robojunkie
08-19-2009, 12:23 PM
So a nice easy (after some work and losses) of removing quite pure oxycodone from the gacky ER oxy time release pills (OC or generics) was recently worked out.
This involves the use of the oxy-only ER's, and the subsequent powdering of them (if you'd call it that, its not really a powder) and the careful exclusion of any moisture, ie water (I'd go into why, but if you've ever tried to bang 'em you've seen the whole "PEG-ylated/hydroxy-alkyl-ether-cellose/clear gel" that can barely be drawn and certainly can't survive simple acid base ext.
However, as a 14-OH 3-MeO ether compound, the salt of OC-HCl, is soluble in ethanol/methanol/IPA (I recommend ethanol, absolute), and one can grind the pills and soak with stirring overnight the slurry in ethanol (it has to be dry no vodka, 95% or everclear level or higher is needed). The OC salt, typically in the water phase in an A/B extraction, goes into the alcohol, but nearly all the polymers and modified celloses and gums (these are the ER producers and kitchen chemist's enemy in purifications, they are also used in Sudafed which isn't easily purified the old way) remain insoluble without water. A/B won't work because these polymers are designed like wicked long "ropes" that entangle the desired molecule in the water solution even when basified and the whole thing becomes one big surfactant-induced emulsion.
However the ethanolic solution can be filtered and rinsed over celite and evap'd under reduced pressure to yield high purity and high return OC. This can then be refluxed in conc. HBr (if not present made from Metal-Br salt and H2SO4 with the HBr gas going into water until saturated). for about 30 minutes and then cooled. This can be neutralized and the now present oxymorphone salt (about 50% yield, well worth it, kills dilaudid) and extracted with a good amount of chloroform after careful neutralization with ammonia to about pH 9 or so. The CHCl3 is evaporated and the oxymorphone HCl can be made using an ethanolic HCl soution with some ether and precip'd with ether. Very powerful and nice hit. IMO better than dilaudid, for which this same general procedure will work, as in turning purified hydrocodone into hydromorphone.
For future dreams imagine purified buprenorphine reacted with either Br-CN or ethyl chloroformate (this will make an amide that is plus charged out of the cyclopropyl methyl attached N) and the Br will attack the carbon (usually the methyl, but no methyl here, this is how agonists from nature or modified are turned into antagonists in pharm labs, remove the N-methyl, put on N-allyl/cyclopropyl/butylmethyl group via allyl or whatever bromide in acetone). With bupe I would bet (no literature I can find on this reaction type being used on non-N-methyl tert. amines) one would get no attack at the piperidine alpha carbon (the one that sticks out of the page in typical drawings) and attack at both the methyl of the cylcopropyl methyl as well as the benzylic methyl, probably more at the former which is what we want) yielding the carbamate of the bupe version of demethylated etorphine. Then simple LiAlH4 reduction would yield the N-methyl pure agonist and whatever percent of the likely either inactive or mixed partial agonist/antagonist deriviate that could be chromatographed out. Then one would essentially have the dihydro t-butyl (instead of n-propyl) version of etorphine. I so wish I could try this one just to see what the chemoselectivity (which bond gets cleaved in highest ratio) would be (and of course to use it, haha).
Oh yeah, with Br-CN its called the "von Braun reaction".
This involves the use of the oxy-only ER's, and the subsequent powdering of them (if you'd call it that, its not really a powder) and the careful exclusion of any moisture, ie water (I'd go into why, but if you've ever tried to bang 'em you've seen the whole "PEG-ylated/hydroxy-alkyl-ether-cellose/clear gel" that can barely be drawn and certainly can't survive simple acid base ext.
However, as a 14-OH 3-MeO ether compound, the salt of OC-HCl, is soluble in ethanol/methanol/IPA (I recommend ethanol, absolute), and one can grind the pills and soak with stirring overnight the slurry in ethanol (it has to be dry no vodka, 95% or everclear level or higher is needed). The OC salt, typically in the water phase in an A/B extraction, goes into the alcohol, but nearly all the polymers and modified celloses and gums (these are the ER producers and kitchen chemist's enemy in purifications, they are also used in Sudafed which isn't easily purified the old way) remain insoluble without water. A/B won't work because these polymers are designed like wicked long "ropes" that entangle the desired molecule in the water solution even when basified and the whole thing becomes one big surfactant-induced emulsion.
However the ethanolic solution can be filtered and rinsed over celite and evap'd under reduced pressure to yield high purity and high return OC. This can then be refluxed in conc. HBr (if not present made from Metal-Br salt and H2SO4 with the HBr gas going into water until saturated). for about 30 minutes and then cooled. This can be neutralized and the now present oxymorphone salt (about 50% yield, well worth it, kills dilaudid) and extracted with a good amount of chloroform after careful neutralization with ammonia to about pH 9 or so. The CHCl3 is evaporated and the oxymorphone HCl can be made using an ethanolic HCl soution with some ether and precip'd with ether. Very powerful and nice hit. IMO better than dilaudid, for which this same general procedure will work, as in turning purified hydrocodone into hydromorphone.
For future dreams imagine purified buprenorphine reacted with either Br-CN or ethyl chloroformate (this will make an amide that is plus charged out of the cyclopropyl methyl attached N) and the Br will attack the carbon (usually the methyl, but no methyl here, this is how agonists from nature or modified are turned into antagonists in pharm labs, remove the N-methyl, put on N-allyl/cyclopropyl/butylmethyl group via allyl or whatever bromide in acetone). With bupe I would bet (no literature I can find on this reaction type being used on non-N-methyl tert. amines) one would get no attack at the piperidine alpha carbon (the one that sticks out of the page in typical drawings) and attack at both the methyl of the cylcopropyl methyl as well as the benzylic methyl, probably more at the former which is what we want) yielding the carbamate of the bupe version of demethylated etorphine. Then simple LiAlH4 reduction would yield the N-methyl pure agonist and whatever percent of the likely either inactive or mixed partial agonist/antagonist deriviate that could be chromatographed out. Then one would essentially have the dihydro t-butyl (instead of n-propyl) version of etorphine. I so wish I could try this one just to see what the chemoselectivity (which bond gets cleaved in highest ratio) would be (and of course to use it, haha).
Oh yeah, with Br-CN its called the "von Braun reaction".