Very unexpected results from morphine a/b extraction

[Swerlz]

Why is nobody appreciating this fine sense of humour here? What a shame...

I chuckled a little, Murph %)

 

[Fail Fighter]

Morphine is a base, and as such, it should dissolve at lower pH, and precipitate out at a higher pH. This is one of the reasons that morphine is commercially prepared as either the hydrochloride or sulphate salt - to increase water solubility. Unless I have somehow forgotten something from my four years of medicinal chemistry and 8 years as a pharmacist

Yes, it is soluble in acidic solution, which is why sometimes it is advised to do an initial filtration at pH 4.5 - 5.5 before basifying the solution. However, if you make the initial pod solution using distilled water, the pH will already be around 5.5, so there's no need to further acidify. I can't stress enough the importance of using distilled water over tap water.

Something you might want to try as a solvent is ethyl alcohol. It should do wonders for your solubility, and correct me if I'm wrong but most of the people I've known to do extractions use KOH as their agent rather than CaOH... Or maybe it's only a matter of preference?

CaOH is just cheap and can be bought down the street at the local grocery store. And when I'm done using it, I can put it away in the kitchen cabinets. So basically there's no trace of my chemical toilings. And it's a good buffer solution to boot, with the excess simply falling out of solution.

For 50g of pods, you should have a fair amount of morphine extract. To my knowledge, the sap from P. somniferum pods yields a raw morphine content not less than 9% by weight. If you could get your hands on a fresh pod, not dried, you might significantly increase your morphine output from mere milligrams to potential grams, assuming any loss during precipitation is negligible. Using more water might help as it may be an issue of saturation.

Unfortunately, the morphine content of dried pods is roughly 0.5% by weight. So 50g should yield 250mg.

The recipe you're following seems quite elaborate even to the point of needlessness, but hey, I've never made it myself so I might be naive to this. However, I still stand by my the mantra, simplicity is the ultimate sophistication (thank you DaVinci for that one).

Let me tell you, it's very, very, difficult to pull off. It's all fun and games when you're reading about it online, but doing it in practice is... let's just say I'm done trying.


For the record, the strange precipitation occurred for a few days, then I again vacuum filtered the solution. I did a repeat filtration after adding activated charcoal which made a world of a difference and left the solution crystal clear, yet still slightly brown in color. The solution was then reheated and the NH4Cl added until the pH was 8.9 @ 70*C. The pH becomes roughly 9.2 as the solution cools to room temperature. Immediately when the solution cooled, about 50% of the morphine precipitated out. After letting it sit for 2 days, the rest fell out.

It looked like a pretty good yield, until I actually removed the morphine base. Once dry, there wasn't much at all. I dissolved it in a 10% HCL solution and evaporated it which left a small amount of white/tan crystals (the color will depend on how many times you filter with activated carbon).

Anyway, the final yield was maybe 50mg (just an educated guess, as I don't have a scale that can make such small measurements). All in all, it was a big waste of my time and I tossed out the yield. Stupid pods.

P.s., had I known beforehand that the yield from dry pods was so low, I never would have wasted my time with this.

 

[Trambunox]

^^^Nice, didn't know most of that and it's good to hear before I went wasting some time. Seems like people ought to just drink the tea and be satisfied...

I am curious though, you answered most every question I could come up with but I'm still curious as to how using ethyl alcohol as a solvent might improve your results.

Thoughts/experiences anyone?

 

[colors]

I did a repeat filtration after adding activated charcoal which made a world of a difference and left the solution crystal clear

the activated charcoal probably absorbed your morphine. why did you use it?

 

[Fail Fighter]

The charcoal will undoubtedly absorb some of the morphine because it does retain some moisture, but most of the morphine will remain in solution because it is soluble. The charcoal only removes insolubles.

The charcoal/carbon actually seems to be very important if you're going for purity. Without it, you'll end up with tainted, dark brown "crystals." I put that in quotes because the impurities interfere with actual crystal formation. After doing a few washes with the carbon, the solution becomes clear and you end up with white crystals that actually have a crystal formation (the final morphine hcl looked a bit like table salt). And FYI, the raw morphine base itself precipitates out as dust and does not form crystals.

Also, the impurities greatly interfere with the final morphine precipitation. Having a purer solution helps the morphine base fall out. That's why the vacuum filtration is so vital. I've tried this procedure in the past without the millipore filtration (I used a coffee filter) and it didn't work, i.e. I couldn't get the morphine base to precipitate out.

But all in all, I wouldn't suggest anyone even try this. It's a joke and a big waste of time. I would definitely try this with actual opium, but don't waste your time with pods. And for those wondering why I didn't just make PPT, well I tried that once and became deathly ill for 2 days, perhaps due to micotoxins. I vowed to never try that again, and seeing as I still had a large box of pods, I decided to play with the rest via a/b extraction.

 

[colors]

The charcoal only removes insolubles

that can't be true - we use it to filter elements that are fully dissolved in tap water for example. i dont know how much of the morphine it would pull, but it most hold a lot if it's used medically in cases of overdose etc.

 

[superponce]

2g opium dissolved in 10ml with heat. Filter. Make strongly basic with a minimum of NaOH, filter through glass wool. Add enough acetic acid to acidify and evaporate off water with heat and a stream of air to yeild a goo with some crystaline material.

Add 15ml acetic anhydride, stopper and heat flask in a boilling water bath for 4 hours, swirlling occasionally. Add saturated sodium carbonate solution until all the acetic anhydride has been neutralised and the solution is basic, then extract 3x with 10ml portions of dichloromethane. Dry the extracts with Mg2SO4 and evaporate to yeild a small quantity of beige heroin.

 

[Fail Fighter]

that can't be true - we use it to filter elements that are fully dissolved in tap water for example. i dont know how much of the morphine it would pull, but it most hold a lot if it's used medically in cases of overdose etc.

I was under the assumption that it filtered out microscopic solids that are not actually soluble (i.e. not weakly bonded to the polar water molecules) but are small enough to be held in suspension.

But again, I didn't make up any of these steps I've posted; this procedure, including the carbon filtration, is used in clandestine labs during morphine extraction from opium. I just researched how to do it and then tried it myself. It was, however, noted in most articles that the carbon did in fact carry away some minute amount of morphine. This is to be expected though, as most additional purification steps reduce yield slightly. Some amount of morphine is even lost during solvent extractions.

 

[MurphyClox]

Active charcoal actually removes lipophilic substances by adsorption. It's a pure physical effect.

 

[macbrown21]

You guys seems pretty smart... How much Calcium Hydroxide should i add to one batch (5 Pods) of PPT?

 

[Fail Fighter]

You guys seems pretty smart... How much Calcium Hydroxide should i add to one batch (5 Pods) of PPT?

None? The solution is only basified to isolate the morphine. If you want to consume all of the active alkaloids, then you'll want to acidify it.

That's "textbook" advice of course. In reality, acidifying/basifying the solution won't do anything if you're just going to filter and drink it.

 

[CloudyHazeD]

Im wondering....why are you guys trying to precipitate the morphine in solution? Couldn't you just use a nonpolar solvent to soak up the freebase alkaloids and then evaporate?

Like: make tea as normal with water; filter out pod material; make tea basic; add some petroleum distillates and load up the sep funnel. end with evaporating solvent

or am i missing something?

 

[Beenhead]

To be honest, the best way of extractinng such alkaloids is probably chromatography using an ion exchange resin

What do you mean by this? I ahve used Ionexhange chrom. to quantify. I though that a charged particle goes into the column, and the resin loses Hydrogen which is in turn taken by the charged particles.

SO are you introducing Morphine salt into the column, collecting many different aliquots, then analysing them with a light that Morphine loves to absorb? The peak is your morphine? Merck index puts λ max at 285 nm in acid

Ion Exchange Resins are the same are they not?

 

[macbrown21]

None? The solution is only basified to isolate the morphine. If you want to consume all of the active alkaloids, then you'll want to acidify it.

That's "textbook" advice of course. In reality, acidifying/basifying the solution won't do anything if you're just going to filter and drink it.

Well I read about 20 posts saying adding some form of calcium(hydroxide the best) makes your tea way stronger. Just for making tea that is. I woulda posted in that thread, but it's closed.

 

[Fail Fighter]

Im wondering....why are you guys trying to precipitate the morphine in solution? Couldn't you just use a nonpolar solvent to soak up the freebase alkaloids and then evaporate?

Like: make tea as normal with water; filter out pod material; make tea basic; add some petroleum distillates and load up the sep funnel. end with evaporating solvent

or am i missing something?

You're missing a lot. First of all, the basifying is done to make the morphine and codeine soluble. At high pH there is a MASSIVE precipitation, and from a clear solution there will magically be several ounces of crap that falls out and settles to the bottom of the glassware. You could further do a solvent extraction to remove the crap that didn't fall out, but again, the good stuff is SOLUBLE at this point, so it's staying in solution.

After this, you could drop the pH back to 9.1 and do a solvent extract I suppose. But it's actually easier just to throw the flask in a corner for a few days and let the M fall out of solution.

Basically all these complex steps are to isolate morphine from the other alkaloids, and more specifically, from codeine. And for the record, if you're trying to make tea, none of this thread applies to you.

Well I read about 20 posts saying adding some form of calcium(hydroxide the best) makes your tea way stronger. Just for making tea that is. I woulda posted in that thread, but it's closed.

People on this forum love to "say" all kinds of things. But how many have actually tried anything? I spent a lot of money on laboratory equipment and glassware and did months of testing on this subject. I've seen/done/tested it all, and I can tell you firsthand that 99% of what's said on this forum concerning PPT/PST/pods/etc. is complete bullshit. For example, everyone always says not to boil opium alkaloids because it destroys them. Which is nonsense! I don't care what the books say. After learning that heat is necessary to convert the alkaloids back and forth between salts and freebases, I started to boil everything, always. And I never once experienced any change in yield. If there are losses, it's negligible. FWIW, morphine supposedly breaks down at ~70*C and water boils at ~90*C at my altitude.

I can't believe I'm even posting here, because I gave up on this crap a long time ago. Anything involving pods or seeds is a big God-damned waste of time and my advice is to not bother with any of it. I sure wish I hadn't. I now have a large box of useless lab equipment sitting in my attic collecting dust.

But if you insist on dicking with this PPT nonsense, and you want to get maximum alkaloids out of the plant matter, just make the tea with distilled or highly purified water (bottled water will work, but make sure it doesn't have "added minerals for taste," such as sodium). Purified water has a lower pH than tap water and the alkaloids will be more soluble. There is no benefit to basifying the water, unless you want to filter out all the non-active crap you'll be drinking. And there's no need to acidify. You can if you want, but it won't do anything. On paper, the alkaloid solubility will be higher, but in reality it doesn't matter because soluble or not, the alks will be suspended in the solution and will not be accidentally filtered out.


Cliffs:
-Use distilled water for best results
-Acidifying does nothing
-Basifying does nothing, unless you want to filter out a bunch of crap (that I personally wouldn't want to drink).

If you already have the CaOH, just pour in a bunch. There's no risk of "over doing" it because once it reaches a certain pH (about 12), the extra CaOH will just fall to the bottom of the container. For a single batch of tea, probably a spoonful is all that will dissolve before it starts settling out. At this point you'll also notice the massive precipitation I've been talking about. It's rather impressive.

Steps for purifying the tea with CaOH:
-Add CaOH to the tea until it stops dissolving (It takes very little CaOH, about a teaspoon for ~250ml of tea)
-Bring the tea to a brief boil (about 1-2 mins).
-Filter the tea as best you can to remove all the gunk that precipitated out

At this point the tea no longer contains morphine, it contains calcium morphinate. Who knows what the bioavailability of that is. And I'm not even sure if you can drink it, because the solution is caustic. You might want to Add lemon juice/lime juice/vitamin C/any other household acid to the tea to bring the pH back down before consuming. Of course that will convert some of the morphinate back into morphine base... which has a low BA.

You know what, this is all very basic shit and once you know what it all means it will seem so simple to you. There is no mystique or confusion about any of this. It's very straight forward (although I was admittedly a bit baffled when I made this thread).

Cliffs x2

If it were ME, and I was making the tea, I would do this:
-Break open pods and discard seeds
-Turn pods into dust with a blender
-Add pod dust to distilled water to make tea
-Let the tea sit in a water bottle for as long as you can, and shake it every now and then. Let it sit for at least an hour. It will honestly continue to soak for about 12 hours, so leaving it overnight is best.
-Pour the mix into a pot and boil briefly to sterilize
-Filter the hot solution through a vacuum filtration/millipore filter to make it as clean as possible. Of course if all you have are coffee filters, you can use those. Double them up for best results, albeit slower/more tedious filtering.

And that's it. I would not bother with adding any acids or bases. It's a waste of your time and effort, and I guarantee that anyone who claims that acidifying/basifying made it "way stronger" is just a sucker for the placebo effect.

 

[alkap555]

If you are really trying to just isolate morphine and nothing else, then you probably would probably run an alumina column with the freebase extract that was stripped to an oil. If you just want to get the alkaloids in general just do some acid/base chemistry. You could try precipitation in acetone/ether via addition of conc HCl or better yet dry HCl gas, or to minimize water content you could use conc sulfurc acid. ....

Fail Fighter:
Activated charcoal doesn't only remove insolubles,, that is far from the truth. It will adsorb anything that is willing to hang around/orbital overlap with the pie cloud of the carbon (vanderwaals etc). Morphine base would likely coordinate to the activated charcoal surface, but I'm not sure how well the stuff adsorbs amine bases

 

[alkap555]

and you do NOT need to boil amine bases to do acid/base chemistry with them. To deprotonate a hydrochloride salt ya you could add some heat and that will deff speed it up, but as far as protonation, that is goddamn instantaneous and no heat needed esp with a strong acid.


also the best method of filtration I have found is using a funnel with a fritted glass disc, medium porosity is fine. its MUCH easier to scrape out all the yummy ppt.

 

[Fail Fighter]

I'm not looking for opinions on the matter; my efforts all failed miserably until I started using heat. The empirical results are all I care about.

 

[macbrown21]

You're missing a lot. First of all, the basifying is done to make the morphine and codeine soluble. At high pH there is a MASSIVE precipitation, and from a clear solution there will magically be several ounces of crap that falls out and settles to the bottom of the glassware. You could further do a solvent extraction to remove the crap that didn't fall out, but again, the good stuff is SOLUBLE at this point, so it's staying in solution.

After this, you could drop the pH back to 9.1 and do a solvent extract I suppose. But it's actually easier just to throw the flask in a corner for a few days and let the M fall out of solution.

Basically all these complex steps are to isolate morphine from the other alkaloids, and more specifically, from codeine. And for the record, if you're trying to make tea, none of this thread applies to you.









People on this forum love to "say" all kinds of things. But how many have actually tried anything? I spent a lot of money on laboratory equipment and glassware and did months of testing on this subject. I've seen/done/tested it all, and I can tell you firsthand that 99% of what's said on this forum concerning PPT/PST/pods/etc. is complete bullshit. For example, everyone always says not to boil opium alkaloids because it destroys them. Which is nonsense! I don't care what the books say. After learning that heat is necessary to convert the alkaloids back and forth between salts and freebases, I started to boil everything, always. And I never once experienced any change in yield. If there are losses, it's negligible. FWIW, morphine supposedly breaks down at ~70*C and water boils at ~90*C at my altitude.

I can't believe I'm even posting here, because I gave up on this crap a long time ago. Anything involving pods or seeds is a big God-damned waste of time and my advice is to not bother with any of it. I sure wish I hadn't. I now have a large box of useless lab equipment sitting in my attic collecting dust.

But if you insist on dicking with this PPT nonsense, and you want to get maximum alkaloids out of the plant matter, just make the tea with distilled or highly purified water (bottled water will work, but make sure it doesn't have "added minerals for taste," such as sodium). Purified water has a lower pH than tap water and the alkaloids will be more soluble. There is no benefit to basifying the water, unless you want to filter out all the non-active crap you'll be drinking. And there's no need to acidify. You can if you want, but it won't do anything. On paper, the alkaloid solubility will be higher, but in reality it doesn't matter because soluble or not, the alks will be suspended in the solution and will not be accidentally filtered out.


Cliffs:
-Use distilled water for best results
-Acidifying does nothing
-Basifying does nothing, unless you want to filter out a bunch of crap (that I personally wouldn't want to drink).

If you already have the CaOH, just pour in a bunch. There's no risk of "over doing" it because once it reaches a certain pH (about 12), the extra CaOH will just fall to the bottom of the container. For a single batch of tea, probably a spoonful is all that will dissolve before it starts settling out. At this point you'll also notice the massive precipitation I've been talking about. It's rather impressive.

Steps for purifying the tea with CaOH:
-Add CaOH to the tea until it stops dissolving (It takes very little CaOH, about a teaspoon for ~250ml of tea)
-Bring the tea to a brief boil (about 1-2 mins).
-Filter the tea as best you can to remove all the gunk that precipitated out

At this point the tea no longer contains morphine, it contains calcium morphinate. Who knows what the bioavailability of that is. And I'm not even sure if you can drink it, because the solution is caustic. You might want to Add lemon juice/lime juice/vitamin C/any other household acid to the tea to bring the pH back down before consuming. Of course that will convert some of the morphinate back into morphine base... which has a low BA.

You know what, this is all very basic shit and once you know what it all means it will seem so simple to you. There is no mystique or confusion about any of this. It's very straight forward (although I was admittedly a bit baffled when I made this thread).

Cliffs x2

If it were ME, and I was making the tea, I would do this:
-Break open pods and discard seeds
-Turn pods into dust with a blender
-Add pod dust to distilled water to make tea
-Let the tea sit in a water bottle for as long as you can, and shake it every now and then. Let it sit for at least an hour. It will honestly continue to soak for about 12 hours, so leaving it overnight is best.
-Pour the mix into a pot and boil briefly to sterilize
-Filter the hot solution through a vacuum filtration/millipore filter to make it as clean as possible. Of course if all you have are coffee filters, you can use those. Double them up for best results, albeit slower/more tedious filtering.

And that's it. I would not bother with adding any acids or bases. It's a waste of your time and effort, and I guarantee that anyone who claims that acidifying/basifying made it "way stronger" is just a sucker for the placebo effect.

Thanks at leeast someone gave me a straightforward answer in regards to science!

 

[chi chi laroux]

Jus about to do a quick morphine extraction on some poppy tea I've had sittin around for ages...
Fail Fighter, it sounds like you've come up with a pretty neat method that skips a bunch of steps and goes straight for the goodies, I cant figure out why no one appreciates it! perhaps it is because you're calling your tek "acid/base" an it's nothin like an acid base extraction in the traditional sense.
anyway I don't have any ph indicators and from what I can tell that won't matter, I can just err on the side of excess. Ya think there'll be any risk of burning my morphine?
I'd like to have a li'l stash as I don't have healthcare...