Nullification of Caffeine in Codeine CWE??

[dus_aster]

Greetings-

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Please note that this is **not** a thread on /removing/ the caffeine from co-codamol extractions; rather, it is discussion of the **mitigation** of the caffeine.
___

So: anyone have any experience in the nullification of caffeine in CWEs? I began SSRI therapy six months ago, and, while the 40mg of Citalopram/day has been an immense boon to my mental health, it has noticeably decreased the efficacy of codeine, to the extent that the caffeine completely eradicates all the pleasurable elements of the opiate.
It isn't tolerance, as, on an empty stomach, I get five to ten minutes of solid opiate effects before the caffeine is fully metabolized. At which point, it's minor malaise, twitching, inability to nod, et cetera. Dosages used range from 160/300 - 240/450 codeine to caffeine.
I love caffeine, and have a moderate tolerance to it, but...this sucks.
I've been experimenting with ways to make it less noticeable, and have yet to find anything that will work reliably.
Anyone have any experience with this?


What I've tried so far:

A 2:1 to 4:1 L-Theanine to caffeine ratio (dissolved into the mixture) : caffeine less jittery, codeine only marginally more noticeable (this might be placebo).

Two units of ethanol consumed an hour prior to the CWE : definite improvement, but nothing mind-blowing. Added concerns of interaction between residual APAP and alcohol in the liver.

300mg of 5:1 Valerian root extract powder (dissolved into mixture): improvement upon the metabolization of the Valerian, which, unfortunately, is substantially slower than the ultra-fast codeine or the still speedy caffeine metab. Seemed to help enough to warrant further exploration, but it could have just been individual factors on that particular day.

25-75mg Diphenhydramine (T-30min): perhaps a minor boost in noticeable effects, but I find that DPH reduces the pleasure of the opiate high?



Any thoughts, anyone??? Open to any ideas, but I do *not* have access to benzos, harder opiates (save for Kratom), or Rx muscle relaxants (in the past, I found cyclobenzaprine useful)
I'm going to try the Valerian root at T-45, see if that helps.
Curious about Phenibut, as well, taken an hour and a half prior to ingestion of the CWE, but after a two nasty dependencies and withdrawals with the stuff, am hesitant to order more unless I have anecdotal evidence of it's efficacy.


Anyways--- anyone with experience, or anyone wanting to discuss their experiences with caffeine and CWEs, feel free to share! ^.^

 

[SS373dOH]

One possibility is to use the same method coffee manufacturers use to decaffeinate their coffee. There's multiple methods involving solvents, but it seems the easiest and most organic method is charcoal adsorption. Check out the wiki page, maybe its something you can do. Also I know nicotine decreases its half-life by nearly 50%, but nicotine mimics adrenaline, so it might be counter productive.



- Hopeless Soul

 

[adder]

This might actually work as codeine phosphate shouldn't be adsorbed much at activated carbon. However, that is essentially removal of caffeine, I don't think there is any way to mitigate caffeine's effects, you do need to remove it physically from the solution. Another way is extracting caffeine with an organic solvent while keeping codeine salt in aqueous layer.

 

[belligerent drunk]

Why don't you just want to remove caffeine from the solution as adder has suggested? Co-codamol shouldn't contain caffeine to start with anyway.

 

[Ligaturd]

I typically do 3 rinses with distilled water. Ensuring to keep everything in solution for a good amount of time and utilizing variations in temperature (from hot to cold) and a good amount of shaking to make sure to extract all of the codeine. I have proof that doing one rinse with just cold water is not effective at all and the codeine yield is horrible.

The typical CWE methods posted around the internet aren't very effective. It is definitely worth it to take the time and do it properly.

When you have all 3 rinses and evaporate it down to a powder, you can put it into 10mls of warm water and load it into a 10ml oral synringe with a cotton ball loaded into the front and stick it into the freezer until its cold. After filtering it through the coton ball you are left with most of the codeine and only as much caffeine and acetaminophen as can fit into 10mls of cold water which is not even worth noting.

This does take quite a while but it has absolutely been worth it. Caffeine and large amounts of apap destroy any possible enjoyability one can get from t1's. I don't get anything out of codeine any more but for those who are doing this to stave off dope sickness, it's worth it to do it properly as not doing so will just trade off dope sickness for the sickness of apap overdose and too much caffeine.

 

[aced126]

I typically do 3 rinses with distilled water. Ensuring to keep everything in solution for a good amount of time and utilizing variations in temperature (from hot to cold) and a good amount of shaking to make sure to extract all of the codeine. I have proof that doing one rinse with just cold water is not effective at all and the codeine yield is horrible.

The typical CWE methods posted around the internet aren't very effective. It is definitely worth it to take the time and do it properly.

When you have all 3 rinses and evaporate it down to a powder, you can put it into 10mls of warm water and load it into a 10ml oral synringe with a cotton ball loaded into the front and stick it into the freezer until its cold. After filtering it through the coton ball you are left with most of the codeine and only as much caffeine and acetaminophen as can fit into 10mls of cold water which is not even worth noting.

This does take quite a while but it has absolutely been worth it. Caffeine and large amounts of apap destroy any possible enjoyability one can get from t1's. I don't get anything out of codeine any more but for those who are doing this to stave off dope sickness, it's worth it to do it properly as not doing so will just trade off dope sickness for the sickness of apap overdose and too much caffeine.

Why would the codeine yield be bad after 1 rinse? The more rinses you do the lower the codeine yield. Codeine is extremely soluble in water, and provided the tablets have been crushed fully, all the codeine will be perfectly dissolved in the water.

I find that 1 rinse is probably good enough for removing sufficient amounts of APAP. The aim is not to remove all the APAP; in fact for every 1 mL of water at room temperature, 12.78mg APAP will dissolve. The aim is to lower the APAP to non-toxic amounts (under 3g is probably safe for infrequent use). After the first rinse itself, significant APAP residue is visible, and the solution is close to opaque. Nevertheless, subsequent filtrations take much less time, but also remove much less APAP.

 

[Ligaturd]

Why would the codeine yield be bad after 1 rinse? The more rinses you do the lower the codeine yield. Codeine is extremely soluble in water, and provided the tablets have been crushed fully, all the codeine will be perfectly dissolved in the water.

I find that 1 rinse is probably good enough for removing sufficient amounts of APAP. The aim is not to remove all the APAP; in fact for every 1 mL of water at room temperature, 12.78mg APAP will dissolve. The aim is to lower the APAP to non-toxic amounts (under 3g is probably safe for infrequent use). After the first rinse itself, significant APAP residue is visible, and the solution is close to opaque. Nevertheless, subsequent filtrations take much less time, but also remove much less APAP.

I had an actual overdose in my teens on unextracted tylenol 1's. A year or so later I extracted a whole bottle with one rinse, filtered and with way too much water. In the morning I felt really sick so, fearing overdose I went to the hospital and they found no appreciable amounts of codeine. It was embarassing but I learned from it. The subsequent rinses are to remove more codeine and the final filtration with 10mls volume of water is to ensure that there is as little apap and caffeine as possible in the resultant solution.

This is proof that you need to spend some time allowing codeine to enter into solution. Heating up and cooling down will help it enter into solution and generally for extractions you should do 3 rinses, to ensure you get most of everything out. Each subsequent rinse will have less and less in it but there will be extra codeine. Evaporating all 3 rinses together will ensure that you have the lions share of the actives out.

 

[aced126]

I had an actual overdose in my teens on unextracted tylenol 1's. A year or so later I extracted a whole bottle with one rinse, filtered and with way too much water. In the morning I felt really sick so, fearing overdose I went to the hospital and they found no appreciable amounts of codeine. It was embarassing but I learned from it. The subsequent rinses are to remove more codeine and the final filtration with 10mls volume of water is to ensure that there is as little apap and caffeine as possible in the resultant solution.

This is proof that you need to spend some time allowing codeine to enter into solution. Heating up and cooling down will help it enter into solution and generally for extractions you should do 3 rinses, to ensure you get most of everything out. Each subsequent rinse will have less and less in it but there will be extra codeine. Evaporating all 3 rinses together will ensure that you have the lions share of the actives out.

Fair enough, I guess your incident points out another issue of using too much water. It might be tempting to use jugs of water to increase yield, but in doing so you are just letting grams of APAP dissolve into your solution. Still, however, I think 10mL water compromises yield a bit too much. I think 100mL water cooled down to 0 degrees celsius will mean that there is not more than a gram of APAP dissolved in the solution.

 

[belligerent drunk]

I find that 1 rinse is probably good enough for removing sufficient amounts of APAP. The aim is not to remove all the APAP; in fact for every 1 mL of water at room temperature, 12.78mg APAP will dissolve. The aim is to lower the APAP to non-toxic amounts (under 3g is probably safe for infrequent use). After the first rinse itself, significant APAP residue is visible, and the solution is close to opaque. Nevertheless, subsequent filtrations take much less time, but also remove much less APAP.

I see no point in more than 1 rinse either. Codeine is perfectly soluble in ~100 ml of water (I would say that it's safe to assume that ~100% of it is dissolved in that amount of water). I usually take 1 g of codeine at a time, and I use around 150 ml of water (yeah, yeah, all that APAP, but my liver function and kidney which I test regularly, has been absolutely fine, and I supplement some "liver-repairing" (of obviously questionable efficacy) things in conjunction). I do not believe the same liquid-liquid extraction principle (the more extractions with less liquid - for example 3 extractions with 30 ml of a solvent is more efficient than a single 90 ml extraction) applies. If the pills dissolve, and I see no reason for the codeine not to dissolve in water if appropriate volume is used of around 100 ml, then additional rinses will just increase the APAP amount ingested with insignificant improvement in codeine yield.

Assuming codeine dissolves perfectly in 150 ml, then the CWE I do is about 90% efficient, as I recover about 90% of the water from 100-120 pills.

By the way, I wouldn't be so sure that the suspension which gives the milky appearance to the liquid is only APAP. It may be insoluble binders and other stuff in the pills. And getting rid of the fine particles is not that easy - I tried vacuum filtering with a glass filter (and very fine paper filter on top) with very small pore diameter, and the result was pretty much the same as just using a coffee filter - something I actually did not expect to happen, it means that the particles are very fine. Another reason believing this is that I tried doing the CWE at close to zero degrees, got my slightly milky solution (hard to call it that, just a few fine particles floating around), and then heated it up to ~40 C, and the milky appearance didn't change, which it should have considering APAP's solubility increases with temperature increase. So if it didn't, then it can't be just APAP.

And to those wondering how much the suspension and the solution holds APAP, evaporating ~100 ml of CWE performed with the same technique, only without codeine (using plain paracetamol pills), yielded about or under a gram of white powder.

 

[Skorpio]

What was the mass, brand, and the amount of apap of the pill before the cwe in your test trial? Without those data points, conclusions drawn will be weak.

 

[sekio]

Extracting caffeine from codeine cwes is not difficult, for that matter extracting the codeine freebase from the decaffeinated cwe isn't hard either, i've posted about how to do it before.

There's also a technique that involves freeze precipitating caffeine out of your CWE too, that works as well.

The problem with Canadian T1's is that for any CWE you will automatically have 2x the dose of codeine in caffeine. That's 200mg caffeine for every 100mg codeine, and that's a dose that's pretty much impossible to counteract with stuff like diphenhydramine. You'll still feel tweaky.

Whenever I extarct codeine I always filter twice, once while it's hot to remove the goopy binders, then again after cooling it to ~10C to remove precipitated APAP. Mind you, I'm using a vacuum Buchner filter & plenty of Celite so I'm kind of spoiled there...

the resulting liquid has almost no APAP left in it and only a slight opalescence. I'm using about 200mL water for every 100 pills.

 

[dus_aster]

The reason for the specific exclusion of discussion regarding removal was that, the last time I started a thread (on a less reputable forum) inquiring about total removal, I was told it was impossible...something about experimenters finding that charcoal filters removed the codeine, as well, but I'm not sure how much of that was anecdotal.
If it is indeed possible to remove the caffeine entirely, that would obviously be very much preferable!

And @sekio, yes, that is the problem with the accursed Canadian T1s. One feels obligated to hand it to whoever came up with that: it does indeed make (ab)use more difficult.

Thank you for all the helpful responses!
I'll do some googling, but if anyone has a particular technique for removal of caffeine without restricted chemicals (solvents? Chemistry luddite, but would like to expand my knowledge base) that they've had success with, and would feel so inclined as to PM/link me, I would be grateful.
(No worries if not, I'm sure I'll be able to dig it up.)

Y'all are such a fantastic community- rad.


My two cents regarding the milkiness being indicative of APAP content-
I've found different brands produce varying levels of milkiness when run through identical extraction processes/temperatures... imho purity is better gauged by weighing the leftover gunk (though, ime, the clearer solutions *are* generally purer?)

 

[adder]

something about experimenters finding that charcoal filters removed the codeine, as well, but I'm not sure how much of that was anecdotal.

Charged molecules are generally poorly adsorbed at activated carbon, so codeine salt dissolved in water should not appreciably be adsorbed, however, whether or not you remove codeine along with caffeine is also a matter of the amount of activated carbon used. Similarly, when you dry a solution of an organic compound with e.g. MgSO4, water is strongly adsorbed, however, organic compounds are too to some extent, so when big excess of MgSO4 is added and no water left is present, some product loss is possible. Anyway, I guess the right way to do it can only be found out experimentally, so acid-base extraction may be a better idea. By playing with pH you can make codeine go to either aqueous or organic layer, thus getting rid of caffeine, paracetamol, and aspirin.

 

[aced126]

Charged molecules are generally poorly adsorbed at activated carbon, so codeine salt dissolved in water should not appreciably be adsorbed, however, whether or not you remove codeine along with caffeine is also a matter of the amount of activated carbon used. Similarly, when you dry a solution of an organic compound with e.g. MgSO4, water is strongly adsorbed, however, organic compounds are too to some extent, so when big excess of MgSO4 is added and no water left is present, some product loss is possible. Anyway, I guess the right way to do it can only be found out experimentally, so acid-base extraction may be a better idea. By playing with pH you can make codeine go to either aqueous or organic layer, thus getting rid of caffeine, paracetamol, and aspirin.

At low pH, wouldn't caffeine be protonated and go into aqueous layer as well?

 

[sekio]

Caffeine doesn't protonate very well, the nitrogens are planar amides & it doesn't form a stable salt in water (caffeine citrate decomposes to caffeine+citric acid)

All you need to do is extract a codeine CWE with dichloromethane** a couple times to effect total removal of the caffeine. Make sure the pH is slightly acidic (anywhere from pH 3-6) to ensure you don't pull the codeine out.

The activated carbon method doesn't work very well because if you look at the mass fractions of what you're trying to purify, codeine is literally the lowest concentration compared to everything else, and if I remember right, that means a larger fraction of codeine will be removed than e.g. the caffeine, defeating the purpose entirely.

The "milkiness" (more correctly, opalescence) of a T1 extraction is not dissolved APAP, either. I've filtered CWEs *exceedingly* well and had colored, slightly-cloudy liquid result. I think it has to do with a component of the pill binders getting suspended in the water - like I said, it's not APAP. (proven with GCMS). Some brands will produce a more darkly-colored filtrate than others, and I'm not sure why, either - but the yields seem to be the same across the board.

Actually, a way to tell for sure if you've done your CWE properly, is let your CWE sit for a few minutes in the fridge/freezer. Stir it gently every few minutes. If you see white stuff settling out on the bottom of your vessel - that's APAP coming out of solution.

If your solution is clear but has a slight haze to it and nothing precipitates even when cold, you're fine.

** In a pinch, any solvent that dissolves caffeine and is water-immiscible will do the trick. Try ethyl acetate or chloroform as substitutes. Toluene or diethyl ether could work too. I don't think naptha or other hydrocarbons will work however, caffeine is polar after all.

I did a whole guide on this ages ago, there was a handy chart I prepared with the solubilities of each of the components of a T1 in mg/l in various solvents.

 

[aced126]

Why doesn't the double bonded nitrogen in the imidazole ring get protonated? (Imidazole c. acid pka=7.05)

 

[sekio]

It's a sp2-hybridized i.e. planar nitrogen atom, and part of an aromatic heterocycle. Protonating it would destroy the aromaticity.

 

[aced126]

Pyridine gets protonated though even though it is sp2 hybridised (conjugate acid pKa=5.5, a lot less basic than normal imines)?

 

[sekio]

That may be the case, but with all the extra crap on caffeine it's not very favorable for it to pick up a proton. I'm pretty sure this is a combination of sterics & the caffeine molecule existing as an energetically favored planar molecule. Note that even at "pH 0" there's still ~80% of the caffeine non-protonated.

 

[aced126]

That may be the case, but with all the extra crap on caffeine it's not very favorable for it to pick up a proton. I'm pretty sure this is a combination of sterics & the caffeine molecule existing as an energetically favored planar molecule. Note that even at "pH 0" there's still ~80% of the caffeine non-protonated.

Okay, still not convinced by the explanation, however I found out some more interesting stuff.

-Normal aliphatic amines have pkas at around 11 (Piperidine conjugate acid pka=11.2). Tertiary alkyl amines have greater pkas than primary amines because the neighbouring carbons push electron density towards the nitrogen.

-Imines have slightly lower pkas (~9). Why is this so?

Here's where I'm confused:
-imidazole pka is 7. Why is this slightly lower than normal imines?
-pyridine pka is 5.5. Why is this still even lower?

-pyridazine pka drops massively to 2.3. Why? It is however higher than both its isomers pyridine (1.3) and pyrazine (0.65) supposedly due to the alpha effect. However, how can one explain the massive drop in basicity when 2 sp2 nitrogens are in a 6 membered aromatic ring compared to 1 nitrogen (pyridine)? Maybe caffeine having incredibly low basicity (-0.96) could have something to do with these observations?