alternative to CWE for Codeine OTC purification
Tylenol #1 and ACC/222's and Acetaminophen with caffeine and codeine are always a popular topic online in the forums. Everyone wants to do the CWE and obtain a "pure" codeine product. The headline news is that a pure codeine product from any of those products without the aid of a high speed rotary evaporator or thin film/wiped film evaporator and some higher end solvents is simply not going to happen. Hydrocodone products are a little better, as are dihydrocodeine and oxycodone but codeine itself just doesn't have the stability to make it through such a volumus evaporation with heat in the presence of oxygen and light. Heat and light degrade codeine quite rapidly to a number of products which is why a rotary evaporator at high vaccuum in the dark or a wiped film is ideal to reduce the volume of a CWE prior to making basic and extracting with chloroform or toluene (two best), or benzene or ether or dcm/tce (ok). If the rotary is stopped about half way and again at about 3/4 of the way through evaporating and chilled/filtered then away goes the caffeine and tylenol or aspirin. (ACC is by far FAR the better pill, its very easily filtered from the granular aspirin).
The problem is that how many of us have a functional roto or wiped film evap in our kitchens?
SWIM and SEWIM decided the other day to once and for all put this CWE thing to bed and what they found was a method of producing close to pure codeine sulfate or base hydrate with a small fraction of pill matter contaminant that could be removed by another xtallization. For a single bottle of 200 8mg codeine phosphate 15mg caffeine and 3**mg aspirin or tylenol the following procedure was agreed upon as for them, the most logical way to proceed in the future with this extraction:
-pills ground in grinder to powder then put in mortar and ground to air float with pestle
-pill matter wetted with bottled water to the consistancy of dilute pancake batter
-solid NaOH beads added and ground in until a PH of over 11-12 was accomplished and steady holding, mixture had an ice cube plopped in and was permitted about twenty minutes to cool down
-toluene, about half by volume of pill matter/water was added and ground with the mix currently occupying the mortar, grinding continued for five minutes then transferred to bottle with lid and shaken strongly for thirty seconds then another half volume of toluene was added to the bottle to assist in the separation.
-toluene was separated and put in a bottle with CaCl2 to dry and put in freezer, extraction with toluene was again repeated with the same volumes, remember codeine base is soluble in water at 1gram per 200ml, you'll have at least that much water so you really have to extract it thoroughly to get all your base out, of course the other materials dissolved help to push it out.
-combine toluene fractions and continue drying/cooling for an hour
-choose a dry acid, organic acids are nice like ascorbic, citric, fumaric, glacial acetic anhydrous, benzoic, cinnamic, hydrocinnamic, tartaric. anhydrous mineral acids are good if totally anhydrous but should be made into a reagent, personally I hate pumping from a generator, the suck back can happen so fast you won't know what hit you. Pump your HCl or HBr into cold acetone, alcohols are not soluble in toluene in small amounts. When you pour it into the cold dry toluene containing the base codeine it ppts beautiful pure xtalline ppt powder of codeine.acid salt.
If any water whatsoever gets in that toluene it will cause precipitation of toluene soluble pill matter like waxes etc.. which will bind the first ppt'd codeine it can find and you won't find it again until you use your codeine in a future reaction, if you are consuming the codeine.acid this is of little or no concern. Likely the addition of a solvent capable of blending water into toluene like acetone or IPA may counter this effect, swim has used that technique before but as more an engineer than theoretical chemist swim can't put a mechanism or theory to why that may work, input or opinions on why that works would be appreciated. Swims thoughts are that the polarity of the water or its lipophobicity is hidden when solvated in toluene by way of acetone/alcohol.
It has been determined that this works on:
tylenol #1, acetaminophen w codeine phosphate
ACC, 222's
hydrocodone bitartrate preparations (Norco, lortab, vicoden, dicodid)
dihydrocodeine preparations
some dextromethorphan preparations
.
this process works somewhat but is slightly different than what would be done on Contin tablets, that is in another thread but is practically identical. The only difference is an acid base partition after solvent extraction to an aqueous solution, washed with solvent then based and back into a clean solvent for drying/ppting. The necessity there comes from all the solvent soluble waxes and crap in the contin tabs.
What is exciting here gentlemen is that the above process........so far has shown itself valuble in the extraction of pseudoephedrine from preparations containing tylenol, heheheheehe..mwwwwaaahahahahaaha. Please refrain from getting hyperexcited and spending you roll on daytime PE, let swim and sopwam figure out exactly the solvent system etc.. required first. Initial trial on two three gram boxes one utilizing toluene, the other dietether both provided PE, the hcl by aqueous extract of toluene followed by evap and base from ether via evap in amounts within 10% of expected after an acid base partition purification.
I digress. Back to CWE codeine, Summary. Here is a process for the purification of codeine from otc codeine pharmaceutical preparations. It requires minimal chemistry technical knowledge and experience and produces not an aqueous solution of codeine salt but rather a dry codeine salt of reasonable purity, further purification by recrystallization would yield a pure product. The benefits to this method over CWE is many fold, no contamination from other APIs, accurate dosing, dosing/delivery options (insufflation, rimming [cramming, rectal routering, up the hershey highway] of course this requires a delivery instrument known as the stool tool, a no.0 gel cap and a latex glove).
Finally this is a way of processing large amounts of codeine at a time so one needs not extract on a per dose basis. So the next time your best female friend whilst snapping her gum and twirling her hair with her middle finger looking for splitenz says " hey, do you have more of that koneduneen stuff 'er that?" you can puff out the chest and do the nose shrug/snuff and pull out your nice neat and tidy sealed container of gleaming white powder that cost you a mere grand and half per half ball, hehehehe, but thats only because of your far reaching contacts within organized crime...hehehehe. She'll be impressed, thats when you spring upon her "you know, I REALLY only save this for my BEST and CLOSEST female friends, you know? the ones I really feel like I've bonded with....'er that....hmmhmmhmmhmmhehehehehe.
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