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CH449040A - Process for the production of new araliphatic amines and their salts - Google Patents

Process for the production of new araliphatic amines and their salts

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Publication number
CH449040A
CH449040A CH1391765A CH1391765A CH449040A CH 449040 A CH449040 A CH 449040A CH 1391765 A CH1391765 A CH 1391765A CH 1391765 A CH1391765 A CH 1391765A CH 449040 A CH449040 A CH 449040A
Authority
CH
Switzerland
Prior art keywords
salts
phenyl
acid
new
araliphatic amines
Prior art date
Application number
CH1391765A
Other languages
German (de)
Inventor
Hennig Ingeborg
Lindner Ernst
Original Assignee
Hoechst 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
Application filed by Hoechst Ag filed Critical Hoechst Ag
Publication of CH449040A publication Critical patent/CH449040A/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/46Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C215/48Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
    • C07C215/54Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups linked by carbon chains having at least three carbon atoms between the amino groups and the six-membered aromatic ring or the condensed ring system containing that ring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/13Amines
    • A61K31/135Amines having aromatic rings, e.g. ketamine, nortriptyline
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/54Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C217/56Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
    • C07C217/62Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms linked by carbon chains having at least three carbon atoms between the amino groups and the six-membered aromatic ring or the condensed ring system containing that ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Description

  

  



  Verfahren zur Herstellung von neuen araliphatischen Aminen und deren Salzen
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von neuen araliphatischen Aminen und deren Salzen, die auf das Herz und den Kreislauf wirken.



   Es wurde gefunden, dass man araliphatische Amine der Formel I
EMI1.1     
 worin   R1    ein   Wasserstoff-oder    Halogenatom,   R2    einen gegebenenfalls im Phenylkern durch eine niedrig  molelculare    Alkyl-oder Alkoxygruppe substituierten Benzylrest oder einen   Cyclopentyl-bzw.      Cyclohexylrest    mit 1 oder 2 C-Atomen steht, und deren Salze, erhält, wenn man ein Amin der Formel II
EMI1.2     
 mit l-Phenyl-2-halogen-propan bzw.-propen umsetzt und eine gegebenenfalls vorhandene Doppelbindung hydriert und gegebenenfalls die erhaltenen basischen Verbindungen mit anorganischen oder organischen Säuren in die entsprechenden Salze überführt.



   Als solche   l-Phenyl-2-halogen-propane      bzw.-pro-    pene kommen beispielsweise in Frage :    l-Pheny-2-chlor-propan, 1-Phenyl-2-brom-propan    oder   l-Phenyl-2jod-propan    sowie die entsprechenden   l-Phenyl-2-halogen-propene. Diese Verbindungen kön-    nen durch Halogenierung von   Methyl-benzyl-carbinol    erhalten werden   (vgl.    Beilstein Bd. 5, 391 und Bd. 5   I.   



  Brg. Werk 190).



   Diese Umsetzung wird zweckmässig in geeigneten Lösungsmitteln, beispielsweise in aromatischen Kohlenwasserstoffen, wie Benzol oder Toluol, durch   länge-    res Erhitzen durchgef hrt. Zur Bindung des frei werdenden Halogenwasserstoffes setzt man vorteilhaft   1    Mol 1-Phenyl-2-halogen-propan bzw.-propen mit 2 Molen Amin um. Die Halogenwasserstoffbindung kann auch durch die üblichen basischen Mittel erfolgen, wie Alkali-und Erdalkali-carbonate oder-hydroxyde, sowie organische Basen, wie Pyridin oder Chinolin, die gegebenenfalls gleichzeitig als Lösungsmittel dienen können. Die Aufarbeitung erfolgt in üblicher Weise durch Abtrennung des halogenwasserstoffsauren Salzes der eingesetzten Base, beispielsweise durch Ausfällen mit   itther    oder Ausschütteln mit Wasser.

   Das basische Verfahrensprodukt kann dann durch Destillation oder durch Überführung in ein geeignetes Salz gereinigt werden. Werden Propen-halogenide verwendet, wird die Doppelbindung anschliessend nach den dafür üblichen bekannten Methoden hydriert.



   Die   Verfahrenserzeugnisse    k¯nnen als basische Verbindungen mit Hilfe von anorganischen oder organischen Säuren in die entsprechenden Salze übergeführt werden. Als anorganische Säuren kommen   bei-    spielsweise in Betracht : Halogenwasserstoffsäuren wie Chlorwasserstoffsäure und Bromwasserstoffsäure sowie SchwefelsÏure, Phosphorsäure und AmidosulfonsÏure.



     AIs    organische Säuren seien beispielsweise genannt :
Ameisensäure, Essigsäure, Propionsäure,   Milch-    säure, Glykolsäure, Gluconsäure, Maleinsäure, BernsteinsÏure, WeinsÏure, Benzoesäure, SalicylsÏure, ZitronensÏure, AcetursÏure, OxÏthansulfonsÏure und   Athylendiamintetra-Essigsäure. Man kann    die   Verfah-      renserzeugnisse    auch mit Hilfe von Alkylhalogeniden in entsprechende quaternäre Salze überführen, wenn der basische Rest ein tertiäres Stickstoffatom enthält.



   Die Verfahrensprodukte weisen eine ausserordentlich gute Herz-und   Kreislaufwirkung    auf. So führt z. B. die Verabreichung von   1-Phenyl-2- [1'-phenyl-      l'-cydohexyl-propyl-(3')]-amino-propan im Versuch    am isolierten Kaninchenherzen nach   Langendorff    bei einmaliger   Injok : tion    von nur 2, 5 y zu einer starken Coronargefässerweiterung, die im Vergleich zu dem normalen unbehandelten Herzen einer Zunahme der Coronardurchströmung von ca. 50   zozo    entspricht. 



   Die   Verfahrenserzeugnisse    sind den bereits bekann  ten Verbindungen ähnlicher Struktur    erheblich überlegen, so ist   b-ispielsweise    von dem bereits bekannten 1-Phenyl-2-[1',1'-diphenyl-propyl-(3')]-amino-propan die Applikation der   doppelten Dosis (5 γ) erforderlich,    wenn eine gleich starke coronargefässerweiternde Wirkung erreicht werden soll.



   Beispiel    22,      5    g 1,2-Diphenyl-4-amino-butan werden mit 10   g 1-Phenyl-2-brom-propan in    150 ccm Toluol 6 Stunden lang unter   Rückfluss    gekocht. Nach dem Abk hlen versetzt man mit 100 ccm Wasser, trennt die   Schichten    und destilliert aus der Toluollösung nach Trocknen mit   Natrium-sulfat    das Lösungsmittel unter vermindertem Druck ab. Der ¯lige R ckstand wird mit   2n-Salzsaure    in das Hydrochlorid des 1-Phenyl-2-[1', 2'  diphenyl-butyl- (4')]-amino-propans    vom Schmelzpunkt 162-l63¯C (¯thanol)  berf hrt.



  



  Process for the production of new araliphatic amines and their salts
The invention relates to a process for the preparation of new araliphatic amines and their salts, which act on the heart and circulation.



   It has been found that araliphatic amines of the formula I
EMI1.1
 wherein R1 is a hydrogen or halogen atom, R2 is a benzyl radical optionally substituted in the phenyl nucleus by a low molecular weight alkyl or alkoxy group or a cyclopentyl or. Cyclohexyl radical with 1 or 2 carbon atoms, and the salts thereof, obtained when an amine of the formula II
EMI1.2
 with 1-phenyl-2-halo-propane or -propen and hydrogenated an optionally present double bond and optionally converts the basic compounds obtained with inorganic or organic acids into the corresponding salts.



   Examples of such l-phenyl-2-halo-propanes or -propenes are: l-pheny-2-chloro-propane, 1-phenyl-2-bromopropane or l-phenyl-2-iodo-propane and the corresponding l-phenyl-2-halo-propene. These compounds can be obtained by halogenating methyl-benzyl-carbinol (cf. Beilstein Vol. 5, 391 and Vol. 5 I.



  Brg. Plant 190).



   This reaction is expediently carried out in suitable solvents, for example in aromatic hydrocarbons such as benzene or toluene, by prolonged heating. To bind the liberated hydrogen halide, it is advantageous to react 1 mole of 1-phenyl-2-halo-propane or -propene with 2 moles of amine. The hydrogen halide can also be bonded by the usual basic agents, such as alkali and alkaline earth carbonates or hydroxides, and organic bases, such as pyridine or quinoline, which can optionally also serve as solvents. Working up is carried out in the customary manner by separating off the hydrohalic acid salt of the base used, for example by precipitation with itther or shaking out with water.

   The basic process product can then be purified by distillation or by conversion into a suitable salt. If propene halides are used, the double bond is then hydrogenated using the known methods customary for this purpose.



   The products of the process can be converted into the corresponding salts as basic compounds with the aid of inorganic or organic acids. Examples of inorganic acids are: hydrohalic acids such as hydrochloric acid and hydrobromic acid, and also sulfuric acid, phosphoric acid and sulfamic acid.



     Examples of organic acids are:
Formic acid, acetic acid, propionic acid, lactic acid, glycolic acid, gluconic acid, maleic acid, succinic acid, tartaric acid, benzoic acid, salicylic acid, citric acid, aceturic acid, oxythanesulfonic acid and ethylenediaminetetra-acetic acid. The process products can also be converted into corresponding quaternary salts with the aid of alkyl halides if the basic radical contains a tertiary nitrogen atom.



   The products of the process have an extraordinarily good cardiovascular effect. So z. B. the administration of 1-phenyl-2- [1'-phenyl- l'-cydohexyl-propyl- (3 ')] -amino-propane in an experiment on isolated rabbit hearts according to Langendorff with a single injection of only 2.5 y to a strong coronary vasodilatation, which corresponds to an increase of the coronary perfusion of approx. 50 zozo compared to the normal untreated heart.



   The products of the process are considerably superior to the already known compounds of a similar structure, for example the application of the already known 1-phenyl-2- [1 ', 1'-diphenyl-propyl- (3')] -amino-propane twice the dose (5?) is required if an equally strong coronary vasodilator effect is to be achieved.



   Example 22, 5 g of 1,2-diphenyl-4-aminobutane are refluxed with 10 g of 1-phenyl-2-bromopropane in 150 cc of toluene for 6 hours. After cooling, 100 cc of water are added, the layers are separated and, after drying with sodium sulfate, the solvent is distilled off from the toluene solution under reduced pressure. The oily residue is converted into the hydrochloride of 1-phenyl-2- [1 ', 2' diphenyl-butyl- (4 ')] aminopropane with a melting point of 162-163¯C (¯thanol) with 2N hydrochloric acid transferred.

 

Claims (1)

PATENTANSPRUCH Verfahren zur Herstellung von neuen araliphatischen Aminen der Formel EMI2.1 worin Rt ein Wasserstoff- oder Halogenatom, R2 einen gegebenenfalls im Phenylkem durch eine niedrigmoleku- lare Alkyl-oder Alkoxygruppe substituierten Benzylrest oder einen Cyclopentyl- oder Cyclohexylrest bedeuten und X für einen Kohlenwasserstoffrest mit l oder 2 C Atomen steht, dadurch gekennzeichnet, dass man ein Amin der Formel EMI2.2 mit l-Phenyl-2-halogen-propan bzw.-propen umsetzt und eine gegebenenfalls vorhandene Doppelbindung hydriert. PATENT CLAIM Process for the preparation of new araliphatic amines of the formula EMI2.1 where Rt is a hydrogen or halogen atom, R2 is a benzyl radical optionally substituted in the phenyl nucleus by a low molecular weight alkyl or alkoxy group or a cyclopentyl or cyclohexyl radical and X is a hydrocarbon radical with 1 or 2 carbon atoms, characterized in that one Amine of the formula EMI2.2 with 1-phenyl-2-halo-propane or -propen and hydrogenated any double bond present. UNTERANSPRUCH Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass man die erhaltenen basischen Verbin- dungen mit anorganischen oder organischen Säuren in ihre Salze iiberfiihrt. SUBClaim Process according to patent claim, characterized in that the basic compounds obtained are converted into their salts with inorganic or organic acids.
CH1391765A 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts CH449040A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF32534A DE1181233B (en) 1960-11-12 1960-11-12 Process for the production of cardiovascular and araliphatic amines

Publications (1)

Publication Number Publication Date
CH449040A true CH449040A (en) 1967-12-31

Family

ID=7094673

Family Applications (5)

Application Number Title Priority Date Filing Date
CH1392065A CH449038A (en) 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts
CH1391865A CH449041A (en) 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts
CH1391765A CH449040A (en) 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts
CH1391965A CH449037A (en) 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts
CH1304861A CH412923A (en) 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts

Family Applications Before (2)

Application Number Title Priority Date Filing Date
CH1392065A CH449038A (en) 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts
CH1391865A CH449041A (en) 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts

Family Applications After (2)

Application Number Title Priority Date Filing Date
CH1391965A CH449037A (en) 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts
CH1304861A CH412923A (en) 1960-11-12 1961-11-10 Process for the production of new araliphatic amines and their salts

Country Status (7)

Country Link
BE (1) BE610231A (en)
CH (5) CH449038A (en)
DE (1) DE1181233B (en)
FR (1) FR1753M (en)
GB (1) GB1001827A (en)
NL (1) NL271206A (en)
OA (1) OA01975A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2482956A1 (en) * 1980-05-22 1981-11-27 Synthelabo Cardiovascular phenyl or cycloalkyl-cyclohexyl-alkylamine derivs. - which increase coronary flow but not cardiac work e.g. n-alpha-methyl-beta-phenyl:ethyl 2-cyclohexyl 2-phenyl ethylamine

Also Published As

Publication number Publication date
FR1753M (en) 1963-04-01
DE1181233B (en) 1964-11-12
GB1001827A (en) 1965-08-18
CH449037A (en) 1967-12-31
CH449041A (en) 1967-12-31
OA01975A (en) 1970-05-05
NL271206A (en)
BE610231A (en) 1962-05-14
CH412923A (en) 1966-05-15
CH449038A (en) 1967-12-31

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