CH110596A - Process for the preparation of tropine carboxylic acid esters. - Google Patents

Process for the preparation of tropine carboxylic acid esters.

Info

Publication number
CH110596A
CH110596A CH110596DA CH110596A CH 110596 A CH110596 A CH 110596A CH 110596D A CH110596D A CH 110596DA CH 110596 A CH110596 A CH 110596A
Authority
CH
Switzerland
Prior art keywords
sep
carboxylic acid
acid esters
preparation
tropine
Prior art date
Application number
Other languages
German (de)
Inventor
Firma E Merck
Original Assignee
Merck Ag E
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 Merck Ag E filed Critical Merck Ag E
Publication of CH110596A publication Critical patent/CH110596A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D451/00—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof
    • C07D451/02—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof containing not further condensed 8-azabicyclo [3.2.1] octane or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane; Cyclic acetals thereof
    • C07D451/04—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof containing not further condensed 8-azabicyclo [3.2.1] octane or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane; Cyclic acetals thereof with hetero atoms directly attached in position 3 of the 8-azabicyclo [3.2.1] octane or in position 7 of the 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring system
    • C07D451/06—Oxygen atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  

  Verfahren zur Darstellung von     Tropinkarbonsäureestern.       Es ist bekannt, dass     Tropinonkarbon-          säureester    durch     Natriumamalgam    in schwach  Saurer Lösung reduziert werden kann.     (Vergl.          Willstätter    und     Bommer,        Ann.    422 (1921),  . 15 ff.).

   Auch hat man     Tropinonkarbon-          Sä        ure,    die aus A     cetondikarbonsäure,        Succin-          clialdehyd    und     Methylamin    erhalten wurde,       mittelst        Na.triumamalgam    reduziert.  



  Die Reduktion mit     Natriumamalgam    ver  läuft aber in beiden Fällen ausserordentlich  langsam und benötigt durch .den ständigen  Zusatz von Amalgam und dadurch, dass die  Lösung dauernd schwach sauer gehalten     wer-          (teil        muss,    viel     Reduldionsmittel,    Zeit und       Arbeit.     



  Bekannt ist auch, dass     man        Tropinon    in  saurer oder schwach saurer oder alkalischer  Lösung auf elektrolytischem Wege zu dem       entsprechenden    Alkohol reduzieren kann.  



  Eine Übertragung der elektrolytischen  Reduktion auf     Tropinka.rbonsäureester    war  ohne weiteres nicht     gegeben,    weil nicht vor  auszusehen war, ob bei der Anwendung die  ser Reduktion die     Estergruppen    erhalten blei-         ben        (vergl.    A.     Moser,    Die elektrolytischen  Prozesse der organischen Chemie (1910),  Seite<B>177,</B> 178 und 182).  



  Es wurde nun gefunden, dass man die Re  duktion der     Tropinonkarbonsäureester    leicht  und bequem elektrolytisch in saurer Lösung  in der Weise durchführen kann, wenn man  Kathoden, die Überspannung .aufweisen, z. B.  aus Quecksilber, Blei, Cadmium oder Wis  mut,     verwendet.     



       Beispiel:     100     2r        Tropinonkarbonsäuremethylester     werden mit 40     %iger    Schwefelsäure unter  Eiskühlung übersättigt und auf 200 cm'  aufgefüllt.. Die Flüssigkeit     wird.    unter Küh  lung in einem nach Tafel     (Ber.    88, 1900,  S.     2209)=    zusammengesetzten Bleigefäss mit       Diaphragma    mit 5 Ampere bei 10 Volt Span  nung     elektrolysiert,    unter     Zutropfen    50     %iger     Schwefelsäure nach Bedarf.

   Die     Reduktion     wird     kolorimetrisch    durch die Abnahme der  Stärke der     Enolfärbung    mit Eisenchlorid       verfolgt    und so lange fortgesetzt,     13is    nur  noch ein geringer Gehalt au unverändertem  Ester zu ermitteln ist.

      
EMI0002.0001     
  
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<tb>  C'hlorlydrat <SEP> sich <SEP> in <SEP> Kristallen <SEP> abseheidet <SEP> und
<tb>  liei <SEP> 195 <SEP>   <SEP> sehmilzt.



  Process for the preparation of tropine carboxylic acid esters. It is known that tropinone carboxylic acid esters can be reduced by sodium amalgam in weakly acidic solution. (See Willstätter and Bommer, Ann. 422 (1921),. 15 ff.).

   Tropinone carbonic acid, obtained from acetone dicarboxylic acid, succinic aldehyde, and methylamine, has also been reduced by means of sodium amalgam.



  The reduction with sodium amalgam, however, proceeds extremely slowly in both cases and requires the constant addition of amalgam and the fact that the solution has to be kept constantly weakly acidic, a lot of reducer, time and work.



  It is also known that tropinone can be electrolytically reduced to the corresponding alcohol in an acidic or weakly acidic or alkaline solution.



  A transfer of the electrolytic reduction to tropine carboxylic acid esters was not readily available, because it was not possible to foresee whether the ester groups would be retained when this reduction was applied (cf. A. Moser, Die elektrolytische Prozess derorgan Chemie (1910) , Pages <B> 177, </B> 178 and 182).



  It has now been found that the reduction of the tropinone carboxylic acid esters can be carried out easily and conveniently electrolytically in acidic solution in the manner when cathodes that have overvoltage, eg. B. from mercury, lead, cadmium or Wis mut, used.



       Example: 100 2r tropinone carboxylic acid methyl ester are supersaturated with 40% sulfuric acid with ice cooling and made up to 200 cm. The liquid is. electrolyzed under cooling in a lead vessel with a diaphragm with 5 amps at 10 volts voltage according to Tafel (Ber. 88, 1900, p. 2209) = with dropwise addition of 50% sulfuric acid as required.

   The reduction is followed colorimetrically by the decrease in the strength of the enol coloration with ferric chloride and is continued until only a small amount of unchanged ester can be determined.

      
EMI0002.0001
  
    The <SEP> received from <SEP> the <SEP> Recluhtion <SEP> <SEP> Gemiseli
<tb> Lestelit <SEP> to the <SEP> smaller <SEP> part <SEP> from <SEP> rl @ egonin meilylester <SEP> and <SEP> to the <SEP> larger <SEP> part <SEP> from <SEP> i -? i, '
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<tb> says <SEP> means <SEP> 128 <SEP>. <SEP> The first <SEP> is <SEP> a <SEP> 0l; <SEP> .is
<tb> C'hlorlydrat <SEP> <SEP> separates into <SEP> crystals <SEP> <SEP> and
<tb> liei <SEP> 195 <SEP> <SEP> sehmilzt.

Claims (1)

EMI0002.0002 RATENTANBPRUCFI <SEP> : <tb> Verfahren <SEP> zur <SEP> Darstellun- <SEP> von <SEP> Tropin harbons < iureestern <SEP> durch <SEP> Reduktion <SEP> von <SEP> Tro pinona@bona.i.n@cest@ <SEP> En <SEP> mit <SEP> Wasserstoff. <SEP> rla duralie@ennzeiclrn@t, <SEP> ilass <SEP> man <SEP> Ti-oliinonl@:ir bonsüure@-ster <SEP> in <SEP> saurer <SEP> Lüaung <SEP> an <SEP> Kathoden <tb> mit <SEP> Überspannung <SEP> der <SEP> Elektroli'ao <SEP> unter wirft. EMI0002.0002 RATENTANBPRUCFI <SEP>: <tb> Method <SEP> for the <SEP> representation- <SEP> of <SEP> tropine harbons <iureestern <SEP> by <SEP> reduction <SEP> of <SEP> Tro pinona @ bona.in @ cest @ <SEP > En <SEP> with <SEP> hydrogen. <SEP> rla duralie @ ennzeiclrn @ t, <SEP> ilass <SEP> man <SEP> Ti-oliinonl @: ir bonsüure @ -ster <SEP> in <SEP> acidic <SEP> air <SEP> on <SEP> Cathodes <tb> with <SEP> overvoltage <SEP> which throws <SEP> Elektroli'ao <SEP> under.
CH110596D 1923-09-15 1924-07-18 Process for the preparation of tropine carboxylic acid esters. CH110596A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEM82537D DE408869C (en) 1923-09-15 1923-09-15 Process for the preparation of tropine carboxylic acid esters

Publications (1)

Publication Number Publication Date
CH110596A true CH110596A (en) 1925-07-01

Family

ID=7319347

Family Applications (1)

Application Number Title Priority Date Filing Date
CH110596D CH110596A (en) 1923-09-15 1924-07-18 Process for the preparation of tropine carboxylic acid esters.

Country Status (3)

Country Link
AT (1) AT100457B (en)
CH (1) CH110596A (en)
DE (1) DE408869C (en)

Also Published As

Publication number Publication date
AT100457B (en) 1925-07-10
DE408869C (en) 1925-01-24

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