Posted by Lone Ranger  
                                
After looking over Rhodium's site for the 100th time, and sending him
numerous complaints about small details on some of the posted methods, I
would like to publicly acknowlege that his is far and away the best site
of it's kind, and the best maintained.

[Thanks, Mr Ranger! -Rho.]

And so I offer this much requested synthesis: 

HYDROXYCODEINONE: The same product obtained from the 30% hydrogen peroxide
treatment of thebaine in acetic acid can also be obtained directly from codeine.

30 grams of codeine in 80ml water with 25grams acetic acid, is treated cold
with a solution of 20grams sodium dichromate in 25ml water. An oily
precipitate forms which becomes crystal after short warming. The mixture is
heated to 80deg with stirring until all the solid goes into solution; the
temperature rises spontateously to 90deg. After short standing, the base is
precipitated from the cold solution as the dichromate by adding an excess
of chromic acid solution. Crystallize from alcohol with a little chloroform
as plates, decomposes at 275deg. Stable to strong acid or alkali. Soluble
in chloroform, ethyl acetate, ligroin. Sparingly in alcohol, insoluble in
ether or water. 

Simple hydrogenation over Pt, Pd, or Ni would satutate the recovered and
purified compound to the potent dihydro version. Hydrogenation over Pt or
Pd in dilute acetic acid give 93% to 97% yields. This product would be
14-hydroxydihydrocodeinone or Oxycodone, either as the dichromate or
possibly acetyl salt. 

What I like about this procedure is that it is simple and fast and uses
only very available reagents. 

What I don't like about it is that no yields are stated. 

Ref: 
1. Chemistry of the Opium Alkaloids, L. small and R. Lutz,
   US Gov printing office, 1932, pg 259
2. Merk and Co, DRP 411530
3. Frdl 12,750 
4. Houben 4, 572
 
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Q: What is "Simple hydrogenation"?

A: The substrate is dissolved in a protonic solvent, such as CH3COOH, and 
   placed in a reaction vessel with a catalytic amount (small) of Pd or Pt on 
   a suitable substrate (ie 5%Pd/C), and shaken or stirred magnetically. H2 
   uptake is monitored (A graduated cylinder inverted in a water bath). The 
   reaction is complete when H2 uptake ceases. The hydrogen is measured by 
   reading the water level in the inverted cylinder. No heat is needed, as 
   this is a simple ring saturation. Raney nickel is OK, but I do not have 
   (off hand) the yield for this catalyst. It is 97% with Pd, 93% with Pt. 
   Another nice reaction, as nothing happens until the stirrer is turned on. 
   At that time the water level rises (to replace the comsumed H2) at an 
   almost visible rate. 

- Lone Ranger

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