Opiate Oxidation

[roddyjojo]

Hi,

I was searching through old posts but couldn't come up with any answers:

KMnO4 is a poor oxidant for codeine directly to anything workable (too strong) from what I have gathered - it oxidizes codeine to codeinone in poor yields.

However I was wondering, would KMnO4 (or dichromates, or even H2O2) oxidize dihydrocodeine to dihydrocodeinone (in poor yields or not)?

Also, Acetyldihydrocodeine is a scheduled substance, but I can't find anything anywhere on the web (including Hive search engine) in regards to effects, dosage, or even confirmed synthesis, and Iw as curious as to what was known about this compound.

Thanks

[Rhodium]

I assume that you are one of those forgetting to check my drug synthesis archive before posting a question?

Oxycodone from Codeine

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/oxycodone.html)

Oxycodone and Oxymorphone from Codeine

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/oxycodone2.html)

Oxymorphone from Oxycodone

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/oxymorphone.html)

[algebra]

i think its a good question. Both codeine and dihydrocodeione are available otc in many places. a simple oxidation from dihydrocodeine would be a really good way to get to something a lot more potent (hydrocodone)- with the advantage that there is no need to do the more complicated hydrogenation. have looked through all of rapoport's work and others and there are no simple oxidations using simple oxidising salts (such as permanganate, dichromate, manganese dioxide)_. from memory i think i have also seen positive stmts that dichromate salts wont oxidise the hydroxy to a keto group when the ring where the hydroxy is, is saturated - someother point on the skeleton is oxidised (not 14- either) - sorry cant remember exactly. Therefore all the literature stuff has been on Oppenhaur variations - using a ketone (cyclohexanone or benzophenone) and alkali metal alkoxide.

Maybe the way to go is catalytic transfer hydrogenation. Oxidise with MnO2 in acetone followed by CTH using a phosphite salt (covered in literature) or ammonium formate etc and palladium on charcoal. - saves having to construct a complicated hydrogenation setup.

[roddyjojo]

Hi,

Yeah Rhodium I did check your website, but only briefly scanned some of those documents you listed. I did read the document that contains the section on oxidation of dihydrocodeine to dihydrocodeinone, which is got me thinking whether a simpler (perhaps cruder, mayber poorer yielding) oxidation could be performed.

Thanks for the info Algebra. If the compound was oxidised with MnO2 then hydrogrenated, what effect would this have? Wouldn't this just oxidise an 'other' (unknown to me) point on the skeleton then hydrogenate the same point?

Also, I'm still wondering about acetyldihydrocodeine - the more I search the more it piques my curiosity, as it seems to be scheduled in a great number of countries yet I can't find any information as to dosage and effect, nor synthesis.

Cheers

[algebra]

sorry Roddyjojo, if it wasnt clear - in the second part of post (oxidize with MnO2 then hydrogrenate) was talking about codeine not dihydrocodeine.