CH286498A - Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole. - Google Patents

Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole.

Info

Publication number
CH286498A
CH286498A CH286498DA CH286498A CH 286498 A CH286498 A CH 286498A CH 286498D A CH286498D A CH 286498DA CH 286498 A CH286498 A CH 286498A
Authority
CH
Switzerland
Prior art keywords
benz
keto
indole
tetrahydro
preparation
Prior art date
Application number
Other languages
German (de)
Inventor
Ag Haco Gesellschaft
Original Assignee
Haco Ges Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haco Ges Ag filed Critical Haco Ges Ag
Publication of CH286498A publication Critical patent/CH286498A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/90—Benzo [c, d] indoles; Hydrogenated benzo [c, d] indoles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Indole Compounds (AREA)

Description

       

  Verfahren zur Herstellung von     5-Keto-1,3,4,5-tetrahydro-benz(ed)indol.            5-Keto-1,3,4,5-tetrahydro-benz(cd)indol    ist  ein wertvolles Zwischenprodukt. zur Herstel  lung von     Ly        sergsäure    bzw. von mit der     Ly-          sergsäure    verwandten     Verbindungen;    es ist  nach einem kostspieligen Verfahren hergestellt  worden;     vgl:    C.     Uhle,    J. Am.     Chem.        Soc.    71,  761-766 (1949).  



  Es wurde nun gefunden, dass dieses     Keton     besonders vorteilhaft dadurch erhalten wer  den kann, dass man     erfindungsgemäss        5-Oxy-          benz(ed)indolin    in das     5-Keto-1,3,4,5-tetra-          hydro-benz    (cd)     indol    umlagert  
EMI0001.0019     
         5-Oxy-benz(cd)indolin        5-Keto-1,3,4,5-tetra-          hydro-benz    (cd)     indol     Die     Umlagerung    kann in einfacher Weise  durch Erhitzen des     Indolinderivates,

      vorzugs  weise in Gegenwart von     Lösungsmitteln    bzw.  Verdünnungsmitteln und Katalysatoren durch  geführt werden. Geeignete Lösungsmittel sind       beispielsweise    Benzol,     Toluol,        Tetralin    und       Dekalin.    Als Katalysatoren sind die als     Was-          serstoffüberträger    wirksamen Stoffe, wie Pla  tin, Palladium, Nickel, Kobalt und     Nickelchro-          mit,    besonders geeignet.    Das als Ausgangsstoff bei dem neuen Ver  fahren verwendete     5-Oxy-benz(cd)indolin    ist  bis jetzt nicht bekannt geworden.

   Es kann  nach dem in der schweizerischen Patentschrift       Nr.282383    beschriebenen Verfahren herge  stellt werden.  



  Das 5 -     Keto        -1,3,4,5-tetrahydro    -Benz     (ed)-          indol    soll für die     Herstellung    von Heilmitteln  verwendet werden.  



  <I>Beispiel 1:</I>  260 Gewichtsteile 5 -     Oxy    - Benz<B>(cd)</B>     indolin     werden in viel     Xylol    mit 200 Teilen     10 /oaigem          Palladiiun-Kohle-Katalysator    während 40 bis  50 Stunden am     Rückfluss    gekocht. Die noch  heisse Lösung wird vom Katalysator     abfil-          triert,    mit normaler Salzsäure mehrmals extra  hiert und mit Wasser gewaschen.

   Aus der       Xylollösung    wird     beim.    Eindampfen     im    Va  kuum ein mit wenig Öl     verunreinigter    kristal  liner Rückstand erhalten, welcher     durch        Chro-          matographieren    an     Aluminiumoxyd    oder  durch     Sublimation    im Hochvakuum gereinigt  werden     kann.    Es werden 110 bis 120 Gewichts  teile     5-Keto-1,3,4,5-tetrahydro-benz(cd)indol     vom     Schmelzpunkt    162 bis 164  erhalten.  



  Aus den salzsauren Lösungen kann leicht  reines Ausgangsmaterial     zurückgewonnen    wer  den, das für einen neuen Ansatz wieder ver  wendet werden kann.  



       Beispiel   <I>2:</I>  2,5 Gewichtsteile     5-Oxy-benz(cd)indolin     werden in 1600     Volumteilen        Tetralin    mit 3  Gewichtsteilen     Pallacliiun-Kohle-Katalysator         in einer Stickstoffatmosphäre     verrührt    und  während 5 Stunden auf 190 bis 195  erhitzt.  Darauf wird wie in Beispiel 1 aufgearbeitet.  Man erhält 1,3 Gewichtsteile     5-Keto-1,3,4,5-          tetrahydro-benz(cd)indol        und    1 Gewichtsteil  unverändertes Ausgangsmaterial.  



  An Stelle von     Palladium-Kohle    kann auch       Raney-Nickel    verwendet werden. Beim Arbei  ten ohne Katalysator geht die Umlagerung be  deutend langsamer vor sich.



  Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (ed) indole. 5-Keto-1,3,4,5-tetrahydro-benz (cd) indole is a valuable intermediate. for the production of lyseric acid or of compounds related to lyseric acid; it has been made by an expensive process; see: C. Uhle, J. Am. Chem. Soc. 71: 761-766 (1949).



  It has now been found that this ketone can be obtained particularly advantageously by converting 5-oxybenz (ed) indoline according to the invention into 5-keto-1,3,4,5-tetrahydro-benz (cd) surrounded by indole
EMI0001.0019
         5-Oxy-benz (cd) indoline 5-Keto-1,3,4,5-tetra-hydro-benz (cd) indole The rearrangement can be carried out in a simple manner by heating the indoline derivative,

      preference, be carried out in the presence of solvents or diluents and catalysts. Suitable solvents are, for example, benzene, toluene, tetralin and decalin. The substances which act as hydrogen carriers, such as platinum, palladium, nickel, cobalt and nickel chromite, are particularly suitable as catalysts. The 5-oxy-benz (cd) indoline used as the starting material in the new process has not yet become known.

   It can be produced according to the method described in Swiss patent specification 282383.



  The 5 - keto -1,3,4,5-tetrahydro -Benz (ed) - indole is said to be used for the production of medicinal products.



  Example 1: 260 parts by weight of 5 - oxy - benz <B> (cd) </B> indoline are refluxed in a large amount of xylene with 200 parts of 10% palladium-carbon catalyst for 40 to 50 hours cooked. The still hot solution is filtered off from the catalyst, extracted several times with normal hydrochloric acid and washed with water.

   The xylene solution becomes the. Evaporation in vacuo gives a crystalline residue contaminated with a little oil, which can be purified by chromatography on aluminum oxide or by sublimation in a high vacuum. 110 to 120 parts by weight of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole with a melting point of 162 to 164 are obtained.



  Pure starting material can easily be recovered from the hydrochloric acid solutions, which can then be used again for a new approach.



       Example <I> 2: </I> 2.5 parts by weight of 5-oxy-benz (cd) indoline are stirred in 1600 parts by volume of tetralin with 3 parts by weight of palladium carbon catalyst in a nitrogen atmosphere and heated to 190 to 195 for 5 hours. It is then worked up as in Example 1. 1.3 parts by weight of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole and 1 part by weight of unchanged starting material are obtained.



  Instead of palladium-carbon, Raney nickel can also be used. When working without a catalyst, the rearrangement is significantly slower.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von 5-Keto- 1,3,4,5-tetrahydro-benz(ed)indol, dadurch ge kennzeichnet, dass man 5-OYy-benz(ed)indolin umlagert. UNTERANSPRÜCHE: 1. Verfahren nach Patentanspruch, da durch gekennzeichnet, dass man die Umlage rung durch Erhitzen bewirkt. 2. Verfahren nach Patentanspruch, da durch gekennzeichnet, dass man die Umlage rung durch Erhitzen in Gegenwart eines Ver dünnungsmittels bewirkt. 3. PATENT CLAIM: Process for the production of 5-keto-1,3,4,5-tetrahydro-benz (ed) indole, characterized in that 5-OYy-benz (ed) indoline is rearranged. SUBClaims: 1. Method according to patent claim, characterized in that the relocation is effected by heating. 2. The method according to claim, characterized in that the rearrangement is effected by heating in the presence of a diluent Ver. 3. Verfahren nach Patentanspruch, da durch gekennzeichnet., dass man die Umlage rung durch Erhitzen in Gegenwart eines Ka- talysators bewirkt. Process according to patent claim, characterized in that the rearrangement is brought about by heating in the presence of a catalyst.
CH286498D 1950-04-03 1950-04-03 Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole. CH286498A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH286498T 1950-04-03

Publications (1)

Publication Number Publication Date
CH286498A true CH286498A (en) 1952-10-31

Family

ID=4530162

Family Applications (2)

Application Number Title Priority Date Filing Date
CH286498D CH286498A (en) 1950-04-03 1950-04-03 Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole.
CH291985D CH291985A (en) 1950-04-03 1951-03-02 Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole.

Family Applications After (1)

Application Number Title Priority Date Filing Date
CH291985D CH291985A (en) 1950-04-03 1951-03-02 Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole.

Country Status (4)

Country Link
CH (2) CH286498A (en)
DE (1) DE869342C (en)
FR (1) FR1045654A (en)
GB (1) GB702768A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE542760A (en) * 1954-11-12

Also Published As

Publication number Publication date
FR1045654A (en) 1953-11-30
GB702768A (en) 1954-01-20
DE869342C (en) 1953-03-05
CH291985A (en) 1953-07-15

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