkoxy of 1 to 6 carbon atoms, acyl of an organic carboxylic acid of 1 to 6 carbon atoms, benzoyl, —CN, carboxy, carboxy esterified with an alkanol of 1 to 5 carbon atoms, unsubstituted or substituted phenyl, unsubstituted or substituted carbamoyl and
and R
6
are individually selected from the group consisting of hydrogen, alkyl of 1 to 7 carbon atoms unsubstituted or substituted by at least one member of the group consisting of —OH, alkoxy of 1 to 5 carbon atoms and free carboxy or esterified with alkyl of 1 to 5 carbon atoms and unsubstituted or substituted aryl of 6 to 12 carbon atoms and aralkyl of 7 to 12 carbon atoms or taken together with the nitrogen to which they are attached form a 5 to 6 member heterocycle containing or not a second heteroatom selected from the group consisting of —O—, —S— and —NR
A
and —R
A
is selected from the group consisting of hydrogen, alkyl and hydroxy-alkyl of 1 to 5 carbon atoms, halogen, alkoxy of 1 to 4 carbon atoms, unsubstituted or substituted aryl of 6 to 12 carbon atoms and unsubstituted or substituted aralkyl of 7 to 12 carbon atoms and their non-toxic, a pharmaceutically acceptable acid addition salts.
Other preferred compounds of formula I are those wherein the phenyl, aryl and aralkyl are substituted with at least one member of the group consisting of halogen, —OH, alkyl and alkoxy of 1 to 5 carbon atoms, CH
3
S—, —NO
2
, —NH
2
and monoalkyl and dialkylamino. Aralkyl of 7 to 12 carbon atoms is preferably benzyl or phenethyl unsubstituted or substituted with at least one member of the group consisting of methyl, ethyl, isopropyl, tert.-butyl, methoxy, ethoxy or propoxy.
Examples of
as a heterocyclic are pyyrolidino, piperidino, morpholino, piperazinyl, methylpiperazinyl, ethylpiperazinyl, prop

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