DE408870C - Procedure for the representation of Kodeienon - Google Patents

Procedure for the representation of Kodeienon

Info

Publication number
DE408870C
DE408870C DEM82529D DEM0082529D DE408870C DE 408870 C DE408870 C DE 408870C DE M82529 D DEM82529 D DE M82529D DE M0082529 D DEM0082529 D DE M0082529D DE 408870 C DE408870 C DE 408870C
Authority
DE
Germany
Prior art keywords
representation
kodeienon
procedure
yield
codeinone
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
DEM82529D
Other languages
German (de)
Inventor
Dr Wilhelm Krauss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck KGaA
Original Assignee
E Merck 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 E Merck AG filed Critical E Merck AG
Priority to DEM82529D priority Critical patent/DE408870C/en
Priority to AT105077D priority patent/AT105077B/en
Priority to CH111121D priority patent/CH111121A/en
Application granted granted Critical
Publication of DE408870C publication Critical patent/DE408870C/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D489/00—Heterocyclic compounds containing 4aH-8, 9 c- Iminoethano-phenanthro [4, 5-b, c, d] furan ring systems, e.g. derivatives of [4, 5-epoxy]-morphinan of the formula:
    • C07D489/02—Heterocyclic compounds containing 4aH-8, 9 c- Iminoethano-phenanthro [4, 5-b, c, d] furan ring systems, e.g. derivatives of [4, 5-epoxy]-morphinan of the formula: with oxygen atoms attached in positions 3 and 6, e.g. morphine, morphinone

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Road Signs Or Road Markings (AREA)
  • Electroluminescent Light Sources (AREA)
  • Apparatus For Radiation Diagnosis (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

Verfahren zur Darstellung von Kodeiinon. Während sich das für die Chemie der Tropangruppe wichtige Tropin verhältnismäßig leicht und in guter Ausbeute zum entsprechenden Keton Tropinon oxydieren läßt, ist die Durchführung der analogen Reaktion bei den Alkaloiden der Morphingruppe bisher entweder gar nicht oder nur in sehr schlechten Ausbeuten gelungen. So gibt Kn orr (Ber. 36 [19o3], S.3070) an, daß bei der Oxydation des Kodeins zum Kodeinon die Ausbeute viel zu wünschen übriglasse. M a n n i c h (Archiv der Pharmacie, Bd.258 [192o), S.299) bestätigt diesen Befund und weist darauf hin, daß das Kodeinon eine sehr schwer zu beschaffende Verbindung sei. Wenn M a n n i c h diesen Ausdruck noch als euphemistisch bezeichnet, so muß daraus gefolgert werden, daß die Ausbeute nach der Knorrschen Methode sehr gering gewesen sein muß.Method for the representation of codeinon. While that works out for the Chemistry of the tropane group, important tropine, is relatively easy and in good yield oxidizes tropinone to the corresponding ketone, the analogous procedure is carried out Reaction with the alkaloids of the morphine group either not at all or only at all succeeded in very poor yields. Kn orr (Ber. 36 [19o3], p. 3070) states that that in the oxidation of codeine to codeinone the yield leaves much to be desired. M a n n i c h (Archiv der Pharmacie, Vol. 258 [192o), p. 299) confirms this finding and points out that the codeinone is a very difficult compound to obtain may be. If M a n n i c h still calls this expression euphemistic, then it must from this it can be concluded that the yield by the Knorrschen method is very low must have been.

Es wurde nun gefunden, daß die Darstellung des Kodeinons in verhältnismäßig guten Ausbeuten gelingt, wenn man Kodein mit Chromsäure oder Bichromaten in Gegenwart schwacher Säuren oxydiert.It has now been found that the representation of the codeinone in proportion good yields are achieved if codeine is used with chromic acid or bichromates in the presence weak acids oxidized.

'K n o r r hat zwar die Vermutung ausgesprochen (vgl. Ber. 36 [19o3], S. 3070), daß der glatte Verlauf der Reaktion an der Empfindlichkeit des Kodeinons gegenüber Säuren scheitert, eine Bestätigung dieser Vermutung ist aber nirgends in der Literatur zu finden, so daß anzunehmen war, daß die geringe Ausbeute auf andere Einflüsse zurückzuführen sei. Daß die geringe Änderung der Arbeitsbedingungen eine bedeutende Erhöhung der Ausbeute zur Folge hat, ist daher überraschend.'K no r has indeed expressed the assumption (cf. Ber. 36 [19o3], P. 3070) that the smooth course of the reaction is due to the sensitivity of the codeinone against acids fails, but this assumption is nowhere to be confirmed to be found in the literature, so that it was to be assumed that the low yield on other influences. That the slight change in working conditions results in a significant increase in the yield is therefore surprising.

Beispiel. 2o Teile Kodein werden in 8o Teilen Wasser unter Zusatz von 25 Teilen Eisessig gelöst und mit einer Lösung von to Teilen Chromsäure in 2o Teilen Wasser versetzt. Es bildet sich ein öliger Niederschlag. Dann wird auf dem Wasserbad unter Rühren bis auf 5o° erwärmt, wobei klare Lösung eintritt. Beim nun folgenden allmählichenAbkühlen scheiden sich beim Anreiben braune Kristallmassen eines Chromates ab, die nach einem 1/2stündigen Stehen in Eis abfiltriert werden. Dann wird von der Mutterlauge abdekantiert, der Rückstand in einen Scheidetrichter gebracht, mit Ammoniak versetzt und ausgeäthert. Die Mutterlauge wird ebenfalls ainmoniakalisch gemacht und getrennt ausgeäthert. Die beiden Ätherauszüge werden eingedampft, wobei sich weiße Kristallmassen von Kodenon abscheiden, die aus Alkohol umkristallisiert werden.Example. 20 parts of codeine are added to 80 parts of water of 25 parts of glacial acetic acid and dissolved with a solution of to parts of chromic acid in 2o Parts of water are added. An oily precipitate forms. Then on the The water bath is heated to 50 ° with stirring, with a clear solution entering. At the now subsequent gradual cooling, brown crystal masses separate on grinding of a chromate, which are filtered off after standing in ice for 1/2 hour. The mother liquor is then decanted off and the residue is transferred to a separating funnel brought, mixed with ammonia and etherified. The mother liquor is also made ainmoniacal and etherified separately. The two ether extracts become evaporated, whereby white crystal masses of Kodenon separate out, which from alcohol be recrystallized.

Die Ausbeute beträgt 40 Prozent der Theorie an reinem Produkt.The yield is 40 percent of theory of pure product.

Claims (1)

PATrNT-ANSPRUCII; Verfahren zur Darstellung von Kodeinon, dadurch gekennzeichnet, daß man Kodein mit Chromsäure oder Bichromaten in Gegenwart schwacher Säuren oxydiert.PATrNT-ANSPRUCII; Method for the preparation of codeinone, thereby characterized in that one codeine with chromic acid or bichromates in the presence of weak Acids oxidized.
DEM82529D 1923-09-11 1923-09-11 Procedure for the representation of Kodeienon Expired DE408870C (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DEM82529D DE408870C (en) 1923-09-11 1923-09-11 Procedure for the representation of Kodeienon
AT105077D AT105077B (en) 1923-09-11 1924-07-10 Method for the preparation of codeinone.
CH111121D CH111121A (en) 1923-09-11 1924-07-18 Method for the preparation of codeinone.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEM82529D DE408870C (en) 1923-09-11 1923-09-11 Procedure for the representation of Kodeienon

Publications (1)

Publication Number Publication Date
DE408870C true DE408870C (en) 1925-01-24

Family

ID=7319345

Family Applications (1)

Application Number Title Priority Date Filing Date
DEM82529D Expired DE408870C (en) 1923-09-11 1923-09-11 Procedure for the representation of Kodeienon

Country Status (3)

Country Link
AT (1) AT105077B (en)
CH (1) CH111121A (en)
DE (1) DE408870C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2562072A1 (en) * 1984-03-27 1985-10-04 Mallinckrodt Inc PROCESS FOR PREPARING NOROXYMORPHONE FROM MORPHINE, AND INTERMEDIATE COMPOUNDS USED THEREIN
EP0943617A1 (en) * 1998-03-17 1999-09-22 Johnson Matthey Public Limited Company Process for the preparation of opiates

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2562072A1 (en) * 1984-03-27 1985-10-04 Mallinckrodt Inc PROCESS FOR PREPARING NOROXYMORPHONE FROM MORPHINE, AND INTERMEDIATE COMPOUNDS USED THEREIN
EP0158476A1 (en) * 1984-03-27 1985-10-16 Mallinckrodt, Inc. (a Delaware corporation) Preparation of noroxymorphone from morphine
EP0943617A1 (en) * 1998-03-17 1999-09-22 Johnson Matthey Public Limited Company Process for the preparation of opiates
US6235906B1 (en) 1998-03-17 2001-05-22 Johnson Matthey Public Limited Company Preparation of opiates

Also Published As

Publication number Publication date
CH111121A (en) 1925-08-01
AT105077B (en) 1926-12-27

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