14-Hydroxycodeinone -> Oxycodone via Sodium hydrosulfite:
------------- Found in "Oxy" by Otto Snow pg 36: ----------------
By Martin Freund (1924)
Patent US1479293
Patent DE296916
10 grams oxycodeinon (14-hydroxycodeinone) are heated with a solution of 20 grams sodium hydrosulfite (Na2S2O4) in 60 ml water. After a short time complete solution takes place. Upon supersaturating with soda or ammonia 6 grams oxycodone are separated in crystalline form.
Dihydrooxycodeinon (Oxycodone)... crystallizes from alcohol in long jagged columns melting at 222C and yields well crystallized salts. Its hydrochloride C18H20NO4*HCL crystallizes from water or diluted alcohol in columns melting at 268C to 270C. Its free base is precipitated from solutions of the salt by ammonia, soda or alkalies; it is insoluble in excess of alkalies.
References
Freund, Walter (1924) Product of Reduction of Oxycodeinon and Process of Preparing the Same; Merck Index 13th edition (1996) Oxycodone; Dihydrothebenine from thebenine and sodium hydrosulfite, see Speyer and Rosenfeld, Ber (1925) 58, 1120.
Note: Other sulfites might also work [sic?]. See page 47.
------------- Found in "Oxy" by Otto Snow pg 47: ----------------
Etorphine
Process of purifying Oripavines
by Willian R. Hydro,
assignor to the United States of America
as represented by the Secretary of the Army
Patent US3763167
- snip -
The procedure in (a) [sodium metabisulfite] was repeated with the substitution of sodium bisulfite, sodium hydrosulfite, sodium sulfite, or sodium thiosulfite ...
- snip -
------------- My commentary -------------------------------------
Why this is important:
After extensively UTFSE on rhodium.ws and the-hive.ws and google.com for: (hydroxycodeinone AND hydrosulfite) OR (hydroxycodeinone AND dithionite), this reference was never turned up.
Sodium hydrosulfite (aka Sodium Dithionite) can be found OTC at many major supermarkets, and european bees may be able to find it in relation to reducing indigo.
Catalytic hydrogenation is no longer necessary; one does not need to obtain Pd/C or a hydrogen supply.
The patent provides information not included in this short summary, and references a "patent application of Serial Number 485130 filed July 15, 1921, from which this is a divisional application.", indicating that there is more, but I do not know how to find the parent patent.
Theoretically oxy could be created using only things found at a supermarket and a lot of patience. (poppy seeds + 6 months + thebaine extraction + hydrogen peroxide purification + vinegar purification + hydrosulfite + ammonia)
My thoughts about this book:
When I first received this book, I was disappointed, as I bought this book to learn more about the pharmacology of Oxycodone, yet the Oxycodone section is pages 31-42, and only the first 2 of those are pharmacology! Most of the book deals with various species and relatives of papaver which produce alkaloids resembling morphine. However upon closer inspection the references within the chemical section are NOT the same ones available on Rhodium's fine site. It has this one, plus roughly 2 unique routes from thebaine to 14-hydroxycodeinone, plus interesting material regarding the synthesis of Etorphine and the extraction of thebaine. I will be typing out anything else I find that is relevant soon.
I fail to see how Otto Snow believes the Etorphine patent to indicate that other sulfites might also work, but then again I'm not a chemist.
Note: the Na hydrosulfite found in the laundry aisle also contains sodium carbonate anhydrous. I assume this is to reduce the risk of fire due to spontaneous combustion upon contact with moisture in the atmosphere.
My questions from this are:
Out of curiosity, what is the activity of 14-hydroxycodeinone? The
MSDS
(
http://bulkpharm.mallinckrodt.com/_attachments/msds/OXONN.htm) calls it a Narcotic with human lethal dose of 120-250mg.
Is Oxycodone base orally active?
How do I find a patent based on the serial number of its patent application?
I've read that buprenorphine is produced from 14-hydroxycodeinone, does anybody know how?
Enjoy!