CH547801A - 4 and 7-Aminopropoyx-oxindole derivs - useful as anti-arrhythmics and beta-adrenergic blockers - Google Patents

4 and 7-Aminopropoyx-oxindole derivs - useful as anti-arrhythmics and beta-adrenergic blockers

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Publication number
CH547801A
CH547801A CH924871A CH924871A CH547801A CH 547801 A CH547801 A CH 547801A CH 924871 A CH924871 A CH 924871A CH 924871 A CH924871 A CH 924871A CH 547801 A CH547801 A CH 547801A
Authority
CH
Switzerland
Prior art keywords
formula
oxindole
alkyl
compound
compounds
Prior art date
Application number
CH924871A
Other languages
German (de)
Original Assignee
Sandoz Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE793073D priority Critical patent/BE793073A/en
Application filed by Sandoz Ag filed Critical Sandoz Ag
Priority to CH924871A priority patent/CH547801A/en
Priority to SE7207867A priority patent/SE379196B/xx
Priority to US00263768A priority patent/US3825558A/en
Priority to NL7208332A priority patent/NL7208332A/xx
Priority to HUSA002367 priority patent/HU164321B/hu
Priority to GB2874472A priority patent/GB1391828A/en
Priority to RO7483072A priority patent/RO62636A/en
Priority to BE785282A priority patent/BE785282A/en
Priority to DD163906A priority patent/DD99785A5/xx
Priority to IL39742A priority patent/IL39742A0/en
Priority to PL15620572A priority patent/PL83679B1/pl
Priority to DE2230426A priority patent/DE2230426A1/en
Priority to RO7483172A priority patent/RO62637A/en
Priority to JP47063153A priority patent/JPS5820955B1/ja
Priority to ES404174A priority patent/ES404174A1/en
Priority to AT541172A priority patent/AT330169B/en
Priority to FR7222696A priority patent/FR2143343B1/fr
Priority to AU43903/72A priority patent/AU4390372A/en
Priority claimed from DE19722262285 external-priority patent/DE2262285A1/en
Publication of CH547801A publication Critical patent/CH547801A/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D209/00Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04Indoles; Hydrogenated indoles
    • C07D209/30Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32Oxygen atoms
    • C07D209/34Oxygen atoms in position 2

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)

Abstract

Title cpds of formula (I): (where R1=H or 1. alkyl, X=OCH2CH (OR3)CH2NHR2 in 4- or 7- posn, R2=alkyl, cycloalkyl, alkoxyalkyl with >=2C atoms sepg O and N, phenylalkyl opt substd. by alkyl, or O alkyl with >=2C atoms sepg Ph and N, alkinyl, or carbalkoxyalkyl, and R3=H or COA where A is alkyl, 1. alkylcycloalkyl or a 5-6 membered oxyheterocyclic residue) are prepd by condensing the corresp. epoxypropoxy, substd cpds with H2NR2, or with an N-benzylamine followed by hydrogenation.

Description

  

  
 



   Die Erfindung hat ein Verfahren zur Herstellung neuer Oxindole der Formel 1, worin   Rl    für Wasserstoff oder einen niederen Alkylrest steht und R2 einen Alkinylrest, dessen Dreifachbindung nicht   in x,3-Stellung    steht zum Stickstoffatom. woran der Alkinylrest gebunden ist oder einen Carbalkoxyalkylrest bedeutet und ihrer Säureadditionssalze zum   Gegen', tattl.   



   Steht   9,    für niederes Alkyl, so enthält dieser Alkylrest insbesondere 1 bis 4. vorzugsweise 1 Kohlenstoffatom.



   Stellt   R2    eine Alkinylgruppe dar, so enthält diese insbesondere 3 bis 7 Kohlenstoffatome. Eine bevorzugte Gruppe dieser Reihe ist   1,1 -Dimethyl-2-propinyl.   



   Stellt   R..    eine Carbalkoxyalkylgruppe dar, so enthält deren Alkoxyrest insbesondere 1 bis 4, vorzugsweise 1 oder 2 Kohlenstoffatome und deren Alkylrest insbesondere 1 bis 6 Kohlenstoffatome.



   Besonders bevorzugt sind Verbindungen in denen   Rl    Wasserstoff bedeutet und worin R2 am   a-Kohlenstoffatom    verzweigt ist.



   Erfindungsgemäss gelangt man zu den Oxindolen der Formel I und ihren Säureadditionssalzen, indem man Verbindungen der Formel II, worin R, obige Bedeutung besitzt, mit Aminen der Formel III, worin R2 obige Bedeutung besitzt, umsetzt, und die so erhaltenen Verbindungen der Formel I als freie Basen oder als Säureadditionssalze gewinnt.



   Aus den freien Basen lassen sich in bekannter   Weise    Säureadditionssalze herstellen und umgekehrt.



   Die Umsetzung der Verbindungen der Formel II mit Aminen der Formel III kann nach bekannten Methoden erfolgen und wird beispielsweise in einem unter den Reaktionsbedingungen inerten organischen Lösungsmittel, z.B. in einem aromatischen Kohlenwasserstoff wie Benzol, Toluol, Xylol, in einem cyclischen Äther wie Dioxan, Tetrahydrofuran, in Amylalkohol durchgeführt.



   Die Reaktionstemperatur kann zwischen 20 und   1500    liegen: im allgemeinen arbeitet man vorzugsweise bei Siedetemperatur des Reaktionsgemisches am Rückfluss. Die Reaktionsdauer ist von der Reaktionstemperatur abhängig.



   Die nach dem obigen Verfahren hergestellten Verbindungen der Formel I können nach bekannten Methoden aufgearbeitet und gereinigt werden.



      Die Verbindungen detu pe,- FSîe IrIrSn    z.B. durch Umsetzung der Natriumsalze der entsprechenden 4-Hydroxyoxindole der Formel IV, worin   R1    obige Bedeutung besitzt, mit Epibromhydrin in Dimethylsulfoxyd als Lösungsmittel erhalten werden.



   Nach Beendigung der Reaktion giesst man in Wasser und extrahiert mit Essigester. Die Essigesterextrakte werden bis zur Kristallisation des Epoxypropoxyindols eingeengt.



   Von den Verbindungen der Formel IV sind 4-Hydroxyoxindol und   4-Hydroxy-l methyloxindol    bekannt. Die neuen Verbindungen der Formel IV können, wie 4-Hydroxy-l-methyloxindol, z.B. durch Cyclisierung der entsprechenden N   -Alkyl-N-chloroacetyl.o-anisidine    und Dimethylierung (Ätherspaltung) der so erhaltenen   1 -Alkyl-4-methoxyoxindolen    hergestellt werden,
Soweit die Herstellung der Ausgangsverbindungen nicht beschrieben ist, sind diese bekannt oder analog zu bekannten Methoden herzustellen.



   Die neuen Verbindungen der Formel I und ihre pharmakologisch verträglichen Säureadditionssalze besitzen bei geringer Toxizität interessante pharmakodynamische Eigenschaften und können daher als Heilmittel verwendet werden,
Die neuen Substanzen zeigen am spontanschlagenden isolierten Meerschweinchenvorhof eine Hemmung der positivinotropen Adrenalinwirkung und führen am narkotisierten Ganztier (Katze, Hund) zu einer starken Hemmung der durch Isoproterenol   [1(3 ,4-Dihydroxyphenyl)-2-isopropylamino-    äthanols bedingten Tachycardie und Blutdrucksenkung.

  Die Verbindungen besitzen demnach eine Blockerwirkung auf die adrenergenen   3-Rezeptoren,    und können daher u.a. zur Prophylaxe und Therapie von Koronarerkrankungen, insbesondere zur Behandlung von Angina pectoris, zur Behandlung des hyperkinetischen Herzsyndroms und der aus einer muskulär-hypertrophen, subvalvulären Aortenstenose resultierenden Zustände eingesetzt werden.



   Aufgrund ihrer antiarrhythmischen Wirkungen sind die Verbindungen ausserdem zur Behandlung von Herzrhythmusstörungen geeignet.



   Die zu verwendenden Dosen variieren naturgemäss je nach der Art der verwendeten Substanz, der Administration und des zu behandelnden Zustandes.



   In den nachfolgenden Beispielen, welche die Erfindung näher erläutern, ihren Umfang jedoch in keiner Weise einschränken sollen, erfolgen alle Temperaturangaben in Cel   siusgraden    und sind unkorrigiert.
EMI1.1     




   Beispiel I
4-[2-h   ydroxy-3-(2-methyl-3-butin-2-ylamino)-    propoxyl]-oxindol
3 g 4-(2,3-Epoxypropoxy)oxindol, 9 g 3-Amino-3-methylbutin und 40 ml Tetrahydrofuran werden 2 Tage unter Rühren zum Sieden erhitzt. Man filtriert die heisse Lösung und lässt kristallisieren. Die Titelverbindung schmilzt von 172 bis   174".   



   Das als Ausgangsmaterial verwendete 4-(2,3-Epoxypropoxy)-oxindol wurde wie folgt hergestellt:
273 g 4-Hydroxyoxindol, 1300 ml Dimethylsulfoxyd und 55,8 g   80%iges    Natriumhydrid werden 1 /2 Stunden auf   60      erwärmt, dann eine Lösung von 376 g Epibromhydrin in 500 ml Dimethylsulfoxyd bei Raumtemperatur zugetropft und 16 Stunden gerührt. Man giesst in Wasser, extrahiert mit Essigester und engt bis zur Kristallisation die Essigesterextrakte ein, Smp. 175 bis   177 .   

 

   Beispiel 2   
2-Methyl-2-[2-hydroxy-3-(4-oxindolyloxy) - propyl-amino]propionsäureäthylester   
Man verfährt wie in Beispiel 1 beschrieben, verwendet jedoch anstatt 3-Amino-3-methylbutin   oc-Aminoisobuttersäure-      äthylester.    Die Titelverbindung kristallisiert aus Äther, Smp. 158 bis   160".    



  
 



   The invention relates to a process for the preparation of new oxindoles of the formula 1, in which R1 is hydrogen or a lower alkyl radical and R2 is an alkynyl radical whose triple bond is not in the x, 3-position to the nitrogen atom. to which the alkynyl radical is bonded or denotes a carbalkoxyalkyl radical and its acid addition salts to counter ', tattl.



   If 9 stands for lower alkyl, this alkyl radical contains in particular 1 to 4, preferably 1 carbon atom.



   If R2 represents an alkynyl group, this contains in particular 3 to 7 carbon atoms. A preferred group of this series is 1,1-dimethyl-2-propynyl.



   If R .. represents a carbalkoxyalkyl group, its alkoxy radical contains in particular 1 to 4, preferably 1 or 2 carbon atoms and its alkyl radical contains in particular 1 to 6 carbon atoms.



   Particularly preferred are compounds in which R1 is hydrogen and in which R2 is branched on the a-carbon atom.



   According to the invention, the oxindoles of the formula I and their acid addition salts are obtained by reacting compounds of the formula II in which R has the above meaning with amines of the formula III in which R2 has the above meaning, and the compounds of the formula I thus obtained as wins free bases or as acid addition salts.



   Acid addition salts can be prepared from the free bases in a known manner and vice versa.



   The reaction of the compounds of the formula II with amines of the formula III can be carried out by known methods and is carried out, for example, in an organic solvent which is inert under the reaction conditions, e.g. in an aromatic hydrocarbon such as benzene, toluene, xylene, in a cyclic ether such as dioxane, tetrahydrofuran, in amyl alcohol.



   The reaction temperature can be between 20 and 1500: in general, reflux is preferably used at the boiling point of the reaction mixture. The reaction time depends on the reaction temperature.



   The compounds of the formula I prepared by the above process can be worked up and purified by known methods.



      The connections detu pe, - FSîe IrIrSn e.g. by reacting the sodium salts of the corresponding 4-hydroxyoxindoles of the formula IV, in which R1 has the above meaning, with epibromohydrin in dimethyl sulfoxide as the solvent.



   After the reaction has ended, it is poured into water and extracted with ethyl acetate. The ethyl acetate extracts are concentrated until the epoxypropoxyindole crystallizes.



   Of the compounds of the formula IV, 4-hydroxyoxindole and 4-hydroxy-1 methyloxindole are known. The new compounds of formula IV, such as 4-hydroxy-1-methyloxindole, e.g. by cyclization of the corresponding N -alkyl-N-chloroacetyl.o-anisidines and dimethylation (ether cleavage) of the 1 -alkyl-4-methoxyoxindoles thus obtained,
If the preparation of the starting compounds is not described, these are known or can be prepared analogously to known methods.



   The new compounds of the formula I and their pharmacologically acceptable acid addition salts have interesting pharmacodynamic properties with low toxicity and can therefore be used as medicaments,
The new substances show an inhibition of the positively inotropic adrenaline effect in the spontaneously beating isolated guinea pig atrium and lead to a strong inhibition of the tachycardia and blood pressure lowering caused by isoproterenol [1 (3, 4-dihydroxyphenyl) -2-isopropylaminoethanol in the anesthetized whole animal (cat, dog).

  The compounds accordingly have a blocking effect on the 3 adrenergic receptors and can therefore i.a. for the prophylaxis and therapy of coronary diseases, in particular for the treatment of angina pectoris, for the treatment of hyperkinetic cardiac syndrome and the conditions resulting from muscular-hypertrophic, subvalvular aortic stenosis.



   Because of their antiarrhythmic effects, the compounds are also suitable for the treatment of cardiac arrhythmias.



   The doses to be used naturally vary depending on the type of substance used, the administration and the condition to be treated.



   In the following examples, which illustrate the invention in more detail but are not intended to restrict its scope in any way, all temperatures are given in degrees Celsius and are uncorrected.
EMI1.1




   Example I.
4- [2-hydroxy-3- (2-methyl-3-butyn-2-ylamino) propoxyl] oxindole
3 g of 4- (2,3-epoxypropoxy) oxindole, 9 g of 3-amino-3-methylbutyne and 40 ml of tetrahydrofuran are heated to the boil for 2 days with stirring. The hot solution is filtered and allowed to crystallize. The title compound melts from 172 to 174 ".



   The 4- (2,3-epoxypropoxy) oxindole used as starting material was prepared as follows:
273 g of 4-hydroxyoxindole, 1300 ml of dimethyl sulfoxide and 55.8 g of 80% sodium hydride are heated to 60 for 1/2 hour, then a solution of 376 g of epibromohydrin in 500 ml of dimethyl sulfoxide is added dropwise at room temperature and stirred for 16 hours. It is poured into water, extracted with ethyl acetate and the ethyl acetate extracts are concentrated until crystallization, mp 175 to 177.

 

   Example 2
Ethyl 2-methyl-2- [2-hydroxy-3- (4-oxindolyloxy) propyl-amino] propionate
The procedure described in Example 1 is followed, but instead of 3-amino-3-methylbutyne, oc-aminoisobutyric acid ethyl ester is used. The title compound crystallizes from ether, m.p. 158 to 160 ".

 

Claims (1)

PATENTANSPRUCH PATENT CLAIM Verfahren zur Herstellung neuer Oxindole der Formel I, worin R1 für Wasserstoff oder einen niederen Alkylrest steht und R2 einen Alkinylrest, dessen Dreifachbindung nicht in a,3-Stellung steht zum Stickstoffatom, woran der Alkinylrest gebunden ist oder einen Carbalkoxyalkylrest bedeutet und ihrer Säureadditionssalze, dadurch gekennzeichnet, dass man Verbindungen der Formel II, worin R1 obige Bedeutung besitzt, mit Aminen der Formel III, worin R2 obige Bedeutung besitzt, umsetzt, und die so erhaltenen Verbindungen der Formel I als freie Basen oder als Säureadditionssalze gewinnt. Process for the preparation of new oxindoles of the formula I in which R1 is hydrogen or a lower alkyl radical and R2 is an alkynyl radical whose triple bond is not in the a, 3-position to the nitrogen atom to which the alkynyl radical is bonded or a carbalkoxyalkyl radical and its acid addition salts, thereby characterized in that compounds of the formula II in which R1 has the above meaning are reacted with amines of the formula III in which R2 has the above meaning, and the compounds of the formula I thus obtained are obtained as free bases or as acid addition salts. UNTERANSPRÜCHE 1. Verfahren nach Patentanspruch zur Herstellung von 4- [2-Hydroxy-3- (2-methyl- -butin-2-ylamino)propoxyl] -ox- indol, dadurch gekennzeichnet, dass man als Verbindung der Formel II 4-(2,3-Epoxypropoxy)oxindol und als Verbindung der Formel III 3-Amino-3-methylbutin verwendet, 2. Verfahren nach Patentanspruch zur Herstellung von 2-Methyl-2-[2-hydroxy-3 -(4-oxindolyloxy)propylamino]-pro- pionsäureäthylester, dadurch gekennzeichnet, dass man als Verbindung der Formel II 4-(2,3-Epoxypropoxy)oxindol und als Verbindung der Formel III ,a-Aminoisobuttersäureäthyl- ester verwendet, SUBCLAIMS 1. Process according to claim for the preparation of 4- [2-hydroxy-3- (2-methyl- butyn-2-ylamino) propoxyl] -ox- indole, characterized in that the compound of the formula II is 4- (2 , 3-epoxypropoxy) oxindole and used as a compound of formula III 3-amino-3-methylbutine, 2. The method according to claim for the preparation of 2-methyl-2- [2-hydroxy-3 - (4-oxindolyloxy) propylamino] propionic acid ethyl ester, characterized in that the compound of formula II is 4- (2,3- Epoxypropoxy) oxindole and used as a compound of the formula III, a-aminoisobutyric acid ethyl ester,
CH924871A 1971-06-24 1971-06-24 4 and 7-Aminopropoyx-oxindole derivs - useful as anti-arrhythmics and beta-adrenergic blockers CH547801A (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
BE793073D BE793073A (en) 1971-06-24 Aminoalkoxyoxindole derivs - as beta-adren ergic blockers
CH924871A CH547801A (en) 1971-06-24 1971-06-24 4 and 7-Aminopropoyx-oxindole derivs - useful as anti-arrhythmics and beta-adrenergic blockers
SE7207867A SE379196B (en) 1971-06-24 1972-06-15
US00263768A US3825558A (en) 1971-06-24 1972-06-19 Substituted aminopropoxy-2-indolinones
NL7208332A NL7208332A (en) 1971-06-24 1972-06-19
HUSA002367 HU164321B (en) 1971-06-24 1972-06-20
GB2874472A GB1391828A (en) 1971-06-24 1972-06-20 Oxindole derivatives
DD163906A DD99785A5 (en) 1971-06-24 1972-06-22
BE785282A BE785282A (en) 1971-06-24 1972-06-22 NEW OXINDOLE DERIVATIVES, THEIR PREPARATION AND MEDICINAL PRODUCTS CONTAINING THESE DERIVATIVES
RO7483072A RO62636A (en) 1971-06-24 1972-06-22 PROCESS FOR THE PREPARATION OF OXINDOL DERIVATIVES
IL39742A IL39742A0 (en) 1971-06-24 1972-06-22 Substituted oxindoles,their preparation and pharmaceutical compositions containing them
PL15620572A PL83679B1 (en) 1971-06-24 1972-06-22
DE2230426A DE2230426A1 (en) 1971-06-24 1972-06-22 PROCESS FOR PRODUCING NEW HETEROCYCLIC COMPOUNDS
RO7483172A RO62637A (en) 1971-06-24 1972-06-22 PROCESS FOR THE PREPARATION OF OXINDOL DERIVATIVES
JP47063153A JPS5820955B1 (en) 1971-06-24 1972-06-23
ES404174A ES404174A1 (en) 1971-06-24 1972-06-23 PROCEDURE FOR OBTAINING SUBSTITUTE OXIDOLS.
AT541172A AT330169B (en) 1971-06-24 1972-06-23 Process for the preparation of new oxindoles and their salts
FR7222696A FR2143343B1 (en) 1971-06-24 1972-06-23
AU43903/72A AU4390372A (en) 1971-06-24 1972-06-26 Organic compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH924871A CH547801A (en) 1971-06-24 1971-06-24 4 and 7-Aminopropoyx-oxindole derivs - useful as anti-arrhythmics and beta-adrenergic blockers
DE19722262285 DE2262285A1 (en) 1972-12-20 1972-12-20 Aminoalkoxyoxindole derivs - as beta-adren ergic blockers

Publications (1)

Publication Number Publication Date
CH547801A true CH547801A (en) 1974-04-11

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CH924871A CH547801A (en) 1971-06-24 1971-06-24 4 and 7-Aminopropoyx-oxindole derivs - useful as anti-arrhythmics and beta-adrenergic blockers

Country Status (1)

Country Link
CH (1) CH547801A (en)

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