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Very unexpected results from morphine a/b extraction

Fail Fighter

Fail Fighter

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Joined
Apr 25, 2008
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240
So I decided to give the ol' a/b extraction routine a try.

1. Blended 50g dried poppy pods into dust
2. Mixed powder with 1L distilled water and added to a pot
3. Brought solution to 70* C and let sit for 1 hour
4. Added Calcium Hydroxide to bring pH to 11.4
5. Let sit another 30 mins at 70* C
6. Strained out pod matter and pressed the matter to remove maximum solution
7. Vacuum filtered solution through a 2um micron filter
8. Put filtered solution back in pot and brought back to 70* C


So the next step is to add Ammonium Chloride to bring the pH down to 9.1 to allow the morphine base to precipitate out. But first, I decided to leave the solution at 70* for 2 hours to evaporate it down to a more workable volume. After this, the solution volume was down to just under 0.5L. But the solution had a lot of fats/waxes in in, so I decided to let it cool so I could do a xylene wash.

But here's the weird part: after letting it cool, I came back and discovered that there had been a large crystal precipitation. I double checked the pH, and it's still ~ 11.5.

So what the heck are these crystals?? Aren't all the alkaloids supposed to be soluble in strongly basic solutions?
 
ummm...
i have no idea what you really were trying to do. i have never seen a a/b-extraction without apolar solvent. besides that you have chosen quite strange chemicals as acid and base, and to the best of my knowledge morphine is soluble in water at low pH. i think you should read up a bit on the chemistry behind and acid/base-extration.

the crystals might be CaCl2...

btw: pKa of morphine is 8.21, so there's absolutely no need to go up to 11 anywhere in the process (if it's not necessary to break emulsions like with dmt extraction. i don't know the specifics of extracting morphine from poppies.)
 
That's the standard procedure and acid/base pair for morphine extraction.

After some reading, I guess the crystals are just non morphine/codeine alkaloids. This has never happened before though. Usually raising the pH to 11+ creates an instant precipitation of alkaloid gunk, not crystals. I suppose they were just being kept in suspension as a result of the morphine meconates (and an excess of water).

That doesn't explain how they got past the micron filter though. I dunno, I'm pretty baffled.
 
Typically? Zero grams. :\

I've made three prior attempts and all three failed. First I discovered that it's because the calcium morphinate didn't properly form during my brief heating cycles. This time around, I'm making sure to heat at 70* - 75* C for an hour after adding the CaOH and another hour after adding the NH4CL. I also discovered that impurities in the solution kept the morphine base from precipitating out, so the micron filter should take care of that.

It's going great this time. Experimenting with small amounts of solution resulted in definite morphine base crystals precipitating out. I ran out of ammonium chloride (which I ordered today), so once that arrives next week I'll do the remaining solution.

I'm really just doing this for fun (not planning on consuming the morphine) so I'm not sure if I'll bother with trying to get maximum yield. I was just planning on precipitating out the crystals, but maybe I'll do a xylene wash to see exactly how much yield I could get from 50g of pod powder. I know the solution likes to hold a considerable amount of the morphine base in suspension, even at pH 9.1.
 
Fail Fighter said:
That's the standard procedure and acid/base pair for morphine extraction.

...

I dunno, I'm pretty baffled.
Click to expand...

You're baffled because those instructions suck.

The answer? Don't use shitty instructions that you find on 0pi0phile or the equivalent that try to break down chemistry into retarded kitchen techniques for dummies (not calling you a dummy, but it seems like those "teks" are for kids with down syndrome).

If I was to do this, I would use different chemicals than the ones you listed, thats for sure.
 
That's because the phenolic OH (remember phenol's old name is carbolic acid) group of morphine forms a pheolate salt that is ionic when you use high pH extraction (CaOH, NaOH etc). The only way to do it is to use 0.880 ammonia solution as that's not basic enough to form phenol salts.

Calcium salts of phenolates aren't very soluble from what I can remember
 
This procedure is the standard... you can look it up in many different morphine extraction patents. What's wrong with the chemicals? The CaOH is used because it's a good buffer and the NH4Cl is used because the resulting ammonia helps the morphine base precipitate out. I know using NaOH for the base is not advisable.
 
The method is kind of all over the place. The problem is the steps you posted are basically Compote/'Polish Heroin' with a few alterations. The problem with Kompot is the lack of quality control (to say the least).

Manufacture Of Alkaloids From The Poppy Plant In Hungary
J. Kabay 1/1/1961

"J. Kabay . . . was able to devise a chemical method of determining the morphine content of poppy straw, a task which was entrusted to him by the League of Nations"

"Kabay's original process has been improved in the last twenty-five years, but the method used in the production of alkaloids from poppy straw remains basically the same.

The Kabay process is as follows: The poppy capsules (with stalks not more than 10 cm in length) are thrashed, dried and then treated with an extracting liquid which consists of a solution of sodium bisulphite in water. The resultant aqueous extract is concentrated in vacuo using the "counter-current principle" method until it attains a syrupy consistency. The pasty substance thus obtained, which has a morphine content of 1% to 1.2%, is then treated with alcohol or other organic solvent. The solution-which, besides morphine, contains a lesser amount of other extractable material than the aqueous extract-is then distilled, yielding an extract having a morphine content of 2% to 4%. From this mixture of alkaloids in alkaline medium the morphine base can be precipitated by treating the mixture with ammonium sulphate in the presence of benzene. The product will have a morphine content of over 50%, and, by means of repeated precipitation or crystallization, it is possible to obtain from it the pure morphine base and morphine salts or semi-synthetic derivatives. "

http://www.poppies.org/news/99501931090804.shtml

"The Morphine content of dried poppy straw is something like 0.01%-0.03% of the total weight. Many people say their usual dose of ground dried poppy straw for tea is around 12g: that would mean 12mg-36mg, which is about right for a non-tolerant person to feel high. However it can vary by a lot, depending on crop conditions, strain of p.somniferum, location, etc. "
 
Maybe I'm just drunk, but I'm really confused by why no one gets what I'm doing. It's just a basic morphine extraction.

Step 1: Mix opium/straw/whatever with water
Step 2: Basify to 11.5 to precip. out non-morphine/codeine alkaloids
Step 3: Drop pH to 9.1 to precip. out morphine base

?
 
why do you think the precipitated material is an alkaloid, it could equally be a calcium salt of meconic or any of the other acids that have been liberated from the alkaloids.

It also could be the non phenolic alkaloids dropping out.

test the solid for alkaloid There is a test that gives purple for morphine and various colors for the others,
does it dissolve in neutral solution,
does it precipitate in acid?

this assumes the rest of the phenolic alkaloids are still in solution though there is a problem in that the calcium phenolates are not very soluble as fastandfabulous said.

why don't you filter off the solids and work with the liquid that is left, see what happens.

the process is fine, it is similar to the method used clandestinely in Turkey. though I don't think they use lime.


you are not going to get anyone remotely identifying the solids through teh interwebs,
If you send a small amount of the solids as an attachment (MIME and .alk is fine) to [email protected] they will tell you what it is, though they will take your soul in payment , and your cell mate Bubba will take the rest. :)

the answer you seek is right in front of you but you are going to have to approach it logically and scientifically and (unfortunately) do some work.
 
Hmm, did a xylene wash and it didn't absorb the crystals. It did remove those pesky fats/waxes however. Will filter the solution next!
 
To be honest, the best way of extractinng such alkaloids is probably chromatography using an ion exchange resin
 
Lol, "best"? I bought a pound of Calcium Hydroxide (aka pickling lime) at the grocery store for $2. Clearly I'm not shooting for the "best" method here, just a quick/easy/ghetto method that produces some form of results. I don't care what the percentage yield is, I'll be happy just to end up with something!
 
extractions

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
 
You could crush up your poppies, extract the alkaloids with an organic solvent, evapourate off the solvent, and then do some acid base extraction if you want.
 
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?

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.

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).
 
vecktor said:
If you send a small amount of the solids as an attachment (MIME and .alk is fine) to [email protected] they will tell you what it is, though they will take your soul in payment , and your cell mate Bubba will take the rest. :)
Click to expand...
Why is nobody appreciating this fine sense of humour here? What a shame...
 
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