So I'm trying to do an extraction on some OTC codeine pills from Canada and I'm looking for a method that gets rid of the caffeine which CWE does not. I know that dichloromethane or chloroform would be ideal to seperate the codeine from the caffeine, but I dont have access to those at the moment. I do have pure acetone laying around and was wondering if that would work. I had read on another forum that codeine phosphate is insoluble in acetone, which would be great if it's true. I know that caffeine is soluble in acetone and I've seached all over the internet, but I cant find any trustworthy references to verify that codeine phosphate is insoluble in acetone. If anyone has any links to trustworthy references on the solubility of codeine phosphate in acetone please post a link or let me know. Thanks
Opioids Solubilities of codeine phosphate, caffeine, and APAP in Acetone.
- Thread starter Hchemist
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FlyingHighAgain
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A snippet from this thread; http://www.bluelight.org/vb/threads/629972-Purifying-Caffeine-Paracetamol-Codeine-Mixtures Codeine Phosphate:
1 in 4 of water (250mg/ml)
1 in 0.5 of boiling water (2000mg/ml)
1 in 450 of ethanol (2.2mg/ml)
Insoluble in acetone, ether, dichloromethane
1 in 4 of water (250mg/ml)
1 in 0.5 of boiling water (2000mg/ml)
1 in 450 of ethanol (2.2mg/ml)
Insoluble in acetone, ether, dichloromethane
So I crushed 100 pills, dissolved in acetone, then filtered it to remove APAP and caffeine, and did a cwe on the remaining insolubles (there were a lot of insoluble pill fillers other than codeine). I boiled down the remaining filtrate from the the water extraction but now I have 50mL of a brown oily substance, that I cant see getteing crystals of codeine phosphate from by drying or filtering. Any experienced chemists have any ideas what I do to get pure(ish) codeine phosphate crystals drom this brown oily liquid that probably has a lot of semi-water soluble pill fillers. (BTW i never went over 100 degrees C when evaporating the h2o, and the bp for codeine phosphate is 250C, so no final product was burned.) Not looking for synthesis, just a better way to improve the cwe so I can get out the caffeine and have powder to work with because that cwe water tastes like ass hahaha.
So I evaporated the remaining liquid to yield a brown hash-like product, that in theory should contain as much as 800mg of codeine phosphate. I started with 432g of powdered pills (.8g codeine phos.) and am down to 3.8grams of this codeine hash stuff. So that means I have at least 3 grams of useless crap still left in my 3.8g of product, and thats if I actually obtain my theroretical yield which is extremely unlikely.
So anyway now I need a good solvent to do a recrestallization I think. I probably should do an acid/base extraction and re-filter it again because of how dark it is, and b/c of the large amount of product I have relative to the .8g of codeine im trying to isolate. But I've put way too much time into this experiment, and at this point Im starting to not care and lose interest, considering the low return, waste of lots of time, and large amount of effort required to get two tiny doses of codeine. Especially not worth my effort when I have access to better opiates avalable for cheaper than the equipment and chems I bought for this project. I was just looking for somthing to keep my brain busy over the summer, but I've had enough at the moment. So anyone with ideas on cleaning up what is essentially a cwe that has been evaporated and contains nothing but codeine and inactive fillers let me know what solvent whould be best to do so. Also I have MeOH, tolune, acetone, dilute HCL, activated charcoaol and some CaOH if any of that can be of use that would make my life easier b/c I'm not into spending more on this project. Thanks in advance to anyone with advice on cleaning up my product.
Peace, Love, Dope
So anyway now I need a good solvent to do a recrestallization I think. I probably should do an acid/base extraction and re-filter it again because of how dark it is, and b/c of the large amount of product I have relative to the .8g of codeine im trying to isolate. But I've put way too much time into this experiment, and at this point Im starting to not care and lose interest, considering the low return, waste of lots of time, and large amount of effort required to get two tiny doses of codeine. Especially not worth my effort when I have access to better opiates avalable for cheaper than the equipment and chems I bought for this project. I was just looking for somthing to keep my brain busy over the summer, but I've had enough at the moment. So anyone with ideas on cleaning up what is essentially a cwe that has been evaporated and contains nothing but codeine and inactive fillers let me know what solvent whould be best to do so. Also I have MeOH, tolune, acetone, dilute HCL, activated charcoaol and some CaOH if any of that can be of use that would make my life easier b/c I'm not into spending more on this project. Thanks in advance to anyone with advice on cleaning up my product.
Peace, Love, Dope
Bliss26
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When someone was asking about this last year , someone far smarter than I (I think it was sekio) basically said the problem is anything that separates out the caffeine would also render the resultant solution toxic to drink, at least with any chemical a layperson could reasonably obtain.
IIRC activated charcoal was a suggestion given as well, but there was a problem with that also. I think it was that it wasted too much of the solution.
im Canadian and use T1 in a pinch. I do a CWE and just limit myself to extracting under 20 per dose. The caffeine is high but still within safe parameters, and you'd get 160mg codeine. Not terrific but better than nothing, at times.
IIRC activated charcoal was a suggestion given as well, but there was a problem with that also. I think it was that it wasted too much of the solution.
im Canadian and use T1 in a pinch. I do a CWE and just limit myself to extracting under 20 per dose. The caffeine is high but still within safe parameters, and you'd get 160mg codeine. Not terrific but better than nothing, at times.
Well the acetone should have been able to seperate the caffeine from the codeine if that link ito the other thread (in the first comment) has accurate solubility info. But a lot of other stuff in the pills was insoluble in acetone besides the codeine. So at this point its not the caffeine I want to remove its the pill fillers, most of which I think burned because the product turned brown before hitting the bp of codeine phosphate. and to make this worse I dont know excatly what those fillers are because I dont have the original bottle anymore. I dont want to drink the brown putty/hash that I have at this point. I wanna either put it in caps or convert to morphine using well know proceures. However I need to purify the codeine putty I have first. Any ideas on how to extract codeine from the rest of the pil fillers left?
SS373dOH
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^ You can do a quick search online and find out all the active and inactive ingredients that are in your pills.
The caffeine has been a problem for a long time, and iirc there isnt an easy tek for it, it takes solvents and a decent background in chemistry to even come up with something remotely viable.. I don't remember entirely, but I think the issue is that the caffeine and codeine have nearly the same solubilities, so they're difficult to separate. (Feel free to correct me if I'm wrong.)
Don't they make a codeine product that doesn't include the caffeine? Well if not, jus be grateful that you can get codeine OTC where you live! Junkies in the US would kill for this luxury!
- Hopeless Soul
The caffeine has been a problem for a long time, and iirc there isnt an easy tek for it, it takes solvents and a decent background in chemistry to even come up with something remotely viable.. I don't remember entirely, but I think the issue is that the caffeine and codeine have nearly the same solubilities, so they're difficult to separate. (Feel free to correct me if I'm wrong.)
Don't they make a codeine product that doesn't include the caffeine? Well if not, jus be grateful that you can get codeine OTC where you live! Junkies in the US would kill for this luxury!
- Hopeless Soul
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sekio
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Wash the aqueous solution with ethyl acetate or dichloromethane 3x, discard solvents, gently evaporate aqueous layer to get codene phosphate OR add Na2CO3 to pH 10 and then extract some more...
Oh wait you don't have those solvents, so acid/base extractions w/toluene is the only way for you now. OR try a recrystallization from water. Follow the proper procedure as per Vogel.
Acetone washing crushed pills is a naive way to go about it, codiene phosphate is insoluble in DRY acetone, but not so in WET acetone, and acetone will absorb water from the air if kept in an open container....
btw if you think you are going to convert codeine--> morphine OTC, good fucking luck, the "classical" method uses nasty shit like pyridine hcl (hygroscopic salt formed by fusing absolutle pyridine & hydrochloric acid over an open flame) and u get a max 30% yield of black tarry shite, if you dont want to put the effort in to find DCM as a solvent I doubt you'll be making morphine base any time soon
Oh wait you don't have those solvents, so acid/base extractions w/toluene is the only way for you now. OR try a recrystallization from water. Follow the proper procedure as per Vogel.
Acetone washing crushed pills is a naive way to go about it, codiene phosphate is insoluble in DRY acetone, but not so in WET acetone, and acetone will absorb water from the air if kept in an open container....
btw if you think you are going to convert codeine--> morphine OTC, good fucking luck, the "classical" method uses nasty shit like pyridine hcl (hygroscopic salt formed by fusing absolutle pyridine & hydrochloric acid over an open flame) and u get a max 30% yield of black tarry shite, if you dont want to put the effort in to find DCM as a solvent I doubt you'll be making morphine base any time soon
Last edited:
sekio
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I coulda sworn there was, but just for clarity, here's what works nicest just from memory:
1. Dissolve finely crushed/ground T1 pills in boiling water, I find about 300-400mL per every 100 count works good, mix well for 10-15 minutes. You can add a touch of acid to pH 5 if you wish (to ensure codeine stays as a salt)
2. Add celite to T1/water mix, (be generous)***, Buchner filter the whole mess while hot, wash filter cake 2-3x with boiled hot water. At this stage you have removed the pesky pill binders, and you should have about 300-400mL of liquid collected for every 100 pills. Some water will evaporate due to the lowered pressure during filtering, that's ok, that's what washing the cake is for.
It's normal to have the liquid be a little bit cloudy/hazy at this stage, and you should see the beginnings of the APAP crashing out. A coloration can be present too, it's normal to have it anywhere from clear to peach-juice colored to dark purple. I think it's related to the brand of T1s, but it doesn't seem to change yields or purities.
3. Chill the filtered liquid in Pyrex dish in an ice bath or in the freezer, w/ good stirring every 5 mins, until you reach ~10C. Observe precipitation of shit loads of APAP
4. Decant/filter again on buchner funnel (use a new filter & clean the funnel 1st) to remove precip. APAP. No celite needed this time, filtering the granular APAP is easy compared to the slimy binders
5. Extract liquid with dichloromethane, chloroform or ethyl acetate (~1/4 the volume, 3x). Discard any intermediate white floc that forms between phases (binders/APAP carry over). Now you can either evaporate the solvent reactions (and pref. recover it) to yield high-purity caffeine, or just discard it.
You can't drink the aqueous phase directly at this stage because it will contain residual solvent, but now your solution should contain pretty much only codeine phosphate, water, and a little bit of solvent, so taking it from there isn't hard.
(to get crude phosphate salt)
6. Concentrate aqueous phase by boiling/gentle evaporation until you have a small volume (not much more than 1-2mL per gram codeine). Liquid will probably be pretty dark but it should contain a goodly amount of codeine
7. (optional) Put that liquid in the freezer and collect crystals that precipitate. If you don't get a ppt from water alone then try adding ice cold dry acetone to force ppt.
(or to get freebase)
6. Add base (sodium carbonate works fine, be careful of foaming as it reacts) to aqueous phase to bring pH to ~10 and stir 10-15 min
7. Extract with ether, dichloromethane, chloroform, toluene, etc to yield solution of codeine free base. Be careful of emulsions with dichloromethane or chloroform & salt-saturated water.
8. Dry on MgSO4 and evaporate solvent
The major spot for losses is that first filtration, if you are impatient, don't use enough celite, or are otherwise not careful to ensure you draw as much of the liquid through as feasible as well as washing the cake multiple times, you'll take a hit, usually 25% but can be up to 50% if you're really rushing. Take your time, use more ceilte than you think you need, use the biggest buchner funnel you have, and use a trap on the water vacuum line (you do have a water aspirator line and not a hand vacuum pump, don't you????)
If done correctly and carefully this yields codeine of >80% purity, major impurity being caffeine, and you can recover up to theoretical yields in a few hours at most. Remember that every 8mg codeine phosphate pill has only 6mg codeine freebase in it though.
Disclaimer: Don't do this at scale, it's manufacturing of controlled substances, etc. Don't think you can substitute, either. Use the named solvents only.
*** Celite, or diatomaceous earth, is basically a cheap, fine, chemically inert sand made from dead marine organisms that acts as a "filter aid" by helping give the pill goop a surface to bind to and congeal rather than clogging the filter pores. DOn't think you can skimp on this.
1. Dissolve finely crushed/ground T1 pills in boiling water, I find about 300-400mL per every 100 count works good, mix well for 10-15 minutes. You can add a touch of acid to pH 5 if you wish (to ensure codeine stays as a salt)
2. Add celite to T1/water mix, (be generous)***, Buchner filter the whole mess while hot, wash filter cake 2-3x with boiled hot water. At this stage you have removed the pesky pill binders, and you should have about 300-400mL of liquid collected for every 100 pills. Some water will evaporate due to the lowered pressure during filtering, that's ok, that's what washing the cake is for.
It's normal to have the liquid be a little bit cloudy/hazy at this stage, and you should see the beginnings of the APAP crashing out. A coloration can be present too, it's normal to have it anywhere from clear to peach-juice colored to dark purple. I think it's related to the brand of T1s, but it doesn't seem to change yields or purities.
3. Chill the filtered liquid in Pyrex dish in an ice bath or in the freezer, w/ good stirring every 5 mins, until you reach ~10C. Observe precipitation of shit loads of APAP
4. Decant/filter again on buchner funnel (use a new filter & clean the funnel 1st) to remove precip. APAP. No celite needed this time, filtering the granular APAP is easy compared to the slimy binders
5. Extract liquid with dichloromethane, chloroform or ethyl acetate (~1/4 the volume, 3x). Discard any intermediate white floc that forms between phases (binders/APAP carry over). Now you can either evaporate the solvent reactions (and pref. recover it) to yield high-purity caffeine, or just discard it.
You can't drink the aqueous phase directly at this stage because it will contain residual solvent, but now your solution should contain pretty much only codeine phosphate, water, and a little bit of solvent, so taking it from there isn't hard.
(to get crude phosphate salt)
6. Concentrate aqueous phase by boiling/gentle evaporation until you have a small volume (not much more than 1-2mL per gram codeine). Liquid will probably be pretty dark but it should contain a goodly amount of codeine
7. (optional) Put that liquid in the freezer and collect crystals that precipitate. If you don't get a ppt from water alone then try adding ice cold dry acetone to force ppt.
(or to get freebase)
6. Add base (sodium carbonate works fine, be careful of foaming as it reacts) to aqueous phase to bring pH to ~10 and stir 10-15 min
7. Extract with ether, dichloromethane, chloroform, toluene, etc to yield solution of codeine free base. Be careful of emulsions with dichloromethane or chloroform & salt-saturated water.
8. Dry on MgSO4 and evaporate solvent
The major spot for losses is that first filtration, if you are impatient, don't use enough celite, or are otherwise not careful to ensure you draw as much of the liquid through as feasible as well as washing the cake multiple times, you'll take a hit, usually 25% but can be up to 50% if you're really rushing. Take your time, use more ceilte than you think you need, use the biggest buchner funnel you have, and use a trap on the water vacuum line (you do have a water aspirator line and not a hand vacuum pump, don't you????)
If done correctly and carefully this yields codeine of >80% purity, major impurity being caffeine, and you can recover up to theoretical yields in a few hours at most. Remember that every 8mg codeine phosphate pill has only 6mg codeine freebase in it though.
Disclaimer: Don't do this at scale, it's manufacturing of controlled substances, etc. Don't think you can substitute, either. Use the named solvents only.
*** Celite, or diatomaceous earth, is basically a cheap, fine, chemically inert sand made from dead marine organisms that acts as a "filter aid" by helping give the pill goop a surface to bind to and congeal rather than clogging the filter pores. DOn't think you can skimp on this.
Tryptamite
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Excellent write up sekio we do seem to be seeing a lot of these threads Recently.
I shall save it with threads of similar importance for my self after my failed 500mg extract of 30mg/500mg using NaOH and naphtha (possibly reclaimable) NaOH and.codeine forms a brown crud.
I figured if they could do it like so in Russian krok houses with NaOH and petrol I should manage with NaOH and naphtha.... Wrong!!!
Anyway chloroform via haloform rxn and will purchase dcm and probably ethyl acetate but was not aware this was the fella for opiates along with the chloromethanes??
I shall save it with threads of similar importance for my self after my failed 500mg extract of 30mg/500mg using NaOH and naphtha (possibly reclaimable) NaOH and.codeine forms a brown crud.
I figured if they could do it like so in Russian krok houses with NaOH and petrol I should manage with NaOH and naphtha.... Wrong!!!
Anyway chloroform via haloform rxn and will purchase dcm and probably ethyl acetate but was not aware this was the fella for opiates along with the chloromethanes??