CH374664A - Process for the production of new bisquaternary ammonium compounds - Google Patents

Process for the production of new bisquaternary ammonium compounds

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Publication number
CH374664A
CH374664A CH4217057A CH4217057A CH374664A CH 374664 A CH374664 A CH 374664A CH 4217057 A CH4217057 A CH 4217057A CH 4217057 A CH4217057 A CH 4217057A CH 374664 A CH374664 A CH 374664A
Authority
CH
Switzerland
Prior art keywords
trimethylammonium
pyridinium
pyridine
bromopropyl
dependent
Prior art date
Application number
CH4217057A
Other languages
German (de)
Inventor
John Cavallito Chester
Poe Gray Allan
Original Assignee
Irwin Neisler & Company
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 Irwin Neisler & Company filed Critical Irwin Neisler & Company
Publication of CH374664A publication Critical patent/CH374664A/en

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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
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    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/20—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
    • C07D211/22—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/30—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom
    • C07D211/32—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom by oxygen atoms
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
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    • C07—ORGANIC CHEMISTRY
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/32—Sulfur atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
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    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/20—Spiro-condensed ring systems
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/10—Spiro-condensed systems

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

  

  



  Verfahren zur Herstellung neuer   bisquaternärer    Ammoniumverbindungen ?
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung neuer   bisquatemärer    Ammoniumverbindungen der Formel
EMI1.1     
 in welcher
EMI1.2     
 den Pyridinring oder den durch eine niedere Alkylgruppe, welche gegebenenfalls höchstens zwei Oxy-, Acetoxy-, Phenyl-oder Benzoxygruppen trägt, N-substituierten 1, 2, 5,   6-Tetrahydropyridinring    oder Piperidinring und R,   Rl,    R2,   R3    und R4   nichtionisie-    rende Gruppen oder, jedoch nicht alle, Wasserstoff,

     R5    und   R    niedere aliphatische Gruppen oder   R5    und RU zusammen mit dem Stickstoffatom einen gegebenenfalls ein weiteres Heteroatom aufweisenden Ring bedeuten, R7 eine niedere Alkylgruppe, A eine Alkylenbrücke mit 2 bis 6   Kolilenstoffatomen    und Xe ein Anion bedeuten, wobei die Gruppe
EMI1.3     
 ein Radikalgewicht zwischen 150 und 350 besitzt, wobei, falls
EMI1.4     
 den Pyridinring bedeutet, mindestens einer der Substituenten R und   R4    Wasserstoff ist, und wobei die Gruppe
EMI1.5     
 ein Radikalgewicht zwischen 59 und 117 besitzt.



   Im folgenden wird die Gruppe
EMI1.6     
 als   grössere Ammoniumgruppe   und die Gruppe
EMI1.7     
 als     Icleinere Ammoniumgruppeo    bezeichnet.



   Die Summe der Kohlenstoffatome in den in der kleineren quaternären Ammoniumgruppe gebundenen Substituenten   R5,      R, R soll    vorzugsweise nicht grösser als 7 sein, wobei vorzugsweise wenigstens einer der Substituenten das Methylradikal sein soll.



  Als Substituenten R5,   Rg    und R, dienende Alkylradikale sind beispielsweise die Methyl-, ¯thyl-, n-Propyl-bzw. die Isopropylgruppen zu nennen.



     R.    und   R6    können gemeinsam mit dem   Stickstoff-    atom z. B. eine Pyrrolidin-,   Methylpyrrolidin-oder      Piperidingruppe bilden.    Die heterocyclische Gruppe kann aber auch ein Sauerstoff-oder ein   Schwefel-    atom enthalten, wie dies bei der   Morpholin-und      Thiamorpholingruppe    der Fall ist.



   Als bevorzugte Beispiele für die kleinere Ammoniumgruppe sind die    Trimethylammonium-,   
MethyldiÏthylammonium-,
DimethylÏthylammonium-,
Methyldipropylammonium-,
Dimethylisopropylammonium-,
Methyläthylpropylammonium-,    N-Methylpyrrolidinium-,   
N-Athylpyrrolidinium-,    N-Methylpiperidinium-,   
N-Methylmorpholinium-,
N-Methylthiamorpholinium-und die
N-Methylthiazolidiniumgruppen zu nennen. Andere Beispiele hierfür sind die Triäthylammoniumgruppe, die   N-Athylpiperidinium-,    die N-Propylpyrrolidinium-und die   N-Athylmorpholiniumgruppe.   



   Wie erwähnt, hat die grössere Ammoniumgruppe ein Radikalgewicht zwischen 150 und 350. Die Substituenten können an eine oder mehrere freie Stellungen des Ringes gebunden sein. Falls der Pyridinring vorliegt, so muss von den 2-und 6-Stellungen des Ringes mindestens eine unsubstituiert sein, weil sonst zufolge der sterischen Hinderung die Quaternisierung schwierig ist. Die Substituenten können verschiedene Ringe enthalten ; sie sind aber mit dem Pyridinring nicht anelliert, sondern wirkliche Substituenten. Da das Gewicht des unsubstituierten Pyridylradikals nur 79 beträgt, muss jenes seiner Substituenten so gross sein, dass das Gesamtgewicht des substituierten Pyridylradikals zwischen 150 und 350 liegt.



   Am Pyridin-oder hydrierten Pyridinring sind nichtionisierende Radikale als Substituenten vorhanden. Mit dieser Einschränkung kommen als Substituenten irgendwelche organische Radikale mit ge  nügendem    Radikalgewicht in Betracht, z. B. organische Ringstrukturen, Arylgruppen, Alkylgruppen mit verzweigter Kette, Aralkyl-, Aralkoxy-, Aralkenyl-,   Arylthioalkyl-,      Diarylaminoalkyl-,      Hetero-    cyclylalkyl-,   Cycloalkyl-,    Aryloxyalkyl-, Aralkoxyalkyl-, Aralkylthioalkyl-, Arylcarboxyalkyl-, Arylimidoalkylgruppen und heterocyclische Ringsysteme.



  Jeder dieser Substituenten ist mit dem Pyridinring entweder direkt verknüpft oder über ein   brücken-    bildendes Verbindungsglied, wie z. B. Äther-, Thio äther-, Ester-, Amid-, Sulfonobr ckenglied usw. oder über verschiedene Gruppen, wie z. B. Carbonyl-, Alkenyl-, Alkanylgruppen, verbunden. Vom substituierten Ringsystem der grösseren Ammoniumgruppe kann nur ein Ringatom einen Teil eines andern Ringsystems bilden.



   Für die grössere Ammoniumgruppe werden folgende Beispiele angeführt :
2-und 4-(3-IndolylÏthyl)-pyridinium,
2-und 4-(l-IndolylÏthyl)-pyridinium,
2-und   4- (1-Methyl-3-indolyiäthyl)-pyridinium,   
2-(3-IndolylÏthyl)-5-Ïthylpyridinium,    2- (1-Methyl-3-indolyläthyl)-5-äthylpyridinium,   
2-und   4-(1-Naphthyläthyl)-pyridinium    und
2-und   4-(1-Indenyläthyl)-pyridinium.   



   Andere Beispiele hierfür sind :
2-und   4- (l-Naphthyläthenyl)-pyridinium,   
2-und   4-(2-Naphthyläthenyl)-pyridinium,   
2-, 3-und 4-(2-Indoly)-pyridinium,
2-und   4- (3-Indolyläthenyl)-pyridinium,   
2-, 3-und 4-(3,3'-Diindolylmethyl)-pyridinium,
2-und   4- (1-Benzotriazolyläthyl)-pyridinium,   
2-, 3-und 4-{6-(Bicyclo-[2. 2.   1]-2-heptenyI)}-    pyridinium,    5- {6- (Bicyclo- [2.    2.   1]-2-heptenyl) -2-picolinium,   
2-, 3-und 4-Benzylpyridinium,
2-, 3-und 4-Carboxanilido-pyridinium,
2-und   4- (Benzoxypropyl)-pyridinium,   
2-, 3-und 4-Benzoylpyridinium,
2-und   4-Stilbazulium,   
2-, 3-und   4- (Phenylthioäthyl)-pyridinium,   
2-, 3-und 4-(tert.

   ButylthioÏthyl)-pyridinium,
2-, 3-und   4- (Benzylthioäthyl)-pyridinium,   
3-und 4-Carbobenzyloxypyridinium,
2-und   4-(Diphenylaminoäthyl)-pyridinium,   
2-und   4- (Phthalimidoäthyl)-pyridinium,   
2-und 4-Hexylpyridinium,
2-und 4-Decylpyridinium,
2-und   4-(2-Oxocyclohexyläthyl)-pyridinium,       2- (3, 4-Dichlorbenzyl)-pyridinium,   
2-, 3-und 4-(Diphenyl-methyl)-pyridinium,
3-und   4- (Triphenyl-methyl)-pyridinium,   
2-, 3-und   4-(Benzyloxyäthyl)-pyridinium,   
2-und   4- (9-Fluorenyloxypropyl)-pyridinium,   
2-, 3-und 4-(Benzyloxymethyl)-pyridinium,
2-, 3-und 4- (Diphenyl-methoxymethyl) pyridinium,
2-, 3-und   4- (9-Fluorenyl-carboxypropyl)-    pyridinium,

  
2-und   4- [l- (l-Benzyl-3-indolyl)-2-propyl]-    pyridinium,
2-und   4- [- (l-MethyI-3-indoIyI)-c-cycIohexyI-     Ïthyl]-pyridinium,
2-und 4-(l-Methyl-3-oxindolylÏthyl) pyridinium,
2-, 3-und 4-   hiazolylthioäthyl)-    pyridinium,    2- (2-Pyridylamino)-pyridinium,   
2-und 4- (9-Fluorenyläthyl)-pyridinium,
2-und   4- (9-Fluorenyl)-pyridinium,   
2-und 4-(3-BenzothiophenylÏthyl)-pyridinium,
2-und   4- (9-Carbazolyldthyl)-pyridinium,   
2-und   4-(3, 4-Dichlorphenyläthyl)-pyridinium,        2,    4-Dibenzylpyridinium,    2, 5-bis-(Phenylthioäthyl)-pyridinium,   
2,   4-bis-     -pyridinium,
2-und   4-(2-Thienyläthyl)-pyridinium,

     
2-und   4-(2-Furyläthyl)-pyridinium,   
2,   4-bis-(2-Furyläthenyl)-pyridinium,   
2-und   4- (2-Benzofuryläthyl)-pyridinium,   
2-und   4-Phenylpyridinium,   
2-und   4- (2-Naphthyl)-pyridinium,       2-(2-Phthalimidoäthyl)-5-äthylpyridinium,   
2-und   4- (2-Benzisosulfonazoyläthyl)-    pyridinium,
2-Hexyl-5-Ïthylpyridinium,
2, 4-bis- (2-Pyrrolyläthyl)-pyridinium,
2-und   4-(2-Phenyl-l-pyrrolyläthyl)-pyridinium,   
2-und   4- (l-Oxindolyläthyl)-pyridinium,   
2-und 4-(2-Indanyl)-pyridinium,    a- (2-Indanyliden)-4-picolinium, a- (1-Indanyliden)-2-picolinium,  α

  -(Cyclohexyliden)-4-picolinium,   
4-   8-Methyl-ss-phenyläthenyl)-pyridinium,   
2-und   4- (b-Phenylbutadienyl)-pyridinium,   
2-und   4- (Benzoylpropyl)-pyridinium    und    5-(Cyclohexylthioäthyl)-2-picolinium.   



   Au¯erdem kommt für die grössere Ammoniumgruppe das l-(nieder-Alkyl)-piperidin in Betracht, das den oben angeführten Typen entspricht, in welchen der Pyridinring durch einen   1- (nieder-Alkyl)-    piperidinring ersetzt wurde. Ebenso verwendbar sind Piperidine, wie spiro-[(1-Methyloxindol)-3,4'-(1'-methyl piperidinium)],    spiro- [Fluorenyl-9, 4'- (1'-methylpiperidinium)],   
1-Benzylpiperidinium,
1-PhenylÏthylpiperidinium,    1-(2-Oxy-2-phenyläthyl)-piperidinium,   
1-Octylpiperidinium,
1-Dodecylpiperidinium,   
1-(2-Oxydecyl)-piperidinium,
1- (2-Oxyoctyl)-piperidinium,       1- (2-Acetoxyoctyl)-piperidinium    und    1- (2-Benzoxyoctyl)-piperidinium.   



   Die elektrostatischen Ladungen der beiden quaternären Ammoniumteile werden durch zwei Anionen abgesättigt. Diese beiden Anionen können gleich oder voneinander verschieden sein. Die genaue Natur dieser Anionen ist für die erwähnte Verwendung der nach dem erfindungsgemässen Verfahren hergestellten Verbindungen nicht wesentlich, weil jedes Anion nur dazu dient, die ansonsten freie elektrische Ladung des Stickstoffatoms zu binden und weil bei den Bedingungen, unter welchen die Verbindungen für pharmadynamische Präparate verwendet werden, die Menge irgendeines Anions nicht ausreicht, um einen bemerkenswerten physiologischen Effekt hervorzurufen. Brauchbare Anionen sind z. B.   lialogen-,    Sulfat-, Zitrat-, Tartrat-, Azetat-und Phosphationen.



   Man kann die Struktur der neuen nach dem erfindungsgemässen Verfahren herstellbaren Verbindungen so auffassen, dass bei ihnen ein mehrere Kohlenstoffatome enthaltendes, niederes Alkan an zwei verschiedenen Kohlenstoffatomen substituiert ist, und zwar einerseits durch eine quaternäre Ammo  niumgruppe    von verhältnismässig niederem Radikalgewicht und anderseits durch eine zweite, einen Pyridinring oder hydrierten Pyridinring enthaltende quaternÏre Ammoniumgruppe mit einem grösseren Radikalgewicht ais die erste Gruppe. Die quaternären Ammoniumgruppen sind mit dem niederen Alkan durch die   Onium-Stickstoffatome    verbunden.



  In den   Molekularstrukturen,    welche den angeführten Bedingungen entsprechen, sind andere ionare Substi  tuenten    als jene, welche die beiden quaternären Ammoniumfunktionen bilden, ausgeschlossen. Die gemäss der Erfindung hergestellten Verbindungen sind feste Stoffe mit verhältnismässig hohen Schmelzpunkten. Sie besitzen eine ungewöhnliche   blutdrucksenkende Wirkung    verschieden langer Dauer sowie ganglienblockierende Eigenschaften. Diese beiden Merkmale können durch Anderungen der molekularen Struktur in verschiedenen Teilen der Verbindung voneinander unabhängig beeinflusst werden.



   Die neuen bisquaternären Ammoniumverbindungen werden erfindungsgemäss so hergestellt, dass ein Amin der Formel II
EMI3.1     
 mit einem quaternären Ammoniumsalz der Formel III
EMI3.2     
 in der   X'ein    Chlor-, Brom-oder Jodatom bedeutet, umgesetzt wird.



   Bei der praktischen Durchführung können die Reaktionspartner in äquimolaren Mengen oder einer derselben, je nach Zugänglichkeit des Ausgangsmaterials und je nach der Leichtigkeit, mit der das Produkt gereinigt werden kann, im   tÇberschuss    verwendet werden.



   Bei Durchführung der Reaktion können als Lösungsmittel Azetonitril, Dimethylformamid, aliphatische Alkohole, z. B.   iisthanol, Methanol,    Isopropylalkohol, Propylalkohol oder Isoamylalkohol, Nitrobenzol, Nitroalkane, wie Nitromethan und Nitro äthan, Mischungen von Dioxan und einem Alkohol und ähnliche polare Lösungsmittel und Lösungsmittelmischungen verwendet werden. Die Reaktion kann auch mit einem   grossen Uberschuss    der Ausgangsbase   durcngeführt    werden, welche anstelle des  Lösungsmittels tritt. Für die Herstellung von Verbindungen des in den Beispielen 16 bis 18   erläuter-    ten Typus werden Alkohole und Alkohole enthaltende Gemische vorgezogen, obgleich irgendeines der angeführten polaren Lösungsmittel ebenfalls verwendet werden kann.



   Man arbeitet am besten bei Temperaturen, welche zwischen Raumtemperatur und   150     C liegen, unter Atmosphärendruck oder in einem geschlossenen Reaktionsgefäss ; das Arbeiten unter Rückflusskühlung bei etwa   80  C    wird bevorzugt. Die Anwendung der angegebenen niederen Temperatur unter längerem Zeitaufwand ist zweckmässig, weil über   200  C    die Umkehr der Quaternisierungsreaktion zu unerwünschten Komplikationen führt.



   Die erfindungsgemäss hergestellten Verbindungen zeigen besonders blutdrucksenkende Wirkungen, die mit der Stärke der   ganglienblockierenden    Wirkung nicht in Beziehung stehen. Durch diese pharmakologische Erkenntnis wird die therapeutische Ver  wendungsmöglichkeit    der Verbindung erhöht, und die Verwendung der jeweils gewünschten Verbindungen zeigt keine der gewöhnlich auftretenden unangenehmen Nebenwirkungen wie heftige posturale Blutsenkung, Verstopfung, Dilatation und   Lähmung    der Pupille, trockener Mund, herabgesetzte Potenz usw.



   Beispiel 1    1-(4-Benzylpyridinium)-3-(trimethylammonium)-    propandibromid
Eine Lösung von 10, 4 g (0, 04 Mole) 3-Brom  propyltrimethylammoniumbromid    und 9, 0 g (0, 06 Mole) 4-Benzylpyridin in 35 cm3 Azetonitril wurde 6 Stunden lang auf Rückflusstemperatur erwärmt.



  Der gebildete Niederschlag wurde gesammelt und aus   n-Propylalkohol    und Athylazetat umkristallisiert. Es ergaben sich 7, 6 g   (44    der theoretischen Ausbeute) 1- (4-Benzylpyridinium)-3- (trimethylammonium)-propandibromid. Nach drei weiteren Rekristallisationen aus Isopropylalkohol wurde ein Produkt erhalten, das bei 172-174  C schmilzt.



  Analyse :
Berechnet : C 50, 25 H 6, 09 Br 37, 15
Gefunden : 50, 32 6, 38 36, 72
Beispiel 2    1- (2-Benzylpyridinium)-3- (trimethylammonium)-    propandibromid
Einer Lösung von 6, 8 g (0, 026 Mole) 3-Brompropyl-trimethylammoniumbromid in Isopropylalkohol wurden 6, 8 g (0, 04 Mole) destilliertes Benzylpyridin zugesetzt. Diese Lösung wurde 30 Stunden auf Rückflusstemperatur erwärmt. Aus der kalten Lösung wurde dann durch Zusatz von Athylazetat das   1- (2-Benzylpyridinium)-3- (trimethylammonium)-    propandibromid als hygroskopische, feste Substanz ausgefällt.



   Beispiel 3   
1- [4- (t-Butylthioäthyl)-pyridinium]-3- (trimethyl- ammonium)-propandibromid   
Dem Beispiel   1    entsprechend, wurde   4- (t-Butyl-      thioäthyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [4- (t-Butylthioiithyl)-pyridi-    nium]-3- (trimethylammonium)-propandibromid umgesetzt. Diese Verbindung ist eine hygroskopische, feste Substanz.



   Beispiel 4    1- [4- (n-Propylthioäthyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid
Dem Verfahren gemäss Beispiel 1 folgend, wurde durch Umsetzen von   4- (n-Propylthioäthyl)-    pyridin mit 3-Brompropyl-trimethylammoniumbromid das   1- [4- (n-Propylthioäthyl)-pyridinium]-3-      (trimethylammonium)-propandibromid    als hygroskopische, feste Substanz erhalten.



   Beispiel 5    1- [4- (Benzoxypropyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid
Dem Verfahren gemäss Beispiel 1 folgend, wurde durch Umsetzen von   4- (Benzoxypropyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid das 1- [4   (Benzoxypropyl)-pyridinium]-3-(trimethylammonium)-    propandibromid erhalten. Diese Verbindung ist eine feste Substanz, die bei 225-226  C unter Zersetzung schmilzt.



  Analyse :
Berechnet : C 50, 21 H 6, 02 Br 31, 82
Gefunden : 50, 20 5, 94 31, 20
Beispiel 6   
1- [4- (Carbobenzyloxy)-pyridinium]-3- (trimethyl- ammonium)-propandibromid   
Dem Verfahren gemäss Beispiel   1    folgend, wurde durch Umsetzen von Benzyl-4-picolinat mit 3-Brompropyl-trimethylammoniumbromid das   1- [4- (Carbo-       benzyloxy)-pyridinium]-3-(trimethylammonium)-pro-    pandibromid erhalten.



   Beispiel 7   
1- [4- (Phenylthiodthyl)-pyridinium]-3- (trimethyl- ammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 1 folgend, wurde durch Umsetzen von   4-(Phenylthioäthyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid das 1- [4  (Phenylthioäthyl)-pyridinium]-3-    (trimethylammonium)-propandibromid erhalten. Diese Verbindung schmilzt bei   170-172     C.



  Analyse :
Berechnet : C 47, 91 H 5, 92 Br 33, 55
Gefunden : 47, 35 5, 83 34, 00 
Beispiel 8   
1-[2-(Phenylthioäthyl)-pyridinium]-3-(trimethyl- ammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 1 folgend, wurde durch Umsetzen von 2-(Phenylthioäthyl)-pyridin mit 3-Brompropyltrimethylammoniumbromid das   1- [2-    (Phenylthioäthyl)-pyridinium]-3- (trimethylammo  nium)-propandibromid    als hygroskopische, feste Substanz erhalten.



  Analyse :
Berechnet : Br 33, 55
Gefunden : 33, 20
Beispiel 9   
1- (4-Benzylpyridinium)-3- (l-methylpyrrolidinium)-    propandibromid
Dem Verfahren gemäss Beispiel   1    folgend, wurde durch Umsetzen von   4-Benzylpyridin    mit 3-Brom  propyl-l-methylpyrrolidiniumbromid    das   1- (4-Benzyl-    pyridinium)-3-   (l-methylpyrrolidinium)-propandi-    bromid als hygroskopische, feste Substanz erhalten.



  Analyse :
Berechnet (+ 1   H20)    : Br 33, 70
Gefunden : 33, 85
Beispiel 10   
1- (4-Benzylpyridinium)-3- (l-methylpiperidinium)-    propandibromid
Dem Verfahren gemäss Beispiel 1 folgend, wurde durch Umsetzen von   4-Benzylpyridin    mit 3-Brom  propyl-l-methylpiperidiniumbromid    das   1- (4-Benzyl-    pyridinium)-3- (1-methylpiperidinium)-propandibromid erhalten. Diese Verbindung schmilzt bei 227 bis 230  C.



  Analyse :
Berechnet :   (+ 1, Z2 H2O)   
C 52, 61 H 6, 53 Br 33, 34   H20    1, 85
Gefunden :
52, 19 6, 12 32, 77 1, 02
Beispiel 11
1-   (4-Benzylpyridinium)-6- (trimethylammonium)-    hexandibromid
Dem Verfahren gemäss Beispiel   1    folgend, wurde durch Umsetzen von   4-Benzylpyridin    mit 6-Brom  hexyl-trimethylammoniumbromid    das   1- (4-Benzyl-    pyridinium)-6-   (trimethylammonium)-hexandibromid    erhalten.



   Beispiel 12    1- [4- (Diphenylaminodthyl)-pyridiniuml-3- (tri-    methylammonium)-propandibromid
Dem Verfahren gemäss Beispiel 1 folgend, wurde durch Umsetzen von   4- (Diphenylaminoäthyl)-pyridin    mit 3-Brompropyltrimethylammoniumbromid das   1- [4- (Diphenylaminoäthyl ;)-pyridinium]-3- (trimethyl-      ammonium)-piopandibromid    erhalten.



   Beispiel 13   
1-[2-(2-Oxocyclohexyläthyl)-pyridinium]-
3-(trimethylammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 1 folgend, wurde durch Umsetzen von   2- (2-Oxocyclohexyläthyl)-pyri-    din mit 3-Brompropyltrimethylammoniumbromid das   1-[2-(2-Oxocyclohexyläthyl)-pyridinium]-3-(trimethyl-    ammonium)-propandibromid als hygroskopische, feste Substanz erhalten.



   Beispiel 14   
1- (4-Benzoylpyridinium)-3- (trimethylammonium)-    propandibromid
Dem Verfahren gemäss Beispiel 1 folgend, wurde durch Umsetzen von 4-Benzoylpyridin mit 3-Brompropyl-trimethylammoniumbromid das   1- (4-Benzoyl-       pyridinium)-3- (trimethylammonium)-propandibromid    erhalten. Diese Verbindung ist eine feste Substanz, die bei   221-222     C unter Zersetzung schmilzt.



  Analyse :
Berechnet (+   1/2      H, O)    :
C 47, 69 H 5, 57 Br 35, 26   H20    1, 99
Gefunden :    47,    97 5, 63 35, 52 2, 80
Beispiel 15    1- [4- (4,    5, 6,   7-Tetrachlorphthalimidoäthyl)-       pyridinium]-3- (trimethylammonium)-    propandibromid
Dem Verfahren gemäss Beispiel 1 folgend, wurde durch Umsetzen von   4- (4,    5, 6, 7-Tetrachlorphthalimidoäthyl)-pyridin mit 3-Brompropyl-trimethylammoniumbromid das   1- [4- (4,    5, 6, 7-Tetrachlorphthal  imidoäthyl)-pyridinium]-3-    (trimethylammonium)propandibromid erhalten.



   Beispiel 16   
1- (4-Benzyl-1-methylpiperidinium)-3- (trimethyl- ammonium)-propandibromid   
Eine Lösung von 7, 0 g (0, 037 Mole) 4-Benzyl  1-methylpiperidin    und 10, 5 g (0, 04 Mole) 3-Brompropyl-trimethylammoniumbromid in 50   cm8 Iso-    propylalkohol wurde 24 Stunden auf Rückflusstemperatur erwärmt. Der bei Verdünnung mit   Athylazetat    anfallende, kristalline Niederschlag wurde zweimal aus Isopropylalkohol und Athylazetat   umkristalli-    siert. Es ergaben sich 8, 6 g   (500/o    der theoretischen Ausbeute)   1- (4-Benzyl-l-methylpiperidinium)-3- (tri-    methylammonium)-propandibromid. Die Verbindung schmilzt bei   237-238     C.



  Analyse :
Berechnet : C 50, 67 H 7, 61 Br 35, 49
Gefunden : 50, 58 7, 73 35, 03 
Beispiel 17    1-(2-Benzyl-l-methylpiperidinium)-3-(trimethyl-    ammonium)-propandibromid
Nach dem in Beispiel 16 beschriebenen Vorgang wurde   2-Benzyl-l-methylpiperidin    mit 3-Brompro  pyl-trimethylammoniumbromid    umgesetzt. Dabei wurde das   1- (2-Benzyl-l-methylpiperidinium)-3- (tri-    methylammonium)-propandibromid als weisse, hygroskopische Substanz gewonnen.



  Analyse :
Berechnet : Br 35, 49
Gefunden : 35, 13
Beispiel 18    l- [4- (3-0xypropyl)-l-methylpiperidinium]-
3-(triäthylammonium)-propandibromid   
Nach dem in Beispiel 16 beschriebenen Vorgang wurde   4- (3-Oxypropyl)-l-methylpiperidin    mit 3-Brompropyl-trimethylammoniumbromid quaternisiert. Nach Umkristallisieren aus Athanol und Athylazetat wurde mit etwa   43    der theoretischen Ausbeute das   I- [4-       (3-Oxypropyl)-I-methylpiperidinium] 3- (triäthyl-    ammonium)-propandibromid erhalten, das bei   250     C schmilzt.



  Analyse :
Berechnet : C 43, 07 H 8, 19 Br 38, 21
Gefunden : 42, 93 8, 02 37, 93
Beispiel 19    1- [4- (3-Indolyläthyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid
Eine Lösung von 6, 4 g (0, 028 Mole)   4- (3-Indolyl-      äthyl)-pyridin    und 7, 9 g (0, 03 Mole) 3-Brompropyltrimethylammoniumbromid in 50 cm3 Azetonitril wurde 28 Stunden am Wasserbad auf Rückflusstemperatur erwärmt. Das kristalline   Präzipitat    wurde gesammelt und zweimal aus Athanol und Äthylazetat umkristallisiert. Es ergaben sich 8, 7 g   (65 /o    der theoretischen Ausbeute)   l-t4-(3-Indolyläthyl)-      pyridinium]-3-    (trimethylammonium)-propandibromid in Form blassgrüner Kristalle.

   Die Substanz schmilzt unter Gasentwicklung bei   218     C.



  Analyse :
Berechnet : C 52, 18 H 6, 05 Br 33, 07
Gefunden : 52, 14 6, 25 33, 05
Beispiel 20    1- [4- (I-Benzotriazolyldthyl)-pyridiniuml-   
3- (trimetliglammonium)-propandibromid
Dem in Beispiel 19 beschriebenen Verfahren entsprechend, wurde   4-(1-Benzotriazolyläthyl)-pyri-    din mit 3-Brompropyl-trimethylammoniumbromid in   äthylalkoholischer    Lösung zur Reaktion gebracht.



  Durch Umkristallisieren aus Alkohol, Äther und dann Isopropylalkohol wurde das   1- [4- (l-Benzo-      triazolyläthyl)-pyridinium]-3-    (trimethylammonium)propandibromid aIs weisse, kristalline Substanz erhalten.



  Analyse :
Berechnet   (+ I HoO)    :
C 45, 34 H 5, 81 Br 31, 76
Gefunden : 45, 57 6, 03 31, 91
Beispiel 21    1- [2- (3-Indolyrdthyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid
Nach dem in Beispiel 19 beschriebenen Verfahren wurde durch Umsetzen von   2- (3-Indolylmethyl)-pyri-    din mit 3-Brompropyl-trimethylammoniumbromid das   1-t2-(3-Indolyläthyl)-pyridinium]-3-    (trimethyl  ammonium)-propandibromid    erhalten. Diese Substanz schmilzt bei   201-203     C.



  Analyse :
Berechnet : C 52, 18 H 6, 05 Br 33, 07
Gefunden : 52, 23 6, 17 32, 51
Beispiel 22    1-t4-(Phthalimidoäthyl)-pyridinium]-3-(trimethyl-    ammonium)-propandibromid
Dem in Beispiel 19 angegebenen Verfahren entsprechend, wurde durch Umsetzung von   4-Phthal-      imidoäthyl-pyridin    mit 3-Brompropyl-trimethylammoniumbromid das   1- [4- (Phthalimido'dthyl)-pyridiniuml-    3- (trimethylammonium)-propandibromid erhalten.



  Diese Verbindung schmilzt bei 204  C.



  Analyse :
Berechnet : C 49, 14 H 5, 30 Br   31,    14
Gefunden : 49, 46 5, 32 30, 89
Beispiel 23    1-t4-(1-Indenyläthyl)-pyridinium]-3-(trimethyl-    ammonium)-propandibromid
Dem in Beispiel 19 angegebenen Verfahren entsprechend, wurde durch Umsetzung von   4-(1-In-    denyläthyl)-pyridin mit 3-Brompropyl-trimethylammoniumbromid das   1- [4- (l-lndenyldthyl)-pyridi-      nium]-3- (trimethylammonium)-propandibromid    erhalten. Diese Verbindung schmilzt bei   196-197       C.   



  Analyse :
Berechnet : C 54, 78 H 6, 27 Br 33, 14
Gefunden : 54, 52 6, 43 33, 05
Beispiel   24      
1- [2- (2-Benzothiazolthioäthyl)-pyridinium]-
3- (trimethylammonium)-propandibromid   
Dem in den Beispielen 1 und 19 angegebenen Verfahren entsprechend, wurde   2- (2-Benzothiazol-      thioäthyl)-pyridin    mit   3-Brompropyltrimethylamino-    niumbromid zu   1-[2-(2-BenzothiazolthioÅathyl)-pyri-      dinium]-3- (trimethylammonium)-propandibromid    umgesetzt. 



   Beispiel 25   
1-spiro- [ (1-Methyloxindolyl)-3, 4'- (1'-methyl- piperidinium)]-3- (trimethylammonium)-propan-    dibromid
Eine Lösung von 3, 9 g (0, 017 Mole)   spiro-[(l-    Methyl-oxindol)-3,   4'- (1'-methylpiperidin)],    C. Eisleb, Ber. 74, 1433 (1941), und 6, 8 g (0, 026 Mole) 3-Brompropyl-trimethylammoniumbromid in 15   cm3    Athylalkohol wurde 20 Stunden lang am Wasserbad auf Rückflusstemperatur gehalten. Die abgekühlte Lösung wurde mit   Athylazetat verdünnt.    Der dabei ausfallende Niederschlag wurde gesammelt und zweimal aus   n-Propylalkohol    und Äthylazetat umkristallisiert.

   So wurden 3, 6 g   (43 O/o    der theoretischen Ausbeute)   l-spiro-t (l-Methyloxindolyl)-3, 4'-(1'-me-       thylpiperidinium)]-3- (trimethylammonium)-propan-    dibromid erhalten. Diese Verbindung schmilzt bei   251  C.   



  Analyse :
Berechnet : C 48, 89 H 6, 77 Br 32, 53
Gefunden : 48, 79   7,    04 32, 19
Beispiel 26   
1- [4- (3-Indolyllithyl)-l-methyl-piperidiniuml-3- trimethylammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 25 entsprechend, wurde 4- (3-Indolyläthyl)-1-methylpiperidin mit 3-Brompropyl-trimethylammoniumbromid zu 1- [4- (3  Indolyläthyl)-1-methylpiperidinium]-3-    (trimethyl  ammonium)-propandibromid    umgesetzt.



   Beispiel 27    1- [4- (3-Indolyläthyl)-1-äthylpiperidinium]-3-     (trimethylammonium) propandibromid
Dem Verfahren gemäss Beispiel 25 entsprechend, wurde   4- (3-Indolyläthyl)-1-äthylpiperidin    mit 3-Brompropyl-trimethylammoniumbromid zu l- [4- (3-Indolyl   äthyl)-1-äthylpiperidinium]-3- (trimethylammonium)-    propandibromid umgesetzt. Diese Verbindung ist eine hygroskopische, feste Substanz.



  Analyse :
Berechnet : C 53, 39 H 7, 60
Gefunden : 52, 60 7, 54
Beispiel 28    1- (4- {6- {Bicyclo- [2.    2.   1]-2-heptenyl)}-pyridinium)-   
3- (trimethylammonium)-propandibromid
Nach dem in Beispiel 16 angeführten Verfahren wurde 4-{6-(Bicyclo-[2. 2.   1]-2-heptenyl)}-pyridin    in Isopropylalkohol mit 3-Brompropan-trimethylammoniumbromid auf Rückflusstemperatur erwärmt. Dabei wurde   1- (4- {6- (Bicyclo- [2.    2.   1]-2-heptenyl)}-pyridi-      nium)-3- (trimethylammonium)-propandibromid    erhalten, das nach Trocknen im Vakuum über Phosphorpentoxyd als hygroskopische, glasige Substanz anfällt.



  Analyse :
Berechnet : Br 36, 98
Gefunden : 37, 14
Beispiel 29    1- (3-Carbanilidopyridinium)-3- (trimethyl-    ammonium)-propandibromid
Eine Lösung von 5, 9 g (0, 03 Mole) Nikotinsäureanilid und 7, 8 g (0, 03 Mole) 3-Brompropyltrimethylammoniumbromid in Azetonitril wurde am Wasserbad 25 Stunden lang auf Rückflusstemperatur erhitzt. Der Niederschlag wurde gesammelt und aus Athylalkohol umkristallisiert. Es ergaben sich 12, 0 g (87 /o der theoretischen Ausbeute)   1- (3-Carbanilido-       pyridinium)-3- (trimethylammonium)-propandibromid.   



  Diese Verbindung schmilzt bei 179-181,   5     C.



  Analyse :
Berechnet : C 47, 07 H 5, 50 Br 34, 80
Gefunden : 46, 99 5, 51 34, 34
Beispiel 30    1- (3-Carbobenzyloxypyridinium)-3- (trimethyl-    ammonium)-propandibromid
Dem Verfahren gemäss Beispiel 29 folgend, wurde Benzylnicotinat mit 3-Brompropyl-trimethylammoniumbromid zu 1- (3-Carbobenzyloxypyridinium)  3- (trimethylammonium)-propandibromid    umgesetzt.



   Beispiel   31       1- (2-Piperidinopyridinium)-3- (trimethyl-    ammonium)-propandibromid
Dem Verfahren gemäss Beispiel 29 folgend, wurde 2-Piperidinopyridin mit 3-Brompropyl-trimethylammoniumbromid zu   1- (2-Piperidinopyridinium)-      3- (trimethylammonium)-propandibromid    umgesetzt.



   Beispiel 32   
1-[2-(2-Oxo-3-methylpentyl)-pyridinium]-
3- (trimethylammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 1 entsprechend, wurde   2- (2-Oxo-3-methylpentyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu 1-[2-(2-Oxo   3-methylpentyl)-pyridinium]-3- (trimethylammonium)-    propandibromid umgesetzt.



   Beispiel 33
1-[2-(2-Oxo-3-carbäthoxypentyl)-pyridinium]   3- (trimethylammonium)-propandibromid   
Dem Verfahren gemäss Beispiel   1    entsprechend, wurde 2-   (2-Oxo-3-carbäthoxypentyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid umgesetzt, dabei wurde 1- [2-   (2-Oxo-3-carbäthoxypentyl)-       pyridinium]-3- (trimethylammonium)-propandibromid    als feste, hygroskopische Substanz erhalten. 



   Beispiel 34    1- [4- (Diphenylmethyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid
Dem Verfahren gemäss Beispiel 1 folgend, wurde 4-(Diphenylmethyl)-pyridin mit 3-Brompropyl-trimethylammoniumbromid zu   1- [4- (Diphenylmethyl)-      pyridinium]-3-(trimethylammonium)-propandibromid    umgesetzt. Diese Verbindung ist eine feste, hygroskopische Substanz, die bei   145-160     C unter Zersetzung schmilzt.



   Beispiel 35
1-[4-(l,2-DiphenylÏthenyl)-pyridinium]   3- (trimethylammonium)-propandibromid   
Dem Verfahren gemäss Beispiel   1    folgend, wurde   4-(1, 2-Diphenylätbenyl)-pyridin    mit 3-Brompropyltrimethylammoniumbromid zu   1- [4- (1,    2-Diphenyl  äthenyl)-pyridinium]-3-(trimethylammonium)-propan-    dibromid umgesetzt.



   Beispiel 36
1-[4-(Triphenylmethyl)-pyridinium]-3-(trimethyl   ammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 1 folgend, wurde 4- (Triphenylmethyl)-pyridin mit 3-Brompropyl-trimethylammoniumbromid zu   1- [4- (Triphenylmethyl)-    pyridinium]-3-(trimethylammonium) - propandibromid umgesetzt. Diese Verbindung ist eine kristalline Substanz.



   Beispiel 37   
1-(2-[(1-Naphthyl)-äthyl]-pyridinium)-3-(trimethyl-    ammonium)-propandibromid
Dem Verfahren gemäss Beispiel   1    folgend, wurde   2-[(1-Naphthyl)-äthyl]-pyridin mit 3-Brompropyl-tri-    methylammoniumbromid zu   I-    (2- [(l -Naphthyl)  äthylj-pyridinium)-3- (trimethylammonium)-propan-    dibromid umgesetzt. Diese Verbindung schmilzt bei 170-171  C unter Zersetzung.



  Analyse :
Berechnet : C 55, 88 H 6, 12 Br 32, 33
Gefunden : 56, 15 6, 36 31, 58
Beispiel 38   
1-(4-[(1-Naphthyl)-äthyl]-pyridinium)-
3-(trimethylammonium)-propandibromid   
Dem Verfahren gemäss Beispiel   1    folgend, wurde   4- [ (l-Naphthyl)-äthyl]-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   I-    (4-   [ (I-Naphthyl)-      äthyl]-pyridinium)-3-    (trimethylammonium)-propandibromid umgesetzt.



   Beispiel 39
1-   (4- [3- (9 Fluorenylcarboxy)-proyll-pyridinium)-       3- (trimethylammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 1 folgend, wurde   4- [3- (Fluorenylcarboxy)-propyl]-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu 1- (4-   [3- (9-    Fluorenylcarboxy)-propyl]-pyridinium)-3-(trimethylammonium)-propandibromid umgesetzt.



   Beispiel 40   
1-[2-(3-Indolyläthyl)-l-methylpiperidinium]-
3- (trimethylammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 1 folgend, wurde   2- (3-Indolyläthyl)-l-methylpiperidin    mit 3-Brompropyl-trimethylammonium)-propandibromid umgesetzt.



   Beispiel 41   
1- [2- (Phenyläthylamino)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid
Dem Verfahren gemäss Beispiel 1 folgend, wurde   2- (Phenylmethylamino)-pyridin    mit 3-Brompropyltrimethyl-ammoniumbromid zu   1-    [2-   (Phenyläthyl-      amino)-pyridinium]-3- (trimethylammonium)-propan-    dibromid umgesetzt.



   Beispiel 42
1-[2-(2-Pyridylamino)-pyridinium]-3-(trimethyl   ammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 1 folgend, wurde 2, 2'-Dipyridylamin mit 3-Brompropyl-trimethylammoniumbromid zu   1- [2- (2-Pyridylamino)-pyridi-    nium]-3-(trimethylammonium)-propandibromid umgesetzt.



   Beispiel 43    1-spiro- [Fluoren-9, 4'- (1'-methylpiperidinium)]-   
3-(trimethylammonium)-propandibromid
Dem Verfahren gemäss Beispiel 25 entsprechend, wurde   spiro- [Fluoren-9, 4'- (1'-methylpiperidin)]    mit 3-Brompropyltrimethylammoniumbromid zu   1-spiro-      [Fluoren-9,    4'-(1'-methylpiperidinium)]-3- (trimethyl  ammonium)-propandibromid    umgesetzt. Diese Verbindung schmilzt bei 274  C unter Zersetzung.



  Analyse :
Berechnet : C 56, 48 H 6, 71 Br 31, 32
Gefunden : 56, 06 6, 92 30, 87
Beispiel 44    I- [4- (1-Methyl-3-indolyläthyl)-pyridinium]-   
3-(trimethylammonium)-propandibromid
Eine Lösung von 12, 0 g (0, 049 Mole) 4-(1-Me  thyl-3-indolyläthyl)-pyridin    und 9, 15 g (0, 035 Mole) 3-Brompropyl-trimethylammoniumbromid in 50 cm3 Azetonitril wurde 25 Stunden auf Rückflusstemperatur erwärmt. Das Lösungsmittel wurde vom ¯ligen Niederschlag abdekantiert. Das Íl wurde in Äthylalkohol gelöst und mit Ather ausgefällt ; dieser Vorgang wurde wiederholt. Das ölige Produkt wurde über Phosphorpentoxyd im Vakuum bei Raumtemperatur getrocknet.

   So wurden 5, 65   g    (32% der theoretischen Ausbeute)   1- [4- (I-Methyl-3-indolyIäthyl)-pyridinium]-      3- (trimethylammonium)-propandibromid    als orangegelbe, hygroskopische Substanz erhalten, welche aus Isopropylalkohol umkristallisiert, in Form gelber, hygroskopischer Nadeln anfällt.



  Analyse :
Berechnet : C 53, 13 H 6, 28 Br 32, 14
Gefunden : 52, 83 6, 47   3I,    98 
Das gemischte Salz,   1- [4- (1-Methyl-3-indolyl-      äthyl)-pyridinium]-3-    (trimethylammonium)-propanmonochlorid,-monobromid, wird durch 20stündiges Erhitzen äquimolarer Mengen   4- (1-Methyl-3-indolyl-      äthyl)-pyridin    und 3-Chlorpropyl-trimethylammoniumbromid in Dimethylformamidlösung auf   125  C      (Olbadtemperatur)    und Sammlung des in der abgekühlten Reaktionsmischung gebildeten Niederschlages gewonnen. Die Ausbeute betrug   80 /o    der Theorie.



   Eine Lösung von 25 g   1- [4- (l-Methyl-3-indolyl-       äthyl)-pyridinium]-3- (trimethylammonium)-propan-    dibromid in 500   cm3    Methanol wurde durch eine mit     Amberlite-Anionaustauschharz    IRA   401   (vorher    mit einer Natriumchloridlösung   regsneriert)    beschickte Kolonne geleitet. Die Kolonne wurde dann mit frischem Methanol gewaschen. Das Eluat wurde im Vakuum eingeengt und der Rückstand aus   Azeto-    nitril umkristallisiert. Es wurden 16, 5 g   (81 /o    der theoretischen Ausbeute) 1- [4- (l-Methyl-3-indolyl  äthyl)-pyridinium]-3-    (trimethylammonium)-propandichlorid erhalten. Dieses Salz schmilzt bei 195  C unter Zersetzung.



  Analyse :
Berechnet : Cl 17, 36
Gefunden : 17, 30
Beispiel 45    l- [2- (3-Indolyläthyl)-5-äthylpyridinium]-
3- (trimethylammonium)-propandibromid   
Eine Mischung von 10 g (0, 04 Mole) 2- (3-In  dolyläthyl)-5-äthylpyridin    und 5, 2 g (0, 02 Mole) 3-Brompropyltrimethylammoniumbromid, gelöst in 50   cms Azetonitril,    wird 24 Stunden lang auf   Rück-      flusstemperatur    erwärmt. Die Lösung wurde gekühlt, der Niederschlag abfiltriert und zweimal aus Isopropylalkohol-Athylazetat sowie schliesslich zweimal aus Isopropylalkohol umkristallisiert.

   Die damit erhaltene, noch unreine Substanz wurde in 25   cml    Azetonitril gelöst und 5 Stunden lang unter Zusatz von 4 g   2- (3-Indolyläthyl)-5-äthylpyridin    auf Rückflusstemperatur erwärmt. Durch Rekristallisation des so erhaltenen Produktes aus Isopropylalkohol wurden 1, 4 g   (13,      510/o    der theoretischen Ausbeute)   
1-[2-(3-Indolyläthyl)-5-äthylpyridinium]-3-(trimethyl-      ammonium)-propandibromid    in Form einer weissen, hygroskopischen Substanz gewonnen.



  Analyse :
Berechnet : Bromion 31, 26
Gefunden : 30, 79
Beispiel 46   
1- [2- (l-Methyl-3-indolyläthyl)-pyridinium]-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 44 beschriebenen Verfahren entsprechend, wurde durch Umsetzung von   2-(1-Me-      thyl-3-indolyläthyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid das   1-    [2- (1-Methyl-3  indolyläthyl)-pyridinium],    3- (trimethylammonium)propandibromid als feste, bei   139-140  C    unter Zersetzung schmelzende Substanz gewonnen.



  Analyse :
Berechnet : C 53, 13 6, 28 Br 32, 14
Gefunden : 53, 26 5, 96 31, 83
Beispiel 47   
1-[2-(1-Methyl-3-indolyläthyl)-5-äthylpyridinium]-
3-(trimethylammonium)-propandibromid   
Dem in Beispiel 44 beschriebenen Verfahren entsprechend, wurde durch Umsetzung von   2-(1-Me-      thyl-3-indolyläthyl)-5-äthylpyridin    mit 3-Brompropyltrimethylammoniumbromid das 1- [2- (1-Methyl-3   indolylathyl)-5-äthylpyridinium]-3- (trimethylammo-    nium)-propandibromid gewonnen. Diese Verbindung ist eine feste Substanz, die bei   173-174  C    unter Zersetzung schmilzt.



  Analyse :
Berechnet : C 54, 86 H 6, 72 Br 30, 42
Gefunden : 54, 21 6, 53 30, 28
Beispiel 48   
1- [4- (l-Benzyl-3-indolyläthyl)-pyridinium]-
3- ? 7-propandibromid   
Dem in Beispiel 19 beschriebenen Verfahren entsprechend, wurde durch Umsetzung von   4- (1-      Benzyl-3-indolylathyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid das l- [4- (l-Benzyl-3-indo  lyläthyl)-pyridinium]-3-    (trimethylammonium)-propandibromid erhalten. Diese Verbindung ist eine feste Substanz, die bei   191-194  C    unter Zersetzung schmilzt.



  Analyse :
Berechnet : C 58, 64 H 6, 15 Br 27, 87
Gefunden : 56, 36 5, 95 27, 34
Beispiel 49    1-(2-[1-(1-Methyl-3-indolyl)-2-propyl]-pyridinium)-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 44 beschriebenen Vorgang entsprechend, wurde durch Umsetzung von   2- [l- (l-Me-      thyl-3-indolyl)-2-propyl]-pyridin    mit 3-Brompropyltrimethylammoniumbromid das 1- (2- [1- (1-Methyl   3-indolyl)-2-propyl]-pyridinium)-3-(trimethylammo-    nium)-propandibromid erhalten.



   Beispiel 50    1- [4- (1-Indolyläthyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid
Dem in Beispiel 19 beschriebenen Vorgang entsprechend, wurde   4-(1-lndolyläthyl)-pyridin mit    3-Brompropyl-trimethylammoniumbromid umgesetzt.



  Es bildet sich das   l-t4-(1-Indolyläthyl)-pyridinium]-      3- (trimethylammonium)-propandibromid,    eine feste, bei 223-225  C unter Zersetzung schmelzende Substanz. 



  Analyse :
Berechnet : C 52, 18 H 6, 05 Br 33, 07
Gefunden : 51, 79 5, 87 32, 63
Beispiel 51    1-[2-(1-Benzotriazolyläthyl)-pyridinium]-   
3-(trimethylammonium)-propandibromid
Dem in Beispiel 19 angegebenen Verfahren entsprechend, wurde 2-   (1-BenzotriazoIäthyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid umgesetzt und dabei das   1-[2-(1-Benzotriazolyläthyl)-      pyridinium]-3- (trimethylammonium)-propandibromid    als weisse hygroskopische Substanz gewonnen.



  Analyse :
Berechnet : Br 32, 88
Gefunden : 32, 30
Beispiel 52   
1- [2- (1-Indenyläthyl)-pyridinium]-3- (trimethyl- ammonium)-propandibromid   
Dem in Beispiel 44 angeführten Verfahren entsprechend, wurde   2-(1-Indenyläthyl)-pyridin mit    3-Brompropyl-trimethylammoniumbromid umgesetzt und dabei das   1-[2-(1-Indenyläthyl)-pyridinium]-      3- (trimethylammonium)-propandibromid    als feste, bei 138-190  C unter Zersetzung schmelzende Substanz gewonnen.



  Analyse :
Berechnet : C 54, 78 H 6, 27 Br 33, 14
Gefunden : 54, 44 6, 42 32, 68
Beispiel 53
1-[2-(1-Methyl-3-oxindolylÏthyl)-pyridinium]
3-(trimethylammonium)-propandibromid
Dem in Beispiel 44 angeführten Verfahren entsprechend, wurde   2-(1-Methyl-3-oxindoläthyl)-pyri-    din mit 3-Brompropyl-trimethylammoniumbromid zu   1-[2-(1-Methyl-3-oxindolyläthyl)-pyridinium]-3-(tri-      methylammonium)-propandibromid    umgesetzt.   



   Beisviel 54
1- [4- (Benzyloxyäthyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid
Dem in Beispiel 19 geschilderten Verfahren entsprechend, wurde   4- (Benzyloxyäthyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [4-      (Benzyloxyäthyl)-pyridinium]-3- (trimethylammonium)-    propandibromid umgesetzt.



   Beispiel 55   
1- [4- (Benzylthioäthyl)-pyridinium]-3- (trimethyl- ammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 1 entsprechend, wurde   4-(Benzylthioäthyl)-pyridin    mit 3-Brompropyltrimethylammoniumbromid zu l-[4-(BenzylthioÏthyl)pyridinium]-3-(trimethylammonium) - propandibromid umgesetzt.



   Beispiel 56   
1- [4- (9-Fluorenthioäthyl)-pyridinium]-3- (trimethyl- ammoniumbromid)-propandibromid   
Dem Verfahren gemäss Beispiel   1    entsprechend, wurde   4-(9-Fluorenthioäthyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   1-    [4- (9  Fluorenthioäthyl)-pyridinium]-3- (trimethylammonium-    bromid)-propandibromid umgesetzt. Diese Substanz schmilzt unter Gasentwicklung bei 202-204  C.



   Beispiel 57    1-(2-{6-(Bicyclo-[2.    2.   1]-2-heptenyl)}-pyridinium)-   
3- (trimethylammonium)-propandibromid
Dem Verfahren gemäss Beispiel 19 entsprechend, wurde 2-{6-(Bicyclo-[2. 2.   1]-2-heptenyl)}-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- (2-    {6-(Bicyclo- [2. 2. 1]-2-heptenyl)}-pyridinium)-3-(trimethylammonium)-propandibromid umgesetzt. Die Verbindung ist eine hygroskope, feste Substanz.



   Beispiel 58 l-(5-{6-(Bicyclo- [2. 2.   1]-2-heptenyI) }-2-picolinium)-       3- (trimethylammonium)-propandibromid   
Dem Verfahren gemäss Beispiel 44 entsprechend, wurde 5-{6-(Bicyclo - [2. 2.   1]-2-heptenyl) }-2-picolin    mit 3-Brompropyl-trimethylammoniumbromid zu l-(5-{6-(Bicyclo-[2. 2.   1]-2-heptenyl) f-2-picolinium)-    3- (trimethylammonium)-propandibromid umgesetzt.



  Die Verbindung ist eine feste, hygroskopische Substanz.



  Analyse :
Berechnet : Br   35,    82
Gefunden : 35, 58
Beispiel 59   
1-(4-[¯-(l-Methyl-3-indolyl)-α-cyclohexylÏthyl]pyridinium)-3- (trimethylammonium)-propandibromid   
Dem in Beispiel 19 beschriebenen Verfahren entsprechend, wurde   4- [- (l-Methyl-3-indoIyl)-a-      cyclohexyläthyl]-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- (4- [, 8- (I-Methyl-3-indolyl)-      c-cyclohexyläthyl)]-pyridinium)-3-    (trimethylammonium)-propandibromid umgesetzt. Diese Verbindung schmilzt bei 237-239  C.



   Beispiel 60   
1-(4-[¯-(l-Methyl-3-indolyl)-α-(4-Ïthylcyclohexyl]  äthyl]-pyridinium)-3-(trimethylammonium)-propan-    dibromid
Dem in Beispiel 19 angegebenen Verfahren entsprechend,   wurde 4-[¯-(l-Methyl-3-indolyl)-α-(4-      äthylcyclohexyl)-äthyl]-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu 1-   (4- [- (l-Methyl-3-      indolyl)-a- (4-äthylcyclohexyL)-äthyl]-pyridinium)-    3-(trimethylammonium)-propandibromid umgesetzt.



  Diese Verbindung schmilzt unter Zersetzung bei   1 50  C.    



   Beispiel 61    1- [3- (2-lndolyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid
Dem in Beispiel 19 angegebenen Verfahren entsprechend, wurde 3- (2-Indolyl)-pyridin mit 3-Brompropyl-trimethylammoniumbromid zu   1- [3- (2-Indo-    lyl) 3- (trimethylammonium)-propandibromid umgesetzt. Diese Verbindung ist eine bei   246-250     C schmelzende Substanz.



  Analyse :
Berechnet : C 50, 12 H 5, 54 Br 35, 11
Gefunden : 50, 06 5, 49 34, 96
Beispiel 62   
1- [4- (2-Indolyl-pyridinium]-3- (trimethyl- ammonium)-propandibromid   
Dem in Beispiel 19 angegebenen Verfahren entsprechend, wurde   4- (2-Indolyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [4- (2-Indo-      lyl)-pyridinium]-3-    (trimethylammonium)-propandibromid umgesetzt. Diese Verbindung schmilzt bei 236-238  C.



  Analyse :
Berechnet : Br 35, 11
Gefunden :   34,    51
Beispiel 63   
1- [4- (3, 3'-Diindolylmethyl)-pyridinium]-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 1 angegebenen Verfahren entsprechend, wurde 4- (3,   3'-Diindolylmethyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [4- (3, 3'-Diindolylmethyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid umgesetzt. Diese Verbindung schmilzt unter Zersetzung bei 220  C.



  Analyse :
Berechnet : C 57, 54 H 5, 52 Br 27, 35
Gefunden : 57, 43 5, 63 26, 72
Beispiel 64   
1- [3- (3, 31-DiindoIylmethyl)-pyridiniuml-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel   1    beschriebenen Verfahren entsprechend, wurde 3- (3,   3'-Diindolylmethyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [3- (3, 3'-Diindolylmethyl)-pyridinium]-3- (trimethyl-    ammonium)-propandibromid umgesetzt.



   Beispiel 65   
1-[2-(3, 3'-Diindolylmethyl)-pyridinium]-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 1 beschriebenen Verfahren entsprechend, wurde 2- (3,   3'-Diindolylmethyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu    1- [2- (3, 3'-Diindolylmethyl)-pyridinium]-3- (trimethyl-      ammonium)-propandibromid    umgesetzt.



   Beispiel 66   
1- (4- [bis- (1-Methyl-3-indolyl)-methyl]-pyridinium)-   
3- (trimethylammonium)-propandibromid
Dem in Beispiel   1    beschriebenen Verfahren entsprechend, wurde   4- [bis- (1-Methyl-3-indolyl)-methyl]-    pyridin mit 3-Brompropyl-trimethylammoniumbromid zu   1- (4- [bis- (1-Methyl-3-indolyl)-methyl]-pyridinium)-      3- (trimethylammonium)-propandibromid    umgesetzt.



   Beispiel 67   
1- [4- ( 1-Methyl-3-indolylathyl)-l-methylpiperidinium]-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 24 beschriebenen Verfahren entsprechend, wurde   4-(1-Methyl-3-indolyläthyl)-1-me-    thylpiperidin mit 3-Brompropyl-trimethylammoniumbromid zu   l- [4- (l-Methyl-3-indolyIäthyl)-l-methyl-       piperidiniumli-3- (trimethylammonium)-propandibro-    mid umgesetzt.



   Beispiel 68    l-r2-(1-Methyl-3-indolyläthyl)-1-methylpiperidinium]-
3-(trimethylammonium)-propandibromid   
Dem in Beispiel 25 beschriebenen Verfahren entsprechend, wurde   2-(1-Methyl-3indolyläthyl)-1-me-    thylpiperidin mit 3-Brompropyl-trimethylammoniumbromid zu l- [2- (l-Methyl-3-indoJyläthyl)-l-methyl   piperidinium]-'3 (trimethylammonium)-propandibro-    mid umgesetzt.



   Beispiel 69    1- (4- {2- (Bicyclo- [2.    2.   1]-heptyl)}-l-methylpiperi-       dinium-3- (trimethylammonium)-propandibromid   
Dem in Beispiel 25 beschriebenen Verfahren entsprechend, wurde   4- {2- (Bicyclo- [2.    2. 1]-heptyl)}-lmethylpiperidin mit   3-Brompropyl-trimethylammo-    niumbromid zu l-(4-{2-(Bicyclo-[2. 2. 1]-heptyl)}-l  methylpiperidinium)-3- (trimethylammonium)-propan-    dibromid umgesetzt. Diese Verbindung schmilzt bei 258-260  C unter Zersetzung.



  Analyse :
Berechnet : C 50, 22 H 8, 43 Br 35, 18
Gefunden : 50, 26 8, 44 34, 58
Beispiel 70
1-[l-(2-Oxy-1-octyl)-piperidinium]-3-(trimethyl ammonium)-propandibromido
Dem in Beispiel 16 beschriebenen Verfahren entsprechend, wurde   1-(2-Oxy-l-octyl)-piperidin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [1-      (2-Oxy-1-octyl) piperidinium]-3¯    (trimethylammo  nium)-propandibromid    umgesetzt.



   Beispiel 71   
1- [1- (2-Azetoxy-l-octyl)-piperidinium]-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 16 beschriebenen Verfahren entsprechend, wurde   1-(2-Azetoxy-l-octyl)-piperidin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [1-       (2-Azetoxy-1-octyl)-piperidinium]-3-trimethylammo-    nium)-propandibromid umgesetzt.



   Beispiel 72    l- [l- (2-Benzoxy-l-octyl)-piperidinium]-   
3- (trimethylammonium)-propandibromid
Dem in Beispiel 16 beschriebenen Verfahren entsprechend, wurde 1-   (2-Benzoxy-l-octyl)-piperidin    mit 3-Brompropyl-trimethylammoniumbromid zu    1- [1- (2-Benzoxy-l-octyl)-piperidinium]-3- (trimethyl-    ammonium)-propandibromid umgesetzt.



   Beispiel 73   
1-rl-(2-Oxy-l-decyl)-piperidinium]-3-(trimethyl- ammonium)-propandibromid   
Dem Verfahren nach Beispiel 16 entsprechend2   nvurde 1-(2-Oxy-1-decyl)-piperidin    mit 3-Brompro  pyl-trimethylammoniumbromid    zu 1- [l- (2-Oxy-l   decyl)-piperidinium]-3-(trimethylammonium)-propan-    dibromid umgesetzt.



   Beispiel 74
1-   [I- (2-Azetoxy-l-decyl)-piperidinium]-       3- (trimethylammonium)-propandibromid   
Dem Verfahren nach Beispiel 16 entsprechend, wurde   1-(2-Azetoxy-l-decyl)-piperidin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [I- (2-Azet-       oxy-1-decyl)-piperidinium]-3- (trimethylammonium)-    propandibromid umgesetzt.



   Beispiel 75   
1- [l- (2-Oxy-l-dodecyl)-piperidinium]-
3- (trimethylammonium)-propandibromid   
Dem Verfahren nach Beispiel 16 entsprechend, wurde   1-(2-Oxy-l-dodecyl)-piperidin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [1- (2-Oxy-       1-dodecyl)-piperidinium]-3- (trimethylammonium)-    propandibromid umgesetzt.



   Beispiel 76    l-tl-(2-Azetoxy-l-dodecy0-piperidinium]-
3- (trimethylammonium)-propandibromid   
Dem Verfahren nach Beispiel 16 entsprechend, wurde   1-(2-Azetoxy-l-dodecyl)-piperidin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [l- (2-Azet-    oxy-l-dodecyl)-piperidinium]-3- (trimethylammonium)propandibromid umgesetzt.



   Beispiel 77   
1- [1- (2, 11-Dioxy-1-undecyl)-piperidinium]-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 16 beschriebenen Verfahren entsprechend, wurde   1-(2, 11-Dioxy-l-undecyl)-piperidin    mit 3-Brompropyl-trimethylammoniumbromid zu    1- [1- (2, 11-Dioxy-l-undecyl)-piperidinium]-3- (trime-    thylammonium)-propandibromid umgesetzt.



   Beispiel 78   
1- [l- (2, 11-Diazetoxy-l-undecyl)-piperidinium]-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 16 beschriebenen Verfahren entsprechend, wurde   1-(2, 11-Diazetoxy-l-undecyl)-pipe-    ridin mit 3-Brompropyl-trimethylammoniumbromid zu 1-   [1-(2, 11-Diazetoxy-l-undecyl)-piperidinium]-      3- (trimethylammonium)-propandibromid    umgesetzt.



   Beispiel 79   
1- [I- (2-Oxy-2-benzyl-4-butyl)-piperidinium]-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 16 beschriebenen Verfahren entsprechend, wurde   1- (2-Oxy-2-benzyl-4-butyl)-pipe-    ridin mit 3-Brompropyl-trimethylammoniumbromid zu   1- [1- (2-Oxy-2-benzyl-4-butyl)-piperidinium]-3- (tri-    methylammonium)-propandibromid umgesetzt.



   Beispiel 80   
1-[I-(2-Phenyl-2-oxyäthyl)-piperidinium]-
3- (trimethylammonium)-propandibromid   
Dem in Beispiel 16 beschriebenen Verfahren entsprechend, wurde   1- (2-Phenyl-2-oxyäthyl)-piperidin    mit   3-Brompropyl-trimethyIammoniumbromid    zu    1- [I- (2-Phenyl-2-oxyäthyl)-piperidinium]-3- (trime-    thylammonium)-propandibromid umgesetzt.



   Beispiel 81   
1-[2-(Benzoxypropyl)-pyridinium]-3-(trimethyl- ammonium)-propandibromid   
Dem in Beispiel   1    beschriebenen Verfahren entsprechend, wurde   2- (Benzoxypropyl)-pyridin    mit 3-Brompropyl-trimethylammoniumbromid zu   1- [2-       Benzoxypropyl)-pyridinium]-3-(trimethylammonium)-    propandibromid umgesetzt.



   Beispiel 82   
1- [3- (9-Fluorencarboxymethyl)-l-methylpiperi- dinium]-3- (trimethylammonium)-propandibromid   
Dem in Beispiel 1 beschriebenen Verfahren entsprechend, wurde   3- (9-Fluorencarboxymethyl)-l-me-    thylpiperidin mit 3-Brompropyl-trimethylammoniumbromid zu   1- [3- (9-Fluorencarboxymethyl)-l-methyl-      piperidinium]-3-    (trimethylammonium)-propandibromid umgesetzt.



   Beispiel 83    1- [3- (Diphenylmethoxymethyl)-l-methylpiperidinium]-   
3- (trimethylammonium)-propandibromid
Dem in Beispiel   1    beschriebenen Verfahren entsprechend, wurde   3-(Diphenylmethoxymethyl)-l-me-    thylpiperidin mit 3-Brompropyl-trimethylammoniumbromid zu   1- [3- (Diphenylmethoxymethyl)-l-methyl-    piperidinium]-3- (trimethylammonium)-propandibromid umgesetzt.



  



  Process for the production of new bisquaternary ammonium compounds?
The invention relates to a process for the preparation of new bisquaternary ammonium compounds of the formula
EMI1.1
 in which
EMI1.2
 the pyridine ring or the N-substituted 1, 2, 5, 6-tetrahydropyridine ring or piperidine ring and R, Rl, R2, R3 and R4 non-ionizing by a lower alkyl group which optionally carries at most two oxy, acetoxy, phenyl or benzoxy groups - generating groups or, but not all, hydrogen,

     R5 and R denote lower aliphatic groups or R5 and RU together with the nitrogen atom denote a ring which may have a further heteroatom, R7 denotes a lower alkyl group, A denotes an alkylene bridge with 2 to 6 carbon atoms and Xe denotes an anion, the group
EMI1.3
 has a radical weight between 150 and 350, where, if
EMI1.4
 denotes the pyridine ring, at least one of the substituents R and R4 is hydrogen, and the group
EMI1.5
 has a radical weight between 59 and 117.



   The following is the group
EMI1.6
 as a larger ammonium group and the group
EMI1.7
 referred to as the minor ammonium group.



   The sum of the carbon atoms in the substituents R5, R, R bonded in the smaller quaternary ammonium group should preferably not be greater than 7, with at least one of the substituents preferably being the methyl radical.



  Alkyl radicals serving as substituents R5, Rg and R, are, for example, methyl, ethyl, n-propyl or. to mention the isopropyl groups.



     R. and R6 can, together with the nitrogen atom, e.g. B. form a pyrrolidine, methylpyrrolidine or piperidine group. The heterocyclic group can, however, also contain an oxygen or a sulfur atom, as is the case with the morpholine and thiamorpholine groups.



   Preferred examples of the smaller ammonium group are the trimethylammonium,
MethyldiÏthylammonium,
DimethylÏthylammonium,
Methyldipropylammonium,
Dimethylisopropylammonium,
Methyläthylpropylammonium-, N-Methylpyrrolidinium-,
N-Ethylpyrrolidinium-, N-Methylpiperidinium-,
N-methylmorpholinium,
N-methylthiamorpholinium and the
Mention N-methylthiazolidinium groups. Other examples of this are the triethylammonium group, the N-ethylpiperidinium, the N-propylpyrrolidinium and the N-ethylmorpholinium group.



   As mentioned, the larger ammonium group has a radical weight between 150 and 350. The substituents can be bonded to one or more free positions on the ring. If the pyridine ring is present, at least one of the 2- and 6-positions of the ring must be unsubstituted because otherwise the quaternization is difficult due to the steric hindrance. The substituents can contain different rings; but they are not fused to the pyridine ring, but real substituents. Since the weight of the unsubstituted pyridyl radical is only 79, that of its substituents must be so large that the total weight of the substituted pyridyl radical is between 150 and 350.



   Nonionizing radicals are present as substituents on the pyridine or hydrogenated pyridine ring. With this restriction, any organic radicals with sufficient radical weight are suitable as substituents, e.g. B. organic ring structures, aryl groups, alkyl groups with branched chain, aralkyl, aralkoxy, aralkenyl, arylthioalkyl, diarylaminoalkyl, heterocyclylalkyl, cycloalkyl, aryloxyalkyl, aralkoxyalkyl, aralkylthioalkyl, arylcarboxyalkyl, arylimidoalkyl groups and Ring systems.



  Each of these substituents is linked to the pyridine ring either directly or via a bridging link, such as. B. ether, thio ether, ester, amide, sulfono bridge member, etc. or via various groups, such as. B. carbonyl, alkenyl, alkanyl groups connected. Of the substituted ring system of the larger ammonium group, only one ring atom can form part of another ring system.



   The following examples are given for the larger ammonium group:
2- and 4- (3-IndolylÏthyl) -pyridinium,
2- and 4- (l-IndolylÏthyl) -pyridinium,
2- and 4- (1-methyl-3-indolyiethyl) pyridinium,
2- (3-indolylethyl) -5-ethylpyridinium, 2- (1-methyl-3-indolylethyl) -5-ethylpyridinium,
2- and 4- (1-naphthylethyl) pyridinium and
2- and 4- (1-indenylethyl) pyridinium.



   Other examples are:
2- and 4- (l-Naphthyläthenyl) -pyridinium,
2- and 4- (2-Naphthyläthenyl) -pyridinium,
2-, 3- and 4- (2-indoly) pyridinium,
2- and 4- (3-indolylethenyl) pyridinium,
2-, 3- and 4- (3,3'-diindolylmethyl) pyridinium,
2- and 4- (1-benzotriazolylethyl) pyridinium,
2-, 3- and 4- {6- (bicyclo- [2. 2. 1] -2-heptenyI)} - pyridinium, 5- {6- (bicyclo- [2. 2. 1] -2-heptenyl) -2-picolinium,
2-, 3- and 4-benzylpyridinium,
2-, 3- and 4-carboxanilido-pyridinium,
2- and 4- (benzoxypropyl) pyridinium,
2-, 3- and 4-benzoylpyridinium,
2- and 4-stilbazulium,
2-, 3- and 4- (phenylthioethyl) pyridinium,
2-, 3- and 4- (tert.

   ButylthioÏthyl) pyridinium,
2-, 3- and 4- (benzylthioethyl) pyridinium,
3- and 4-carbobenzyloxypyridinium,
2- and 4- (diphenylaminoethyl) pyridinium,
2- and 4- (phthalimidoethyl) pyridinium,
2- and 4-hexylpyridinium,
2- and 4-decylpyridinium,
2- and 4- (2-oxocyclohexylethyl) pyridinium, 2- (3, 4-dichlorobenzyl) pyridinium,
2-, 3- and 4- (diphenyl-methyl) -pyridinium,
3- and 4- (triphenyl-methyl) -pyridinium,
2-, 3- and 4- (benzyloxyethyl) pyridinium,
2- and 4- (9-fluorenyloxypropyl) pyridinium,
2-, 3- and 4- (benzyloxymethyl) pyridinium,
2-, 3- and 4- (diphenyl-methoxymethyl) pyridinium,
2-, 3- and 4- (9-fluorenyl-carboxypropyl) -pyridinium,

  
2- and 4- [l- (l-Benzyl-3-indolyl) -2-propyl] pyridinium,
2- and 4- [- (l-MethyI-3-indoIyI) -c-cyclohexyI- Ïthyl] pyridinium,
2- and 4- (l-methyl-3-oxindolylÏthyl) pyridinium,
2-, 3- and 4- hiazolylthioethyl) pyridinium, 2- (2-pyridylamino) pyridinium,
2- and 4- (9-fluorenylethyl) pyridinium,
2- and 4- (9-fluorenyl) pyridinium,
2- and 4- (3-BenzothiophenylÏthyl) pyridinium,
2- and 4- (9-carbazolyldthyl) pyridinium,
2- and 4- (3, 4-dichlorophenylethyl) pyridinium, 2,4-dibenzylpyridinium, 2,5-bis (phenylthioethyl) pyridinium,
2, 4-bis-pyridinium,
2- and 4- (2-thienylethyl) pyridinium,

     
2- and 4- (2-furylethyl) pyridinium,
2,4-bis (2-furylethenyl) pyridinium,
2- and 4- (2-benzofurylethyl) pyridinium,
2- and 4-phenylpyridinium,
2- and 4- (2-naphthyl) pyridinium, 2- (2-phthalimidoethyl) -5-ethylpyridinium,
2- and 4- (2-Benzisosulfonazoyläthyl) - pyridinium,
2-hexyl-5-ethylpyridinium,
2,4-bis (2-pyrrolylethyl) pyridinium,
2- and 4- (2-phenyl-l-pyrrolylethyl) pyridinium,
2- and 4- (l-oxindolylethyl) pyridinium,
2- and 4- (2-indanyl) pyridinium, a- (2-indanylidene) -4-picolinium, a- (1-indanylidene) -2-picolinium,?

  - (Cyclohexylidene) -4-picolinium,
4- 8-methyl-ss-phenylethenyl) pyridinium,
2- and 4- (b-phenylbutadienyl) pyridinium,
2- and 4- (benzoylpropyl) -pyridinium and 5- (cyclohexylthioethyl) -2-picolinium.



   In addition, the l- (lower-alkyl) piperidine, which corresponds to the types listed above, in which the pyridine ring has been replaced by a 1- (lower-alkyl) piperidine ring, comes into consideration for the larger ammonium group. Piperidines, such as spiro - [(1-methyloxindole) -3,4 '- (1'-methyl piperidinium)], spiro- [fluorenyl-9, 4'- (1'-methylpiperidinium)], can also be used,
1-benzylpiperidinium,
1-PhenylÏthylpiperidinium, 1- (2-Oxy-2-phenylethyl) -piperidinium,
1-octylpiperidinium,
1-dodecylpiperidinium,
1- (2-oxydecyl) piperidinium,
1- (2-oxyoctyl) piperidinium, 1- (2-acetoxyoctyl) piperidinium and 1- (2-benzoxyoctyl) piperidinium.



   The electrostatic charges of the two quaternary ammonium parts are saturated by two anions. These two anions can be the same or different from one another. The exact nature of these anions is not essential for the mentioned use of the compounds prepared by the process according to the invention, because each anion only serves to bind the otherwise free electrical charge of the nitrogen atom and because under the conditions under which the compounds are used for pharma-dynamic preparations the amount of any anion is insufficient to produce a remarkable physiological effect. Usable anions are e.g. B. lialogen, sulfate, citrate, tartrate, acetate and phosphate ions.



   The structure of the new compounds which can be prepared by the process according to the invention can be interpreted in such a way that in them a lower alkane containing several carbon atoms is substituted on two different carbon atoms, on the one hand by a quaternary ammonium group of relatively low radical weight and on the other hand by a second, a quaternary ammonium group containing a pyridine ring or hydrogenated pyridine ring and having a greater radical weight than the first group. The quaternary ammonium groups are linked to the lower alkane through the onium nitrogen atoms.



  In the molecular structures which meet the stated conditions, ionic substituents other than those which form the two quaternary ammonium functions are excluded. The compounds prepared according to the invention are solid substances with relatively high melting points. They have an unusual antihypertensive effect of varying duration as well as ganglia-blocking properties. These two characteristics can be independently influenced by changes in the molecular structure in different parts of the compound.



   The new bisquaternary ammonium compounds are prepared according to the invention in such a way that an amine of the formula II
EMI3.1
 with a quaternary ammonium salt of the formula III
EMI3.2
 in which X 'is a chlorine, bromine or iodine atom, is reacted.



   In practice, the reactants can be used in equimolar amounts or one of the same in excess, depending on the availability of the starting material and depending on the ease with which the product can be purified.



   When carrying out the reaction, acetonitrile, dimethylformamide, aliphatic alcohols, e.g. B. iisthanol, methanol, isopropyl alcohol, propyl alcohol or isoamyl alcohol, nitrobenzene, nitroalkanes such as nitromethane and nitro ethane, mixtures of dioxane and an alcohol and similar polar solvents and solvent mixtures can be used. The reaction can also be carried out with a large excess of the starting base, which takes the place of the solvent. For the preparation of compounds of the type set forth in Examples 16-18, alcohols and mixtures containing alcohols are preferred, although any of the polar solvents listed can also be used.



   It is best to work at temperatures between room temperature and 150 ° C., under atmospheric pressure or in a closed reaction vessel; working under reflux cooling at about 80 ° C. is preferred. It is advisable to use the specified low temperature with a relatively long expenditure of time, because above 200 ° C., the reversal of the quaternization reaction leads to undesirable complications.



   The compounds prepared according to the invention show particularly antihypertensive effects which are not related to the strength of the ganglia-blocking effect. This pharmacological finding increases the therapeutic applicability of the compound, and the use of the desired compounds does not show any of the unpleasant side effects usually occurring, such as violent postural blood subsidence, constipation, dilatation and paralysis of the pupil, dry mouth, decreased potency, etc.



   Example 1 1- (4-Benzylpyridinium) -3- (trimethylammonium) propanedibromide
A solution of 10.4 g (0.04 moles) of 3-bromopropyltrimethylammonium bromide and 9.0 g (0.06 moles) of 4-benzylpyridine in 35 cc of acetonitrile was heated to reflux for 6 hours.



  The precipitate formed was collected and recrystallized from n-propyl alcohol and ethyl acetate. 7.6 g (44 of the theoretical yield) of 1- (4-benzylpyridinium) -3- (trimethylammonium) propane dibromide were obtained. After three further recrystallizations from isopropyl alcohol, a product was obtained which melts at 172-174 ° C.



  Analysis:
Calculated: C 50.25 H 6.09 Br 37.15
Found: 50, 32 6, 38 36, 72
Example 2 1- (2-Benzylpyridinium) -3- (trimethylammonium) propane dibromide
To a solution of 6.8 g (0.026 moles) of 3-bromopropyl trimethylammonium bromide in isopropyl alcohol was added 6.8 g (0.04 moles) of distilled benzylpyridine. This solution was heated to reflux temperature for 30 hours. The 1- (2-benzylpyridinium) -3- (trimethylammonium) propanedibromide was then precipitated as a hygroscopic, solid substance from the cold solution by adding ethyl acetate.



   Example 3
1- [4- (t-Butylthioethyl) pyridinium] -3- (trimethylammonium) propane dibromide
Corresponding to Example 1, 4- (t-butylthioethyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide to give 1- [4- (t-butylthioithyl) pyridinium] -3- (trimethylammonium) propane dibromide. This compound is a hygroscopic, solid substance.



   Example 4 1- [4- (n-Propylthioethyl) pyridinium] -3- (trimethylammonium) propane dibromide
Following the procedure according to Example 1, the 1- [4- (n-propylthioethyl) pyridinium] -3- (trimethylammonium) propane dibromide was obtained as hygroscopic by reacting 4- (n-propylthioethyl) pyridine with 3-bromopropyl trimethylammonium bromide , solid substance obtained.



   Example 5 1- [4- (Benzoxypropyl) pyridinium] -3- (trimethylammonium) propane dibromide
Following the process according to Example 1, the 1- [4 (benzoxypropyl) pyridinium] -3- (trimethylammonium) propanedibromide was obtained by reacting 4- (benzoxypropyl) pyridine with 3-bromopropyl trimethylammonium bromide. This compound is a solid substance that melts at 225-226 C with decomposition.



  Analysis:
Calculated: C 50.21 H 6.02 Br 31.82
Found: 50, 20 5, 94 31, 20
Example 6
1- [4- (carbobenzyloxy) pyridinium] -3- (trimethylammonium) propane dibromide
Following the process according to Example 1, the 1- [4- (carbobenzyloxy) pyridinium] -3- (trimethylammonium) propane dibromide was obtained by reacting benzyl 4-picolinate with 3-bromopropyl trimethylammonium bromide.



   Example 7
1- [4- (phenylthiodthyl) pyridinium] -3- (trimethylammonium) propane dibromide
Following the procedure according to Example 1, the 1- [4 (phenylthioethyl) pyridinium] -3- (trimethylammonium) propane dibromide was obtained by reacting 4- (phenylthioethyl) pyridine with 3-bromopropyl trimethylammonium bromide. This compound melts at 170-172 C.



  Analysis:
Calculated: C 47.91 H 5, 92 Br 33.55
Found: 47, 35 5, 83 34, 00
Example 8
1- [2- (phenylthioethyl) pyridinium] -3- (trimethylammonium) propane dibromide
Following the process of Example 1, the 1- [2- (phenylthioethyl) pyridinium] -3- (trimethylammonium) propane dibromide was obtained as a hygroscopic, solid substance by reacting 2- (phenylthioethyl) pyridine with 3-bromopropyltrimethylammonium bromide.



  Analysis:
Calculated: Br 33.55
Found: 33, 20
Example 9
1- (4-Benzylpyridinium) -3- (1-methylpyrrolidinium) propane dibromide
Following the procedure according to Example 1, the 1- (4-benzylpyridinium) -3- (l-methylpyrrolidinium) propane dibromide was obtained as a hygroscopic, solid substance by reacting 4-benzylpyridine with 3-bromopropyl-1-methylpyrrolidinium bromide receive.



  Analysis:
Calculated (+1 H20): Br 33.70
Found: 33, 85
Example 10
1- (4-Benzylpyridinium) -3- (1-methylpiperidinium) propane dibromide
Following the process according to Example 1, 1- (4-benzylpyridinium) -3- (1-methylpiperidinium) propane dibromide was obtained by reacting 4-benzylpyridine with 3-bromopropyl-1-methylpiperidinium bromide. This compound melts at 227 to 230 C.



  Analysis:
Calculated: (+ 1, Z2 H2O)
C 52.61 H6.53 Br33.34 H20.1.85
Found :
52, 19 6, 12 32, 77 1, 02
Example 11
1- (4-Benzylpyridinium) -6- (trimethylammonium) -hexanedibromide
Following the process according to Example 1, 1- (4-benzylpyridinium) -6- (trimethylammonium) -hexanedibromide was obtained by reacting 4-benzylpyridine with 6-bromohexyltrimethylammonium bromide.



   Example 12 1- [4- (Diphenylaminodthyl) pyridiniuml -3- (trimethylammonium) propane dibromide
Following the procedure according to Example 1, the 1- [4- (diphenylaminoethyl;) pyridinium] -3- (trimethylammonium) piopan dibromide was obtained by reacting 4- (diphenylaminoethyl) pyridine with 3-bromopropyltrimethylammonium bromide.



   Example 13
1- [2- (2-oxocyclohexylethyl) pyridinium] -
3- (trimethylammonium) propane dibromide
Following the procedure according to Example 1, the 1- [2- (2-oxocyclohexylethyl) pyridinium] -3- (trimethylammonium) propane dibromide was obtained by reacting 2- (2-oxocyclohexylethyl) pyridine with 3-bromopropyltrimethylammonium bromide obtained as a hygroscopic, solid substance.



   Example 14
1- (4-Benzoylpyridinium) -3- (trimethylammonium) propane dibromide
Following the process according to Example 1, 1- (4-benzoylpyridinium) -3- (trimethylammonium) propane dibromide was obtained by reacting 4-benzoylpyridine with 3-bromopropyltrimethylammonium bromide. This compound is a solid substance that melts at 221-222 C with decomposition.



  Analysis:
Calculated (+ 1/2 H, O):
C 47.69 H 5.57 Br 35.26 H20 1.99
Found: 47, 97 5, 63 35, 52 2, 80
Example 15 1- [4- (4, 5, 6, 7-tetrachlorophthalimidoethyl) pyridinium] -3- (trimethylammonium) propanedibromide
Following the process according to Example 1, the 1- [4- (4, 5, 6, 7-tetrachlorophthalimidoethyl) was obtained by reacting 4- (4, 5, 6, 7-tetrachlorophthalimidoethyl) pyridine with 3-bromopropyltrimethylammonium bromide. pyridinium] -3- (trimethylammonium) propanedibromide.



   Example 16
1- (4-Benzyl-1-methylpiperidinium) -3- (trimethylammonium) propane dibromide
A solution of 7.0 g (0.037 moles) of 4-benzyl 1-methylpiperidine and 10.5 g (0.04 moles) of 3-bromopropyl trimethylammonium bromide in 50 cm8 of isopropyl alcohol was heated to reflux temperature for 24 hours. The crystalline precipitate obtained on dilution with ethyl acetate was recrystallized twice from isopropyl alcohol and ethyl acetate. This gave 8.6 g (500 / o of the theoretical yield) of 1- (4-benzyl-1-methylpiperidinium) -3- (trimethylammonium) propane dibromide. The compound melts at 237-238 C.



  Analysis:
Calculated: C 50.67 H7.61 Br 35.49
Found: 50, 58 7, 73 35, 03
Example 17 1- (2-Benzyl-1-methylpiperidinium) -3- (trimethylammonium) propane dibromide
After the procedure described in Example 16, 2-benzyl-1-methylpiperidine was reacted with 3-bromopropyl-trimethylammonium bromide. The 1- (2-benzyl-1-methylpiperidinium) -3- (trimethylammonium) propane dibromide was obtained as a white, hygroscopic substance.



  Analysis:
Calculated: Br 35.49
Found: 35, 13
Example 18 l- [4- (3-0xypropyl) -l-methylpiperidinium] -
3- (triethylammonium) propane dibromide
Following the procedure described in Example 16, 4- (3-oxypropyl) -l-methylpiperidine was quaternized with 3-bromopropyl-trimethylammonium bromide. After recrystallization from ethanol and ethyl acetate, I- [4- (3-oxypropyl) -I-methylpiperidinium] 3- (triethylammonium) propane dibromide was obtained with about 43% of the theoretical yield.



  Analysis:
Calculated: C 43.07 H 8, 19 Br 38, 21
Found: 42, 93 8, 02 37, 93
Example 19 1- [4- (3-Indolylethyl) pyridinium] -3- (trimethylammonium) propane dibromide
A solution of 6.4 g (0.028 moles) 4- (3-indolylethyl) pyridine and 7.9 g (0.03 moles) 3-bromopropyltrimethylammonium bromide in 50 cm3 acetonitrile was heated to reflux temperature on a water bath for 28 hours . The crystalline precipitate was collected and recrystallized twice from ethanol and ethyl acetate. 8.7 g (65 / o of the theoretical yield) of 1-4- (3-indolylethyl) pyridinium] -3- (trimethylammonium) propane dibromide were obtained in the form of pale green crystals.

   The substance melts with evolution of gas at 218 C.



  Analysis:
Calculated: C 52.18 H 6.05 Br 33.07
Found: 52, 14 6, 25 33, 05
Example 20 1- [4- (I-Benzotriazolyldthyl) -pyridiniuml-
3- (trimetliglammonium) propane dibromide
In accordance with the process described in Example 19, 4- (1-benzotriazolylethyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide in an ethyl alcoholic solution.



  Recrystallization from alcohol, ether and then isopropyl alcohol gave 1- [4- (l-benzotriazolylethyl) pyridinium] -3- (trimethylammonium) propanedibromide as a white, crystalline substance.



  Analysis:
Calculated (+ I HoO):
C 45, 34 H 5, 81 Br 31, 76
Found: 45, 57 6, 03 31, 91
Example 21 1- [2- (3-Indolyrdthyl) pyridinium] -3- (trimethylammonium) propane dibromide
According to the process described in Example 19, the 1-t2- (3-indolylethyl) pyridinium] -3- (trimethyl ammonium) propane dibromide was obtained by reacting 2- (3-indolylmethyl) pyridine with 3-bromopropyl trimethylammonium bromide receive. This substance melts at 201-203 C.



  Analysis:
Calculated: C 52.18 H 6.05 Br 33.07
Found: 52, 23 6, 17 32, 51
Example 22 1-4- (phthalimidoethyl) pyridinium] -3- (trimethylammonium) propane dibromide
In accordance with the procedure given in Example 19, 1- [4- (Phthalimido'dthyl) pyridinium 3- (trimethylammonium) propane dibromide was obtained by reacting 4-phthalimidoethyl-pyridine with 3-bromopropyl-trimethylammonium bromide.



  This compound melts at 204 C.



  Analysis:
Calculated: C 49, 14 H 5, 30 Br 31, 14
Found: 49, 46 5, 32 30, 89
Example 23 1-4- (1-indenylethyl) pyridinium] -3- (trimethylammonium) propane dibromide
In accordance with the procedure given in Example 19, the 1- [4- (1-indenylethyl) pyridine] -3- (trimethylammonium) was obtained by reacting 4- (1-indenylethyl) pyridine with 3-bromopropyltrimethylammonium bromide ) propane dibromide. This compound melts at 196-197 C.



  Analysis:
Calculated: C 54, 78 H 6, 27 Br 33, 14
Found: 54, 52 6, 43 33, 05
Example 24
1- [2- (2-benzothiazolthioethyl) pyridinium] -
3- (trimethylammonium) propane dibromide
In accordance with the procedure given in Examples 1 and 19, 2- (2-benzothiazolthioethyl) pyridine was converted with 3-bromopropyltrimethylaminium bromide to give 1- [2- (2-benzothiazolethioethyl) pyridinium] -3- (trimethylammonium ) propane dibromide implemented.



   Example 25
1-spiro- [(1-methyloxindolyl) -3, 4'- (1'-methyl-piperidinium)] -3- (trimethylammonium) propane dibromide
A solution of 3.9 g (0.017 moles) of spiro - [(1-methyl-oxindole) -3, 4'- (1'-methylpiperidine)], C. Eisleb, Ber. 74, 1433 (1941), and 6.8 g (0.026 moles) of 3-bromopropyl-trimethylammonium bromide in 15 cm3 of ethyl alcohol were kept at reflux temperature on a water bath for 20 hours. The cooled solution was diluted with ethyl acetate. The resulting precipitate was collected and recrystallized twice from n-propyl alcohol and ethyl acetate.

   Thus, 3.6 g (43% of the theoretical yield) of l-spiro-t (l-methyloxindolyl) -3, 4 '- (1'-methylpiperidinium)] - 3- (trimethylammonium) propane dibromide were obtained receive. This compound melts at 251 C.



  Analysis:
Calculated: C 48.89 H 6.77 Br 32.53
Found: 48, 79 7, 04 32, 19
Example 26
1- [4- (3-Indolyllithyl) -1-methyl-piperidinium (3- trimethylammonium) -propanedibromide
In accordance with the procedure of Example 25, 4- (3-indolylethyl) -1-methylpiperidine was reacted with 3-bromopropyltrimethylammonium bromide to give 1- [4- (3 indolylethyl) -1-methylpiperidinium] -3- (trimethyl ammonium) propane dibromide .



   Example 27 1- [4- (3-Indolylethyl) -1-ethylpiperidinium] -3- (trimethylammonium) propanedibromide
Corresponding to the process according to Example 25, 4- (3-indolylethyl) -1-ethylpiperidine was combined with 3-bromopropyl-trimethylammonium bromide to give 1- [4- (3-indolylethyl) -1-ethylpiperidinium] -3- (trimethylammonium) propanedibromide implemented. This compound is a hygroscopic, solid substance.



  Analysis:
Calculated: C 53.39 H 7.60
Found: 52, 60 7, 54
Example 28 1- (4- {6- {Bicyclo- [2. 2. 1] -2-heptenyl)} - pyridinium) -
3- (trimethylammonium) propane dibromide
Following the procedure given in Example 16, 4- {6- (bicyclo- [2.2.1] -2-heptenyl)} -pyridine in isopropyl alcohol was heated to reflux temperature with 3-bromopropane-trimethylammonium bromide. This gave 1- (4- {6- (bicyclo- [2. 2. 1] -2-heptenyl)} - pyridinium) -3- (trimethylammonium) propane dibromide, which after drying in vacuo over phosphorus pentoxide as a hygroscopic , glassy substance accumulates.



  Analysis:
Calculated: Br 36.98
Found: 37, 14
Example 29 1- (3-Carbanilidopyridinium) -3- (trimethylammonium) propane dibromide
A solution of 5.9 g (0.03 moles) of nicotinic anilide and 7.8 g (0.03 moles) of 3-bromopropyltrimethylammonium bromide in acetonitrile was heated to reflux on a water bath for 25 hours. The precipitate was collected and recrystallized from ethyl alcohol. This gave 12.0 g (87 / o of the theoretical yield) of 1- (3-carbanilidopyridinium) -3- (trimethylammonium) propane dibromide.



  This compound melts at 179-181.5 C.



  Analysis:
Calculated: C 47.07 H 5.50 Br 34. 80
Found: 46, 99 5, 51 34, 34
Example 30 1- (3-Carbobenzyloxypyridinium) -3- (trimethylammonium) propane dibromide
Following the process according to Example 29, benzyl nicotinate was reacted with 3-bromopropyl trimethylammonium bromide to give 1- (3-carbobenzyloxypyridinium) 3- (trimethylammonium) propane dibromide.



   Example 31 1- (2-piperidinopyridinium) -3- (trimethylammonium) propane dibromide
Following the procedure according to Example 29, 2-piperidinopyridine was reacted with 3-bromopropyl-trimethylammonium bromide to give 1- (2-piperidinopyridinium) -3- (trimethylammonium) -propanedibromide.



   Example 32
1- [2- (2-Oxo-3-methylpentyl) pyridinium] -
3- (trimethylammonium) propane dibromide
Corresponding to the process according to Example 1, 2- (2-Oxo-3-methylpentyl) pyridine was mixed with 3-bromopropyl trimethylammonium bromide to give 1- [2- (2-Oxo 3-methylpentyl) pyridinium] -3- (trimethylammonium) - Propanedibromide implemented.



   Example 33
1- [2- (2-Oxo-3-carbethoxypentyl) pyridinium] 3- (trimethylammonium) propane dibromide
Corresponding to the method according to Example 1, 2- (2-oxo-3-carbethoxypentyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide, 1- [2- (2-oxo-3-carbethoxypentyl) pyridinium] -3 - (Trimethylammonium) propane dibromide obtained as a solid, hygroscopic substance.



   Example 34 1- [4- (Diphenylmethyl) pyridinium] -3- (trimethylammonium) propane dibromide
Following the process according to Example 1, 4- (diphenylmethyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide to give 1- [4- (diphenylmethyl) pyridinium] -3- (trimethylammonium) propane dibromide. This compound is a solid, hygroscopic substance that melts at 145-160 C with decomposition.



   Example 35
1- [4- (1,2-diphenylÏthenyl) pyridinium] 3- (trimethylammonium) propane dibromide
Following the procedure according to Example 1, 4- (1,2-diphenylammonyl) -pyridine with 3-bromopropyltrimethylammonium bromide to 1- [4- (1,2-diphenylethenyl) -pyridinium] -3- (trimethylammonium) -propane dibromide implemented.



   Example 36
1- [4- (triphenylmethyl) pyridinium] -3- (trimethyl ammonium) propane dibromide
Following the process according to Example 1, 4- (triphenylmethyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide to give 1- [4- (triphenylmethyl) pyridinium] -3- (trimethylammonium) propanedibromide. This compound is a crystalline substance.



   Example 37
1- (2 - [(1-Naphthyl) ethyl] pyridinium) -3- (trimethylammonium) propane dibromide
Following the procedure according to Example 1, 2 - [(1-naphthyl) ethyl] pyridine was converted with 3-bromopropyl trimethylammonium bromide to I- (2- [(1-naphthyl) ethylj-pyridinium) -3- (trimethylammonium ) -propane dibromide implemented. This compound melts at 170-171 C with decomposition.



  Analysis:
Calculated: C 55, 88 H 6, 12 Br 32, 33
Found: 56, 15 6, 36 31, 58
Example 38
1- (4 - [(1-Naphthyl) ethyl] pyridinium) -
3- (trimethylammonium) propane dibromide
Following the procedure according to Example 1, 4- [(1-naphthyl) ethyl] pyridine was mixed with 3-bromopropyl trimethylammonium bromide to give I- (4- [(I-naphthyl) ethyl] pyridinium) -3- (trimethylammonium ) propane dibromide implemented.



   Example 39
1- (4- [3- (9 fluorenylcarboxy) -proyl-pyridinium) -3- (trimethylammonium) -propanedibromide
Following the procedure according to Example 1, 4- [3- (Fluorenylcarboxy) -propyl] -pyridine with 3-bromopropyl-trimethylammonium bromide to 1- (4- [3- (9-Fluorenylcarboxy) -propyl] -pyridinium) -3- (trimethylammonium) propane dibromide implemented.



   Example 40
1- [2- (3-indolylethyl) -l-methylpiperidinium] -
3- (trimethylammonium) propane dibromide
Following the procedure according to Example 1, 2- (3-indolylethyl) -1-methylpiperidine was reacted with 3-bromopropyltrimethylammonium) propane dibromide.



   Example 41
1- [2- (phenylethylamino) pyridinium] -3- (trimethylammonium) propane dibromide
Following the procedure according to Example 1, 2- (phenylmethylamino) pyridine was reacted with 3-bromopropyltrimethylammonium bromide to give 1- [2- (phenylethylamino) pyridinium] -3- (trimethylammonium) propane dibromide.



   Example 42
1- [2- (2-pyridylamino) pyridinium] -3- (trimethyl ammonium) propane dibromide
Following the process according to Example 1, 2,2'-dipyridylamine was reacted with 3-bromopropyltrimethylammonium bromide to give 1- [2- (2-pyridylamino) pyridine] -3- (trimethylammonium) propane dibromide.



   Example 43 1-spiro- [fluorene-9, 4'- (1'-methylpiperidinium)] -
3- (trimethylammonium) propane dibromide
According to the method according to Example 25, spiro- [fluoren-9, 4'- (1'-methylpiperidin)] with 3-bromopropyltrimethylammonium bromide was converted to 1-spiro- [fluoren-9, 4 '- (1'-methylpiperidinium)] - 3- (trimethyl ammonium) propane dibromide implemented. This compound melts at 274 C with decomposition.



  Analysis:
Calculated: C 56.48 H 6.71 Br 31.32
Found: 56, 06 6, 92 30, 87
Example 44 I- [4- (1-methyl-3-indolylethyl) pyridinium] -
3- (trimethylammonium) propane dibromide
A solution of 12.0 g (0.049 moles) 4- (1-methyl-3-indolylethyl) -pyridine and 9.15 g (0.035 moles) 3-bromopropyl-trimethylammonium bromide in 50 cm3 acetonitrile was 25 hours heated to reflux temperature. The solvent was decanted off from the oily precipitate. The oil was dissolved in ethyl alcohol and precipitated with ether; this process was repeated. The oily product was dried over phosphorus pentoxide in vacuo at room temperature.

   Thus, 5, 65 g (32% of the theoretical yield) 1- [4- (I-methyl-3-indolyIäthyl) -pyridinium] - 3- (trimethylammonium) -propanedibromide were obtained as an orange-yellow, hygroscopic substance, which recrystallized from isopropyl alcohol, in the form of yellow, hygroscopic needles.



  Analysis:
Calculated: C 53, 13 H 6, 28 Br 32, 14
Found: 52, 83 6, 47 3I, 98
The mixed salt, 1- [4- (1-methyl-3-indolyl-ethyl) -pyridinium] -3- (trimethylammonium) -propane monochloride, monobromide, is obtained by heating equimolar amounts of 4- (1-methyl-3- indolyl-ethyl) -pyridine and 3-chloropropyl-trimethylammonium bromide obtained in dimethylformamide solution at 125 ° C. (oil bath temperature) and collecting the precipitate formed in the cooled reaction mixture. The yield was 80% of theory.



   A solution of 25 g of 1- [4- (l-methyl-3-indolyl-ethyl) -pyridinium] -3- (trimethylammonium) -propane-dibromide in 500 cm3 of methanol was treated with an Amberlite anion exchange resin IRA 401 (previously with a sodium chloride solution regenerated) fed column passed. The column was then washed with fresh methanol. The eluate was concentrated in vacuo and the residue was recrystallized from azetonitrile. 16.5 g (81 / o of the theoretical yield) of 1- [4- (1-methyl-3-indolyl ethyl) pyridinium] -3- (trimethylammonium) propane dichloride were obtained. This salt melts at 195 ° C. with decomposition.



  Analysis:
Calculated: Cl 17.36
Found: 17, 30
Example 45 l- [2- (3-indolylethyl) -5-ethylpyridinium] -
3- (trimethylammonium) propane dibromide
A mixture of 10 g (0.04 moles) 2- (3-In dolylethyl) -5-ethylpyridine and 5.2 g (0.02 moles) 3-bromopropyltrimethylammonium bromide, dissolved in 50 cms of acetonitrile, is returned for 24 hours - heated river temperature. The solution was cooled, the precipitate was filtered off and recrystallized twice from isopropyl alcohol ethyl acetate and finally twice from isopropyl alcohol.

   The still impure substance thus obtained was dissolved in 25 cml of acetonitrile and heated to reflux temperature for 5 hours with the addition of 4 g of 2- (3-indolylethyl) -5-ethylpyridine. Recrystallization of the product thus obtained from isopropyl alcohol gave 1.4 g (13.510 / o of the theoretical yield)
1- [2- (3-indolylethyl) -5-äthylpyridinium] -3- (trimethylammonium) propane dibromide obtained in the form of a white, hygroscopic substance.



  Analysis:
Calculated: bromine ion 31, 26
Found: 30, 79
Example 46
1- [2- (l-methyl-3-indolylethyl) pyridinium] -
3- (trimethylammonium) propane dibromide
In accordance with the procedure described in Example 44, the 1- [2- (1-methyl-3-indolylethyl) pyridinium] was obtained by reacting 2- (1-methyl-3-indolylethyl) pyridine with 3-bromopropyltrimethylammonium bromide. , 3- (trimethylammonium) propanedibromide obtained as a solid substance that melts at 139-140 C with decomposition.



  Analysis:
Calculated: C 53, 13 6, 28 Br 32, 14
Found: 53, 26 5, 96 31, 83
Example 47
1- [2- (1-methyl-3-indolylethyl) -5-ethylpyridinium] -
3- (trimethylammonium) propane dibromide
In accordance with the method described in Example 44, the 1- [2- (1-methyl-3-indolylethyl) -5- was obtained by reacting 2- (1-methyl-3-indolylethyl) -5-ethylpyridine with 3-bromopropyltrimethylammonium bromide. ethylpyridinium] -3- (trimethylammonium) propane dibromide obtained. This compound is a solid substance that melts at 173-174 C with decomposition.



  Analysis:
Calculated: C 54.86 H 6, 72 Br 30, 42
Found: 54, 21 6, 53 30, 28
Example 48
1- [4- (l-Benzyl-3-indolylethyl) pyridinium] -
3-? 7-propane dibromide
In accordance with the procedure described in Example 19, the 1- [4- (l-benzyl-3-indolylethyl) pyridinium] was obtained by reacting 4- (1-benzyl-3-indolylethyl) pyridine with 3-bromopropyl trimethylammonium bromide. -3- (trimethylammonium) propane dibromide obtained. This compound is a solid substance that melts at 191-194 C with decomposition.



  Analysis:
Calculated: C 58.64 H 6.15 Br 27.87
Found: 56, 36 5, 95 27, 34
Example 49 1- (2- [1- (1-Methyl-3-indolyl) -2-propyl] -pyridinium) -
3- (trimethylammonium) propane dibromide
In accordance with the procedure described in Example 44, the 1- (2- [1- (1st) was obtained by reacting 2- [l- (l-methyl-3-indolyl) -2-propyl] -pyridine with 3-bromopropyltrimethylammonium bromide Methyl 3-indolyl) -2-propyl] pyridinium) -3- (trimethylammonium) propane dibromide.



   Example 50 1- [4- (1-Indolylethyl) pyridinium] -3- (trimethylammonium) propane dibromide
According to the procedure described in Example 19, 4- (1-indolylethyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide.



  The 1-4- (1-indolylethyl) pyridinium] -3- (trimethylammonium) propane dibromide is formed, a solid substance that melts at 223-225 C with decomposition.



  Analysis:
Calculated: C 52.18 H 6.05 Br 33.07
Found: 51, 79 5, 87 32, 63
Example 51 1- [2- (1-Benzotriazolylethyl) pyridinium] -
3- (trimethylammonium) propane dibromide
In accordance with the procedure given in Example 19, 2- (1-BenzotriazoIäthyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide and the 1- [2- (1-benzotriazolylethyl) pyridinium] -3- (trimethylammonium) propane dibromide was used as the white hygroscopic substance obtained.



  Analysis:
Calculated: Br 32.88
Found: 32, 30
Example 52
1- [2- (1-Indenylethyl) pyridinium] -3- (trimethylammonium) propane dibromide
In accordance with the procedure given in Example 44, 2- (1-indenylethyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide and the 1- [2- (1-indenylethyl) pyridinium] -3- (trimethylammonium) propane dibromide was used as the solid substance that melts at 138-190 C with decomposition.



  Analysis:
Calculated: C 54, 78 H 6, 27 Br 33, 14
Found: 54, 44 6, 42 32, 68
Example 53
1- [2- (1-methyl-3-oxindolylÏthyl) pyridinium]
3- (trimethylammonium) propane dibromide
In accordance with the procedure given in Example 44, 2- (1-methyl-3-oxindolethyl) pyridine was treated with 3-bromopropyl trimethylammonium bromide to give 1- [2- (1-methyl-3-oxindolylethyl) pyridinium] -3 - (trimethylammonium) propane dibromide implemented.



   By far 54
1- [4- (benzyloxyethyl) pyridinium] -3- (trimethylammonium) propane dibromide
In accordance with the process described in Example 19, 4- (benzyloxyethyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide to give 1- [4- (benzyloxyethyl) pyridinium] -3- (trimethylammonium) propanedibromide.



   Example 55
1- [4- (benzylthioethyl) pyridinium] -3- (trimethylammonium) propane dibromide
Corresponding to the process according to Example 1, 4- (benzylthioethyl) pyridine was reacted with 3-bromopropyltrimethylammonium bromide to give 1- [4- (benzylthioÏthyl) pyridinium] -3- (trimethylammonium) propanedibromide.



   Example 56
1- [4- (9-fluorothioethyl) pyridinium] -3- (trimethylammonium bromide) propane dibromide
Corresponding to the procedure of Example 1, 4- (9-fluorothioethyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide to give 1- [4- (9 fluorothioethyl) pyridinium] -3- (trimethylammonium bromide) propane dibromide. This substance melts with evolution of gas at 202-204 C.



   Example 57 1- (2- {6- (Bicyclo- [2. 2. 1] -2-heptenyl)} - pyridinium) -
3- (trimethylammonium) propane dibromide
Following the procedure of Example 19, 2- {6- (Bicyclo- [2. 2. 1] -2-heptenyl)} - pyridine with 3-bromopropyl-trimethylammonium bromide to 1- (2- {6- (Bicyclo- [ 2. 2. 1] -2-heptenyl)} - pyridinium) -3- (trimethylammonium) propane dibromide implemented. The compound is a hygroscopic, solid substance.



   Example 58 1- (5- {6- (Bicyclo- [2.2.1] -2-heptenyI)} -2-picolinium) -3- (trimethylammonium) propane dibromide
Following the procedure of Example 44, 5- {6- (Bicyclo - [2. 2. 1] -2-heptenyl)} -2-picoline with 3-bromopropyl-trimethylammonium bromide was given to 1- (5- {6- (Bicyclo - [2.2.1] -2-heptenyl) f-2-picolinium) -3- (trimethylammonium) propane dibromide converted.



  The compound is a solid, hygroscopic substance.



  Analysis:
Calculated: Br 35.82
Found: 35, 58
Example 59
1- (4- [¯- (1-methyl-3-indolyl) -α-cyclohexylÏthyl] pyridinium) -3- (trimethylammonium) propane dibromide
In accordance with the procedure described in Example 19, 4- [- (1-methyl-3-indoIyl) -acyclohexylethyl] pyridine with 3-bromopropyl-trimethylammonium bromide to 1- (4- [, 8- (I-methyl- 3-indolyl) - c-cyclohexylethyl)] - pyridinium) -3- (trimethylammonium) propane dibromide implemented. This compound melts at 237-239 C.



   Example 60
1- (4- [¯- (1-methyl-3-indolyl) -α- (4-thylcyclohexyl] ethyl] pyridinium) -3- (trimethylammonium) propane dibromide
Following the procedure given in Example 19, 4- [¯- (1-methyl-3-indolyl) -α- (4-ethylcyclohexyl) -ethyl] -pyridine with 3-bromopropyl-trimethylammonium bromide was obtained to 1- (4- [ - (L-methyl-3-indolyl) -a- (4-äthylcyclohexyL) -ethyl] -pyridinium) - 3- (trimethylammonium) -propanedibromide implemented.



  This compound melts with decomposition at 150 C.



   Example 61 1- [3- (2-indolyl) pyridinium] -3- (trimethylammonium) propane dibromide
In accordance with the procedure given in Example 19, 3- (2-indolyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide to give 1- [3- (2-indolyl) 3- (trimethylammonium) propane dibromide. This compound is a substance that melts at 246-250 C.



  Analysis:
Calculated: C 50, 12 H 5, 54 Br 35, 11
Found: 50, 06 5, 49 34, 96
Example 62
1- [4- (2-indolyl-pyridinium] -3- (trimethylammonium) propane dibromide
In accordance with the procedure given in Example 19, 4- (2-indolyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide to give 1- [4- (2-indolyl) pyridinium] -3- (trimethylammonium) propane dibromide. This compound melts at 236-238 C.



  Analysis:
Calculated: Br 35, 11
Found: 34, 51
Example 63
1- [4- (3, 3'-diindolylmethyl) pyridinium] -
3- (trimethylammonium) propane dibromide
According to the procedure given in Example 1, 4- (3, 3'-diindolylmethyl) -pyridine with 3-bromopropyl-trimethylammonium bromide to 1- [4- (3, 3'-diindolylmethyl) -pyridinium] -3- (trimethyl- ammonium) propane dibromide implemented. This compound melts with decomposition at 220 C.



  Analysis:
Calculated: C 57.54 H5.52 Br 27.35
Found: 57, 43 5, 63 26, 72
Example 64
1- [3- (3, 31-Diindolylmethyl) -pyridiniuml-
3- (trimethylammonium) propane dibromide
According to the procedure described in Example 1, 3- (3, 3'-diindolylmethyl) -pyridine with 3-bromopropyl-trimethylammonium bromide to 1- [3- (3, 3'-diindolylmethyl) -pyridinium] -3- (trimethyl- ammonium) propane dibromide implemented.



   Example 65
1- [2- (3, 3'-diindolylmethyl) pyridinium] -
3- (trimethylammonium) propane dibromide
According to the procedure described in Example 1, 2- (3, 3'-diindolylmethyl) -pyridine with 3-bromopropyl-trimethylammonium bromide to 1- [2- (3, 3'-diindolylmethyl) -pyridinium] -3- (trimethyl- ammonium) propane dibromide implemented.



   Example 66
1- (4- [bis- (1-methyl-3-indolyl) methyl] pyridinium) -
3- (trimethylammonium) propane dibromide
Following the procedure described in Example 1, 4- [bis- (1-methyl-3-indolyl) -methyl] -pyridine with 3-bromopropyl-trimethylammonium bromide to 1- (4- [bis- (1-methyl-3- indolyl) methyl] pyridinium) - 3- (trimethylammonium) propane dibromide implemented.



   Example 67
1- [4- (1-methyl-3-indolylethyl) -l-methylpiperidinium] -
3- (trimethylammonium) propane dibromide
In accordance with the procedure described in Example 24, 4- (1-methyl-3-indolylethyl) -1-methylpiperidine with 3-bromopropyltrimethylammonium bromide to give 1- [4- (l-methyl-3-indolylethyl) -l- methylpiperidiniumli-3- (trimethylammonium) propanedibromide implemented.



   Example 68 l-r2- (1-methyl-3-indolylethyl) -1-methylpiperidinium] -
3- (trimethylammonium) propane dibromide
In accordance with the procedure described in Example 25, 2- (1-methyl-3-indolylethyl) -1-methylpiperidine was converted with 3-bromopropyltrimethylammonium bromide to give 1- [2- (1-methyl-3-indolylethyl) -l-methyl piperidinium ] - '3 (trimethylammonium) propanedibromide implemented.



   Example 69 1- (4- {2- (Bicyclo- [2.2.1] -heptyl)} - 1-methylpiperidinium-3- (trimethylammonium) -propanedibromide
According to the procedure described in Example 25, 4- {2- (Bicyclo- [2. 2. 1] -heptyl)} - 1-methylpiperidine with 3-bromopropyl-trimethylammonium bromide to give 1- (4- {2- (bicyclo- [2. 2. 1] -heptyl)} - l methylpiperidinium) -3- (trimethylammonium) propane dibromide converted. This compound melts at 258-260 C with decomposition.



  Analysis:
Calculated: C 50, 22 H 8, 43 Br 35, 18
Found: 50, 26 8, 44 34, 58
Example 70
1- [1- (2-Oxy-1-octyl) piperidinium] -3- (trimethyl ammonium) propane dibromido
Following the procedure described in Example 16, 1- (2-Oxy-1-octyl) -piperidine was mixed with 3-bromopropyl-trimethylammonium bromide to give 1- [1- (2-Oxy-1-octyl) piperidinium] -3¯ (trimethylammo nium) propane dibromide implemented.



   Example 71
1- [1- (2-Azetoxy-l-octyl) piperidinium] -
3- (trimethylammonium) propane dibromide
Following the procedure described in Example 16, 1- (2-Azetoxy-1-octyl) -piperidine was made with 3-bromopropyl-trimethylammonium bromide to give 1- [1- (2-Azetoxy-1-octyl) -piperidinium] -3-trimethylammo - nium) propane dibromide implemented.



   Example 72 l- [l- (2-Benzoxy-l-octyl) piperidinium] -
3- (trimethylammonium) propane dibromide
Following the procedure described in Example 16, 1- (2-Benzoxy-1-octyl) -piperidine with 3-bromopropyl-trimethylammonium bromide to 1- [1- (2-Benzoxy-1-octyl) -piperidinium] -3- ( trimethyl ammonium) propane dibromide implemented.



   Example 73
1-rl- (2-Oxy-1-decyl) piperidinium] -3- (trimethylammonium) propane dibromide
In accordance with the method of Example 16, 1- (2-oxy-1-decyl) piperidine with 3-bromopropyl trimethylammonium bromide was used to give 1- [1- (2-oxy-1 decyl) piperidinium] -3- (trimethylammonium) -propane dibromide implemented.



   Example 74
1- [I- (2-Azetoxy-1-decyl) piperidinium] -3- (trimethylammonium) propane dibromide
According to the method of Example 16, 1- (2-Azetoxy-l-decyl) -piperidine with 3-bromopropyl-trimethylammonium bromide to 1- [I- (2-Azetoxy-1-decyl) -piperidinium] -3- (trimethylammonium) - propanedibromide implemented.



   Example 75
1- [l- (2-Oxy-l-dodecyl) piperidinium] -
3- (trimethylammonium) propane dibromide
Following the procedure of Example 16, 1- (2-oxy-1-dodecyl) piperidine was mixed with 3-bromopropyl trimethylammonium bromide to give 1- [1- (2-oxy-1-dodecyl) piperidinium] -3- (trimethylammonium ) - propanedibromide implemented.



   Example 76 l-tl- (2-Azetoxy-l-dodecy0-piperidinium] -
3- (trimethylammonium) propane dibromide
According to the method of Example 16, 1- (2-Azetoxy-l-dodecyl) -piperidine with 3-bromopropyl-trimethylammonium bromide to 1- [1- (2-Azetoxy-l-dodecyl) -piperidinium] -3- (trimethylammonium) propanedibromide implemented.



   Example 77
1- [1- (2, 11-Dioxy-1-undecyl) piperidinium] -
3- (trimethylammonium) propane dibromide
Following the procedure described in Example 16, 1- (2, 11-Dioxy-l-undecyl) -piperidine with 3-bromopropyl-trimethylammonium bromide to 1- [1- (2, 11-Dioxy-l-undecyl) -piperidinium] -3- (trimethylammonium) propane dibromide implemented.



   Example 78
1- [l- (2, 11-diacetoxy-l-undecyl) piperidinium] -
3- (trimethylammonium) propane dibromide
According to the procedure described in Example 16, 1- (2, 11-diazetoxy-l-undecyl) -piperidine with 3-bromopropyl-trimethylammonium bromide to 1- [1- (2, 11-diacetoxy-l-undecyl) - piperidinium] - 3- (trimethylammonium) propane dibromide implemented.



   Example 79
1- [I- (2-Oxy-2-benzyl-4-butyl) piperidinium] -
3- (trimethylammonium) propane dibromide
Following the procedure described in Example 16, 1- (2-oxy-2-benzyl-4-butyl) -piperidine was treated with 3-bromopropyl-trimethylammonium bromide to give 1- [1- (2-oxy-2-benzyl-4 -butyl) -piperidinium] -3- (trimethylammonium) -propanedibromide implemented.



   Example 80
1- [I- (2-phenyl-2-oxyethyl) piperidinium] -
3- (trimethylammonium) propane dibromide
In accordance with the procedure described in Example 16, 1- (2-phenyl-2-oxyethyl) piperidine was mixed with 3-bromopropyl trimethylammonium bromide to give 1- [I- (2-phenyl-2-oxyethyl) piperidinium] -3- ( trimethylammonium) propane dibromide implemented.



   Example 81
1- [2- (benzoxypropyl) pyridinium] -3- (trimethylammonium) propane dibromide
In accordance with the procedure described in Example 1, 2- (benzoxypropyl) pyridine was reacted with 3-bromopropyl trimethylammonium bromide to give 1- [2-benzoxypropyl) pyridinium] -3- (trimethylammonium) propanedibromide.



   Example 82
1- [3- (9-fluorenecarboxymethyl) -1-methylpiperidinium] -3- (trimethylammonium) propane dibromide
According to the method described in Example 1, 3- (9-fluorene carboxymethyl) -l-methylpiperidine with 3-bromopropyl-trimethylammonium bromide to give 1- [3- (9-fluorene carboxymethyl) -l-methyl-piperidinium] -3- ( trimethylammonium) propane dibromide implemented.



   Example 83 1- [3- (Diphenylmethoxymethyl) -l-methylpiperidinium] -
3- (trimethylammonium) propane dibromide
In accordance with the process described in Example 1, 3- (diphenylmethoxymethyl) -l-methylpiperidine was mixed with 3-bromopropyltrimethylammonium bromide to give 1- [3- (diphenylmethoxymethyl) -l-methylpiperidinium] -3- (trimethylammonium) propane dibromide implemented.

Claims (1)

PATENTANSPRUCH Verfahren zur Herstellung neuer bisquaternärer Ammoniumverbindungen der Formel EMI13.1 m welcner EMI13.2 den Pyridinring oder den durch eine niedere Alkylgruppe, welche gegebenenfalls höchstens zwei Oxy-, Acetoxy-, Phenyl-oder Benzoxygruppen trägt, N-substituierten 1, 2, 5, 6-Tetrahydropyridinring oder Piperidinring und R, R1, R2, R3 und R4 nichtionisierende Gruppen oder, jedoch nicht alle, Wasserstoff, Rs und Rg niedere aliphatische Gruppen oder R5 und R zusammen mit dem Stickstoffatom einen gegebenenfalls ein weiteres Heteroatom aufweisenden Ring bedeuten, R7 eine niedere Alkylgruppe, PATENT CLAIM Process for the preparation of new bisquaternary ammonium compounds of the formula EMI13.1 m welcner EMI13.2 the pyridine ring or the N-substituted 1, 2, 5, 6-tetrahydropyridine ring or piperidine ring and R, R1, R2, R3 and R4 nonionizing by a lower alkyl group which optionally carries at most two oxy, acetoxy, phenyl or benzoxy groups Groups or, but not all, hydrogen, Rs and Rg are lower aliphatic groups or R5 and R together with the nitrogen atom represent a ring optionally containing a further heteroatom, R7 is a lower alkyl group, A eine Alkylenbrücke mit 2 bis 6 Kohlenstoffatomen und Xe ein Anion bedeuten, wobei die Gruppe EMI13.3 ein Radikalgewicht zwischen 150 und 350 besitzt, wobei, falls EMI13.4 den Pyridinring bedeutet, mindestens einer der Substituenten R und R4 Wasserstoff ist, und wobei die Gruppe EMI13.5 ein Radikalgewicht zwischen 59 und 117 besitzt, dadurch gekennzeichnet, dass ein Amin der Formel II EMI13.6 mit einem quatemären Ammoniumsalz der Formel III EMI13.7 in der X'ein Chlor-, Brom-oder Jodatom bedeutet, umgesetzt wird. A is an alkylene bridge with 2 to 6 carbon atoms and Xe is an anion, the group EMI13.3 has a radical weight between 150 and 350, where, if EMI13.4 denotes the pyridine ring, at least one of the substituents R and R4 is hydrogen, and the group EMI13.5 has a radical weight between 59 and 117, characterized in that an amine of the formula II EMI13.6 with a quaternary ammonium salt of the formula III EMI13.7 in which X 'denotes a chlorine, bromine or iodine atom, is reacted. UNTERANSPRUCHE 1. Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass die Quaternisierung bei einer zwischen etwa Raumtemperatur und 150 C liegenden Temperatur unter Atmosphärendruck durchgeführt wird. SUBCLAIMS 1. The method according to claim, characterized in that the quaternization is carried out at a temperature between about room temperature and 150 C under atmospheric pressure. 2. Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass bei Rückflusstemperatur des Gemisches der Ausgangsstoffe gearbeitet wird. 2. The method according to claim, characterized in that it is carried out at the reflux temperature of the mixture of starting materials. 3. Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass die Quaternisierung in Gegenwart eines Lösungsmittels durchgeführt wird. 3. The method according to claim, characterized in that the quaternization is carried out in the presence of a solvent. 4. Verfahren nach Unteranspruch 3, dadurch gekennzeichnet, dass als Lösungsmittel ein tXberschuss eines der Ausgangsstoffe verwendet wird. 4. The method according to dependent claim 3, characterized in that an excess of one of the starting materials is used as the solvent. 5. Verfahren nach Unteranspruch 3, dadurch gekennzeichnet, dass als Lösungsmittel Azetonitril verwendet wird. 5. The method according to dependent claim 3, characterized in that acetonitrile is used as the solvent. 6. Verfahren nach Unteranspruch 3, dadurch gekennzeichnet, dass als Lösungsmittel Dimethylformamid verwendet wird. 6. The method according to dependent claim 3, characterized in that dimethylformamide is used as the solvent. 7. Verfahren nach Unteranspruch 3, dadurch gekennzeichnet, dass als Lösungsmittel ein aliphatischer Alkohol verwendet wird. 7. The method according to dependent claim 3, characterized in that an aliphatic alcohol is used as the solvent. 8. Verfahren nach Unteranspruch 3, dadurch gekennzeichnet, dass als Lösungsmittel ein Nitroalkan verwendet wird. 8. The method according to dependent claim 3, characterized in that a nitroalkane is used as the solvent. 9. Verfahren nach Unteranspruch 3, dadurch gekennzeichnet, dass als Lösungsmittel Dioxan verwendet wird. 9. The method according to dependent claim 3, characterized in that the solvent used is dioxane. 10. Verfahren nach Patentanspruch und den Unteransprüchen 2 und 3, dadurch gekennzeichnet, dass eine Lösung von 4- (1-Methyl-3-indolyläthyl)-pyridin und 3-Brompropyl-trimethylammoniumbromid in einem organischen Lösungsmittel auf Rückflusstempe- ratur erwärmt wird, wobei sich 1- [4- (l-Methyl-3- indolyläthyp-. pyridinium]-3- (trimethylammonium)- propandibromid bildet. 10. The method according to claim and the dependent claims 2 and 3, characterized in that a solution of 4- (1-methyl-3-indolylethyl) pyridine and 3-bromopropyl-trimethylammonium bromide in an organic solvent is heated to reflux temperature, wherein 1- [4- (1-methyl-3-indolylethyp. pyridinium] -3- (trimethylammonium) propanedibromide is formed. 11. Verfahren nach Patentanspruch und den Unteransprüchen 2 und 3, dadurch gekennzeichnet, dass eine Lösung von 2- (1-Methyl-3-indolyl)-5-äthylpyridin und 3-Brompropyl-trimethylammoniumbromid in einem organischen Lösungsmittel auf Rückflusstemperatur erwärmt wird, wobei sich 1- [2- (l-Methyl- 3-indolyläthyl)-5-äthylpyridinium]-13-(trimethyl- ammonium)-propandibromid bildet. 11. The method according to claim and the dependent claims 2 and 3, characterized in that a solution of 2- (1-methyl-3-indolyl) -5-ethylpyridine and 3-bromopropyl-trimethylammonium bromide in an organic solvent is heated to reflux temperature, wherein 1- [2- (1-methyl-3-indolylethyl) -5-ethylpyridinium] -13- (trimethylammonium) propane dibromide is formed. 12. Verfahren nach Patentanspruch und den Unteransprüchen 2 und 3, dadurch gekennzeichnet, dass eine Lösung von 4-(1-Indolyläthyl)-pyridin und 3-Brompropyl-trimethylammoniumbromid in einem organischen Lösungsmittel auf Rückflusstemperatur erwärmt wird, wobei sich 1- [4- (I-Indolyrdthyl)-pyri- dinium]-3- (trimethylammonium)-propandibromid bil- det. 12. The method according to claim and the dependent claims 2 and 3, characterized in that a solution of 4- (1-indolylethyl) pyridine and 3-bromopropyl trimethylammonium bromide in an organic solvent is heated to reflux temperature, wherein 1- [4- (I-indolyrdthyl) pyridine] -3- (trimethylammonium) propane dibromide. 13. Verfahren nach Patentanspruch und den Unteransprüchen 2 und 3, dadurch gekennzeichnet, dass eine Lösung von 4- (1-IndenyIäthyl)-pyridin mit 3-Brompropyl-trimethylammoniumbromid in einem organischen Lösungsmittel auf Rückflusstemperatur erwärmt wird, wobei sich 1- [4- (I-Indenyliithyl)-pyri- dinium]-3-(trimethylammonium)-propandibromid bildet. 13. The method according to claim and the dependent claims 2 and 3, characterized in that a solution of 4- (1-indenylethyl) pyridine with 3-bromopropyl-trimethylammonium bromide in an organic solvent is heated to reflux temperature, wherein 1- [4- (I-Indenyliithyl) -pyridinium] -3- (trimethylammonium) -propanedibromide forms. 14. Verfahren nach Patentanspruch und den Unteransprüchen 2 und 3, dadurch gekennzeichnet, dass eine Losung von 2- [ (l-Naphthyl)-äthyl]-pyridin und 3-Brompropyl-trimethylammoniumbromid in einem organischen Lösungsmittel auf Rückflusstemperatur erwärmt wird, wobei sich 1-(2-[(1-Naphthyl)-äthyl]- pyridinium)-3- (trimethylammonium)-propandibromid bildet. 14. The method according to claim and the dependent claims 2 and 3, characterized in that a solution of 2- [(l-naphthyl) ethyl] pyridine and 3-bromopropyl trimethylammonium bromide in an organic solvent is heated to reflux temperature, with 1 - Forms (2 - [(1-naphthyl) ethyl] pyridinium) -3- (trimethylammonium) propane dibromide. 15. Verfahren nach Patentanspruch und den Unteransprüchen 2 und 3, dadurch gekennzeichnet, dal3 eine Lösung von 4- (3-Indolyläthyl)-pyridin und 3-Brompropyl-trimethylammoniumbromid in einem organischen Lösungsmittel auf Rückflusstemperatur erwärmt wird, wobei sich l- [4- (3-lndolyläthyl)-pyri- dinium]-3- (trimethylammonium)-propandibromid bildet 16. Verfahren nach Patentanspruch und den Unteransprüchen 2 und 3, dadurch gekennzeichnet, dass 2- (1-Indenyläthyl)-pyridin mit 3-Brompropyl-trime- thylammoniumbromid als Quaternisierungsmittel behandelt wird, wobei sich 1-[2-(Indenyläthyl)-pyridi- nium]-3- (trimethylammonium)-propandibromid bildet. 15. The method according to claim and the dependent claims 2 and 3, characterized in that a solution of 4- (3-indolylethyl) pyridine and 3-bromopropyl-trimethylammonium bromide in an organic solvent is heated to reflux temperature, wherein l- [4- (3-indolylethyl) pyridine] -3- (trimethylammonium) propane dibromide forms 16. The method according to claim and the dependent claims 2 and 3, characterized in that 2- (1-indenylethyl) pyridine with 3-bromopropyl trim - thylammonium bromide is treated as a quaternizing agent, with 1- [2- (indenylethyl) pyridinium] -3- (trimethylammonium) propane dibromide being formed. 17. Verfahren nach Patentanspruch und den Un teransprüchen 2 und 3, dadurch gekennzeichnet, dass eine Lösung von 2- (3-IndolyläthyV-pyridin und 3-Brompropyl-trimethylammoniumbromid in einem organischen Lösungsmittel auf Rückflusstemperatur erwärmt wird, wobei sich 1-[2-(3-Indolyläthyl)-pyri- dinium]-3- (trimethylammonium)-propandibromid bildet. 17. The method according to claim and the sub-claims 2 and 3, characterized in that a solution of 2- (3-IndolyläthyV-pyridine and 3-bromopropyl-trimethylammonium bromide in an organic solvent is heated to reflux temperature, wherein 1- [2- (3-Indolylethyl) pyridine] -3- (trimethylammonium) propane dibromide. 18. Verfahren nach Patentanspruch und den Unteransprüchen 2 und 3, dadurch gekennzeichnet, dass eine Lösung von 4- (3-Benzoxypropyl)-pyridin und 3-Brompropyl-trimethylammoniumbromid in einem organischen Lösungsmittel auf Rückflusstemperatur erwärmt wird, wobei sich 1- [4- (3-Benzoxypropyl)- pyridinium]-3- (trimethylammonium)-propandibromid bildet. 18. The method according to claim and the dependent claims 2 and 3, characterized in that a solution of 4- (3-benzoxypropyl) pyridine and 3-bromopropyl trimethylammonium bromide in an organic solvent is heated to reflux temperature, wherein 1- [4- (3-Benzoxypropyl) pyridinium] -3- (trimethylammonium) propane dibromide. 19. Verfahren nach Patentanspruch und den Unteransprüchen 2 und 3, dadurch gekennzeichnet, dass eine Lösung von 2-(1-Methyl-3-indolyläthyl)-pyridin und 3-Brompropyl-trimethylammoniumbromid in einem organischen Lösungsmittel auf Rückflusstemperatur erwärmt wird, wobei sich 1- [2- (l-Methyl 3-indolyläthyl-pyridinium]-3- (trimethylammonium)- propandibromid bildet. 19. The method according to claim and the dependent claims 2 and 3, characterized in that a solution of 2- (1-methyl-3-indolylethyl) pyridine and 3-bromopropyl trimethylammonium bromide in an organic solvent is heated to reflux temperature, with 1 - Forms [2- (l-methyl 3-indolylethylpyridinium] -3- (trimethylammonium) - propanedibromide.
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