Esters of oxycodone

[haribo1]

I came across some interesting information on esters of oxycodone:

-Cinnamic ester = 117x
-Propenyl ester = 6.5x
-Acetyl ester = 2.5

So, that cinnamic ester is of great interest. It should also lower the BP enough to make the stuff smokable. My next question is 'can the 14 position be esterified when leaving the 3 position alon?' I mean, can the same trick be done on hydromorphone? I suspect that 3 acetyl 14 cinnamic hydrocodone would be interesting to say the least.

 

[LuxEtVeritas]

 

[Acyl]

You realize the 3rd position of oxycodone is methylated, right?

With hydrocodone... I seriously doubt youd be able to selectively esterify the 14th position. The phenol is much more nucleophillic and seems to be less hindered.

 

[haribo1]

^That's OXYmorphone. Well, if you reflux morphine in acetic acid, only 1 of the -OH groups is esterified, so I assume a similar scheme is possible here.

 

[fastandbulbous]

Getting very close to euthanasia with the amount of synthesis discussion...

 

[Acyl]

What? Oxycodone has a methyl group on 3.

And what oxygen esterified during the acetic acid reflux? Im willing to bet its the hydroxy (position 3) on the aryl ring.

 

[Ham-milton]

Oxycodone has a methoxy at the 3 position. Oxymorphone has a hydroxy group.

oxycodone: 4, 5-epoxy-14-hydroxy-3- methoxy-17-methylmorphinan-6-one
oxymorphone: 4,5α-epoxy-3,14-dihydroxy-17-methylmorphinan-6-one

I'm not sure exactly sure about this?

 

[Acyl]

You're not sure of the naming? lol looks like wiki got them right.

 

[Ham-milton]

no, what the argument was over.

 

[haribo1]

United States Patent 4751307 discloses how to convert naltrexone to nalmefene (swap the 6=O for a 6=CH2) which is interesting. Seems they do a plain Wittig reaction.

 

[Acyl]

Which hydroxy estered first?

 

[haribo1]

Polonvski reaction to remove an N-methyl (should you need to).