monkpea
(Hive Bee) 07-25-04 05:30 No 521474 |
Dihydrocodeine -> Dihydrocodeinone oxidation | |||||||
Does anyone have a definitive answer as to wether gamma-MnO2 or dichromate oxidizes dihydrocodeine to dihydrocodeinone? If it works for codeine whats stopping it working on dihydrocodeine? The TFSE is lacking a straight answer! Is codeineone active in it's own right? What's the dose!? Many thanks, Pea |
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BieneMaya (Hive Bee) 07-26-04 22:36 No 521845 |
If it works for codeine whats stopping it... | |||||||
If it works for codeine whats stopping it working on dihydrocodeine? You can`t oxidize codeine to Hydrocodone aka dihydrocodeinone. First you have to hydrogenate it to DHC. But I guess your question is related to that oxycodone synth. But codeine is first oxidated there to 14- Hydroxycodeinone via dichromates or MnO2. So pos. 14 is oxidated- not pos. 6 what you want. Take a better look at opiats molecules. |
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longimanus (Newbee) 07-27-04 19:40 No 522020 |
alcohols and ketones | |||||||
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BieneMaya (Hive Bee) 07-27-04 23:27 No 522061 |
All my apologies | |||||||
Oh I apologize for my misinformation. You´re very right in that subject and thanks for this pretty ilustration. You know it has been a long time..... Now I understand the threadstarter´s intention. But by the way I know for sure that it is impossible to oxidize pos.14 at the DHC molecule to have later oxycodone. There´s some serious threads around here discribing why it´s impossible. In my memorries it has something to do with that double bond in the lower ring. |
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monkpea (Hive Bee) 07-29-04 17:15 No 522476 |
Just to remove any confusion: ... | |||||||
Just to remove any confusion, this is what I'm talking about: And this is the rxn I am looking at: gamma-MnO2 Oxidation of Codeine to Codeinone ../rhodium /oxycodo In many places dihydrocodeine can be had OTC... |
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BieneMaya (Hive Bee) 07-30-04 12:05 No 522686 |
old german patent DHC --> Hydrocodone (Rated as: excellent) |
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Patent describing conversation of dihydrocodeine to dihydrocodeinone with about 30 % yield Swim has searched a little bit and found out that it should be possible to go the same route via dichromate like described in the old german patents DE411530 (1) or DE 408870 (2)except with Dihydrocodeine not Codeine to oxidize the pos. 6. The patent DE415097 (3) that is dealing with the thematic is from the same inventor Dr. Wilhelm Krauss as the translated document at Rhodium`s site. ../rhodium /oxycodo (middle part by Lone Ranger) that is based on Patent DE411530 (1). Here´s my own translation of patent DE415097(3) (only the very first part): With the method of Patent 408870 it is possible to oxidize codeine with chromic acid or dichromates in a weak acid solution to produce codeinone. It was found now that it is also possible to oxidize dihydrocodeine with chromic acid or dichromates in a weak acid solution to have later dihydrocodeinone in technical satisfied yields. ref: (1)Patent DE411530 Reichspatent from Sept. 1923 codeine -> oxycodeinone (2)Patent DE408870 Reichspatent from Sept. 1923 codeine->codeinone (3)Patent DE415097 Reichspatent from Okt.1923 dihydrocodeine->dihydrocodeinone all patents are from the same inventor Dr. Wilhelm Krauss - Merck/ Darmstadt |
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merbst (Hive Bee) 08-05-04 02:37 No 523711 |
Re: Is codeineone active in it's own right? | |||||||
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BieneMaya (Hive Bee) 08-11-04 16:14 No 524837 |
these old german patents.... | |||||||
Merbst: Nice to hear from you. In my understanding Oxycodeinone as described in Patent DE411530 is just plain 14- Hydroxycodeinone. This patent doesn`t say anything about hydrogenation. So only pos. 6 and pos. 14 are oxidized. But nothing happen to pos. 7 and pos. 8 . In Patent DE408870 only pos. 6 is oxidized to have codeinone. The first part of the patent tells something about Dr. Knorr who experimented before (1903) with codeine -> codeinone however with terrible yields. If you wish I can translate it for you. I can also translate the first part of the Patent DE411530. Because the procedure is allready translated by Lone Ranger as you know. Working as a team sounds good. You know I´m not a 10 fingers typer. Anyway I can translate whatever you want, if you give me enough time and publish it at the Hive so that every bee has a use from it. With Patent DE286431 the inventor tries to explain that a new Thebain( C19H21NO3) derivat with the formula C18H19NO4 was built with H2O2 in an acid solution. The name of it though isn`t stated anywhere. Only Thebaineoxyd is mentioned. But this is related to a previous research (1906 and 1910)when Theabaine was oxidized with H2O2 without the present of an acid. |
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merbst (Hive Bee) 08-18-04 23:07 No 526111 |
You appear to be right about Oxykodeinon, | |||||||
You appear to be right about Oxykodeinon, http://www.finlex.fi/linkit/sops/1936004 "Dihydro-oxykodeinon (jonka eräs suola on rekisteröity nimellä eukodal)," The only word I recognize is Eukodal, which is an old name for oxycodone, so the fact that dihydro-oxykodeinon is Eukodal, means oxykodeinon is 14-hydroxycodeinone. Actually after further investigation I must thank you for pointing out that this patent is the source of the synth Posted By Lone Ranger in ../rhodium /oxycodo Then again, I still have no clue what he is referring to when he says: Frdl 12,750 Houben 4, 572 or where one would find: "Chemistry of the Opium Alkaloids, L. small and R. Lutz, US Gov printing office, 1932, pg 259" If anybody can clarify what these poorly referenced sources are, I'd love to know. It would also be great to translate the first part of that patent, and to find any patents which reference this one, I've never been able to find any further exploration down this line (probably because I can't read german, and because none of the following collections of patents allow searches farther back than 1997! http://gb.espacenet.com http://www.european-patent-office.org/on http://publikationen.dpma.de/qry_pat_beg http://publikationen.dpma.de/qry_pat_xpt http://www.dpma.de/suche/patentdatenbank Actually I did find 1 interesting thing in my search: This is what else "KRAUSS DR WILHELM" did in his career! (http://l2.espacenet.com/espacenet/searc ) In the little diagram in Patent DE286431 it appears that when they say "thebaineoxyd" they are discussing Thebaine-N-oxide. The thebaine derivative which occurs when it is reacted with H2O2 in acid (Peracetic or Performic acid) is 14-hydroxycodeinone. |
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