Dihydrocodeine -> Dihydrocodeinone oxidation

[monkpea]

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

[BieneMaya]

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.

[longimanus]

So pos. 14 is oxidated- not pos. 6 what you want.

 Hm, let`s look at the picture below:

 So, when codeine is oxidized to 14-hydroxycodeinone it`s not only the 14. C-atom but also the 6. that is oxidized.

[BieneMaya]

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.

[monkpea]

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

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

In many places dihydrocodeine can be had OTC...

[BieneMaya]

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.

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

(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}

[merbst]

Is codeineone active in it's own right? What's the dose!?

Codeineone is of similar analgesic potency to codeine or DHC (roughly that range), however its spasmotic action is relatively high, similar to thebaine.  thus it would NOT be an ideal recreational compound due to possible convulsive action/toxicity.  14-hydroxycodeinone is more potent, however also has convulsive activity... my source is my memory of a chart somewhere in the book "Opioid analgesics: chemistry and receptors" By: Alan F Casy & Robert T Parfitt (I'll try to figure out where when I get home)

BieneMaya: Oxycodeinone (Oxykodeinon in the patent) is an old german spelling of the compound today known as Oxycodone!  I would be very interested if you would be able to translate the patent DE411530 for me, as it seems like it contains more useful information than the previously known

Patent DE286431

which it references!  If you want to work as a team on this, I can type up the patent (I'm a very fast typist) and get Babelfish to start on the translation.  PM me!

Patent DE408870

looks like a description of the original research of Thebaine -> Oxycodone... I'll have to look at my reference list later to see if I already knew about this one.

[BieneMaya]

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.

[merbst]

You appear to be right about Oxykodeinon,

http://www.finlex.fi/linkit/sops/19360049

includes the line:
"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

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

referenced as: "Merk and Co, DRP 411530" (I had no clue what DRP meant!)

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/online/#databases

http://publikationen.dpma.de/qry_pat_beg.do

http://publikationen.dpma.de/qry_pat_xpt.do

http://www.dpma.de/suche/patentdatenbanken.html

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/search?CY=gb&LG=en&DB=EPD&LS=1&NA=0&TI=&AB=&PN=&AP=&PR=&PD=&PA=&IN=KRAUSS+DR+WILHELM&EC=&IC=&theSubmit=Search)
)

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.