Hydrocodone => Hydromorphone via Demethylation

[chemboy7]

Well, I have been perusing through various Opiate chemistry sites and came acrossed something that interested me greatly... I cant believe I didnt think of if myself.

If Hydrocodone is demethylated it is going to be converted to Hydromorphone (in quite the yeild too, if you know what your doing, we are talking like 95% ideal yeilds). Being that I believe the general public around here wont understand what they are reading anyways I am not going to post the synth... don't want to encourage kitchen chemists either, stick to crank you tweakers. But I will give this refference:

J. Org. Chem. 3, 204 (1938)

Enjoy, I know I will. Hahaha.

[superman]

what demethylating agent is used in this synth?

personally, if i had the required materials i would rather demethylate codeine since it's so easy to procure in large quantities and would produce a procudt that is readily converted into what we all really want.

[moviebuff927]

Well, I have been perusing through various Opiate chemistry sites and came acrossed something that interested me greatly... I cant believe I didnt think of if myself.

If Hydrocodone is demethylated it is going to be converted to Hydromorphone (in quite the yeild too, if you know what your doing, we are talking like 95% ideal yeilds). Being that I believe the general public around here wont understand what they are reading anyways I am not going to post the synth... don't want to encourage kitchen chemists either, stick to crank you tweakers. But I will give this refference:

J. Org. Chem. 3, 204 (1938)

Enjoy, I know I will. Hahaha.

I did a search and could not turn up anything...

[robojunkie]

I did a search and could not turn up anything...

You would probably have to go to your local university library and use the scientific search engines. You may be able to get the first page over the web without the licenses and shit but I'm not so sure about the entire article. JOC is an ACS journal and they usually don't give out the whole thing free. In fact only the RSC does give out entire articles free as a general policy.

I'll have to look it up though, I'm curious as to whether or not they use the common modern methyl aryl ether demethylation that we all know and love, or at least know. Not sure if that was even known back then.

Oh yeah, where you been, mb? Good to see you back around anyhow.

[moviebuff927]

You would probably have to go to your local university library and use the scientific search engines. You may be able to get the first page over the web without the licenses and shit but I'm not so sure about the entire article. JOC is an ACS journal and they usually don't give out the whole thing free. In fact only the RSC does give out entire articles free as a general policy.

I'll have to look it up though, I'm curious as to whether or not they use the common modern methyl aryl ether demethylation that we all know and love, or at least know. Not sure if that was even known back then.

Oh yeah, where you been, mb? Good to see you back around anyhow.

Oh...I feel like a dumbass.

[Synack]

Since I'm a nice guy and I've got access to this article I'll post a little teaser:

Summary
1. Organomagnesium halides react with morphine derivatives of the
pseudocodeine type, ie., those having an unsaturated linkage in the 6,7
position, with scission of the ether ring, and introduction of an organic
group into the nucleus. This reaction can likewise be applied to the enol
esters of the dihydroketones of the morphine group.

2. The preparation of methyl, ethyl, isopropyl, n-amyl, benzyl, and
phenyl derivatives of dihydrothebaynone is described. In the methyl,
ethyl, and phenyl series, pairs of isomeric substituted dihydrothebainones
are formed, in the isopropyl, n-amyl, and benzyl series, no isomers have
been found.

3. By closure of the 4,5-oxide ring, the alkyl, aralkyl, and aryl dihydrothebainones
can be transformed to the corresponding dihydroco
deinone derivatives, and demethylation of these leads to organic substituted
dihydromorphinones.

4. The nuclear methylated dihydrocodeinone isomers can be converted
to the enol acetates, and these derivatives brought into reaction with
methylmagnesium iodide, whereby a second methyl group is introduced.
The same dimethyldihydrothebainone is formed from both isomers. The
significance of this fact for speculations concerning the structure of the
alkyl dihydrothebainones is discussed.

5. The action of isopropyl- or phenylmagnesium bromide on dihydrothebainone
results to some extent in demethylation at the phenolic ether
group, whereby dihydromorphinone methyl enolate is formed. This
compound can also be prepared by demethylation of dihydrothebaine
under alkaline conditions.

6, Pseudocodeine methyl ether reacts with methylmagnesium iodide to
give a phenolic product containing a new methyl group. Analysis shows
that methylpseudocodehe methyl ether must contain an alicyclic unsaturated
linkage but the compound shows the same extraordinary resistance
to hydrogenation exhibited by phenyldihydrothebaine and the methyldihydrothebaines.


Leave me a comment if you've found this useful...

[Ghost666]

Yeah, I think most are quite confused with this, I know I am...lol. Sucks too, as I sit here after refill day with 180ct 10/325 Norco's.

[Paregoric Kid]

isn't there something in the rhodium archive about this?
I totally agree that codeine would be easier than using hydrocodone, but I'll go one further and say if you are serious about this using thebaine as the first precursor would be even better and easier than using codeine.

[CSiiSEQ]

If you have access to JOC, you should have no problems pulling stuff all the way back to 1936.

[Synack]

PM me if you want the full JOC article on this...

edit: Also, I don't have access to the full JOC - can't afford it ATM - no job... I purchased this one article for you opiophile guys at $25.. so play nice..lol

edit2: Maybe it would be kinda cool to have a seperate subdomain (or I'll host the damn thing on my dollar) of synth information and easy ways to aqquire the tools along with simple tutorials and some college level info?

I love you guys... I need a drink :(

[Paregoric Kid]

there is a synth section on the board and if you are serious check out the rhodium archives and the hive archives and look up synthetikal and other related stuff, get to be friends with people that are majoring in chemistry.
edit: actually look at rhodium they have a section on hydromorphone
Hydrocodone/Hydromorphone


Codeinone from Thebaine (http://www.erowid.org/archive/rhodium/chemistry/codeinone.html)
Catalytic rearrangement of Morphine/Codeine to Hydromorphone/Hydrocodone (http://www.erowid.org/archive/rhodium/chemistry/dihydromorphinones.html)
Quantitative Conversion of Codeine to Hydrocodone (http://www.erowid.org/archive/rhodium/chemistry/hydrocodone.html)
14-Hydroxycodeinone from Codeine (PDF) (http://www.erowid.org/archive/rhodium/pdf/hydroxycodeinone-1.pdf)
14-Hydroxycodeinone from Thebaine (PDF) (http://www.erowid.org/archive/rhodium/pdf/hydroxycodeinone-2.pdf)

[Synack]

Score, thanks! -- once my funds pick up a bit I'll pick up an org chem college book from ebay along with the MIT free courseware on it..

[Synack]

N grams morphine dissolved in (N * 10)ml of alcohol and after the addition of (N/10)g of palladium black, the mixture was refluxed for 4 hours. After the catalyst was filtered off and the solution concentrated, dihydromorphinone crystallized. Yield (N-20%) grams.

It really doesn't seem that hard... I can get a gram of palladium black for about $80

[Paregoric Kid]

hey can't you get palladium out of a catalytic converter from a car/truck?

edit: you can also make hydrocodone from codeine using the above method synack mentioned.

[CSiiSEQ]

edit: Also, I don't have access to the full JOC - can't afford it ATM - no job... I purchased this one article for you opiophile guys at $25.. so play nice..lol


Next time, before you go wasting your $, you should post the article you're looking for. Lots of people have access and don't have to pay and may be willing to help you out. I have no problem pulling articles with the exception of a few journals that list my institution in the page margins - that I won't post!

[Synack]

Next time, before you go wasting your $, you should post the article you're looking for. Lots of people have access and don't have to pay and may be willing to help you out. I have no problem pulling articles with the exception of a few journals that list my institution in the page margins - that I won't post!

True, but I figured if no one posted something at this point, no one had it... so I'd figure I'd take one for the team...lol

[CSiiSEQ]

Well next time if you don't get a response check with me. I can access anything and if I can't I can send a student to pull it and scan it if necessary. The prices they charge for those are outrageous and that's after they have made all the researchers pay the even more ridiculous page charges and color figure charges - don't get me going on that topic.

[Synack]

Will do! Thanks for the offer!