Morphine acid/base extraction from dried poppy-pods. Please help, I'm stuck!

[MeAndMissEmma]

Hi,

This is going to be a long and detailed post, but I will try to be as clear as possible.
Hopefully this will help others, as there isn't a great deal of useful information out there regarding the process of extracting morphine from dried poppy pods.

I have done a lot of research on this topic, looked at various threads on this forum and others, and referred to the Merck index, before coming to what seemed like a good extraction procedure.
I have reasonable chemistry knowledge, but not a lot about organic chemistry.

I got 1KG of dried poppy (papaver somniferum giganteum) pods. Once the seeds were removed, the pods weighed 379G (A lot of seeds!).
To put this in perspective, the seeds removed from the pods filled a 2L jar.
Most of the pods were brown and dry, although some were green and not fully dried.
Some of the pods had black patches (I believe this shows high opium content, it isn't mold)

First, however, I made poppy tea:
I ground up a single pod (and I hadn't yet got a coffee grinder, so I ground it manually, and I didn't do it very well; It was still quite coarse)
I added the powdered pod to about 500mL of water and heated it to ~60C for half an hour, stirring frequently.
Thereafter, I filtered the solution, allowed it to cool, and then drank 2/3 of it.
Aside from the unpleasant "dry poppy" taste, the solution was distinctly bitter (I love bitter tastes)
After about half an hour, I began to feel the familiar effects of morphine, and within an hour I felt quite high (although it felt like a small dose, I have a very low tolerance), my pupils were small, etc, the usual effects.
Note: I woke up with a headache for three days after, and I felt like shit.
I've never felt this before, even after coming down from numerous days of morphine use, I theorise this could be due to the presence of other undesirable alkaloids, and this is what lead me to attempt to extract the pure morphine from the pods, a process which proved very frustrating.

So, considering that the level of "intoxication" (can't think of a better word) seemed roughly similar to a 10mg dose of morphine (yes, very low tolerance) and considering that I only drank 2/3 of the solution, also taking into account the rushed and imperfect extraction procedure, it would be safe to make a conservative estimate of 20 - 25mg of morphine per pod.

There were around 100 pods in 1KG that I got, so that works out to 2 - 2.5G of morphine, so probably about 5G of alkaloids in total. Quite a lot!



So here is the extraction procedure I carried out:

1)
Ground up all the pods in a coffee grinder, until I had a quite fine light-brown powder, a little coarser than flour.

2)
Mixed the powdered pods up with about 3L of water, acidified with hydrochloric acid, adjusted to a pH of 2. (I used pure 36% hydrochloric/muriatic acid, not diluted/impure stuff).
I did not use any heat during the extraction, as morphine (and the other opium alkaloids) are highly soluble in acid, in this case by the formation of alkaloid hydrochloride salts, so I thought that using heat would be unnecessary to extract most of the alkaloids.
I left the solution at room temperature for around 18h, stirring regularly for a good portion of that time.

Note: Perhaps another extraction method, such as using alcohol or heat, could have extracted a little more morphine, but I figured I would get >90% this way.

3)
Strained the solution through a cloth

4)
Filtered the strained solution through lab filter papers to remove any fine particles.
I was left with a light brown - amber solution, about 3L of it!

5)
Adjusted the pH to 8, because morphine hyrochloride is much less inert to heat that morphine base, so I have read, so heating it in acidic solution may damage the molecule.
I used pure sodium hydroxide to increase the pH.

6)
Concentrated the solution to a more manageable volume
To concentrate it, I heated the solution in a double-boiler set-up, to about 70C, and concentrated it down to around 500mL, stirring regularly. This took around 20 hours.

I have read that, although it is ideal to keep the temperature at 70 - 80C, higher temperatures will not result in a great loss in potency.

Now I was left with a much darker, black-coffee-colored solution.

7)
Reduced the pH back to 2, as this more concentrated solution would no longer be able to hold all of the impurities already extracted, however all of the alkaloid salts would stay in solution.

8 )
Left the re-acidified solution overnight in the fridge to allow any impurities to precipitate.

9)
The next day, I filtered out the precipitate, it was a brown waxy sludge, which I dried out and kept (As this was my first extraction attempt, I kept all of the waste products from each stage, in case I needed to carry out another extraction on it)
This dried material seemed exactly like opium, it deliquesced quickly upon cooling and being exposed to air, and adopted a waxy tar-like consistency, however it would contain little or no alkaloids as they would still be in solution.

10)
Increased the pH to 12, again with sodium hydroxide.
This should have reacted with the morphine to form soluble sodium morphenate, while leaving the other alkaloids unreacted and causing them to precipitate out.

11)
Left the solution in the refridgerator overnight again to allow the precipitate to form.

12)
The next day, I filtered out this precipitate. This time is was not waxy, but rather a light-brown powder when dried, with some sparkling crystals visible. This I assumed was a mixture of the other opium alkaloids, and it weighed around 5G, which seemed about right.

13)
Reduced the pH of the filtered solution to 9.1

14)
Left the solution overnight in the refridgerator to, in theory, precipitate the morphine base.
But nothing formed! The solution was still clear the next day, no sign of any precipitate. I checked the pH, and it was still 9.1, and I left it a bit longer, but still nothing formed.

So, just as an experiment, I reduced the pH further to 7.0, still nothing.

So now we get to the puzzling part, I went back and checked the light-brown precipitate obtained in step 12, thinking that maybe the morphine had been precipitated with those. I rinsed the powder with water, and then dried it again, to remove any salt or sodium hydroxide that might be present.
This did not result in much loss in weight, as the powder seems to be insoluble in water.
However, this powder seemed to contain no alkaloids, as it did not taste bitter atall, just an odd acidic taste.
Just to make sure, though, I then dissolved this powder in dilute hydrochloric acid, stirring frequently, the idea behind this was to react any alkaloids present to form alkaloid hydrochlorides.
After a few hours of stirring, I filtered out the insoluble matter (maybe meconic acid) and dried the solution.
I was left with about 3.6G of brown powder, again with some crystals visible.
This, I thought, must be a mixture of alkaloid salts, perhaps including morphine due to some mistake I may have made.
But it was not! It had absolutely no bitter taste whatsoever, just that very odd acidic taste (I think this powder may be meconic acid). Just to make sure, I ate about 100mg of it (maybe a bad idea to eat unknown compounds, but I knew that it could not contain anything dangerous, even if it were pure morphine, 100mg would be safe), and no narcotic effects were felt. Not even any nausea that might have been associated with thebaine, for example. No ill effects resulted either, thankfully.

So where was the morphine hiding?
I then went back to the waxy precipitate I had obtained earlier, and confirmed (guess how), that this neither had any bitter taste, nor narcotic properties.
Therefore, the morphine must still be in solution!
Again, wrong it seems, as the solution had no bitter taste (although it was very unpleasant due to the presence of a lot of sodium chloride), and besides, how could the alkaloids still be dissolved at a pH of 7 - 9? No alkaloids are soluble at this pH.

So the only other place the morphine could be is still in the poppy straw, right?
So I tested this theory, I made some poppy tea with some of the straw. The solution obtained was very light colored (as, it seems, everything had already been extracted from it), and it had no bitter taste, and guess what, no narcotic nature!


I am really puzzled by this, as I have not lost anything in the procedure, yet morphine, and indeed none of the alkaloids, are anywhere to be seen, the morphine fairy has taken them...

The materials I used:
Pure sodium hydroxide (powder)
36% hydrochloric acid
Calibrated digital pH meter
Lab filter papers

The only other theory I had was that, maybe, the alkaloids had been destroyed by the heat, but this seems almost impossible, considering that I kept it at a safe temperature.

Does anyone have any suggestions/experience with this?
I really don't understand it, this should have been a simple process yet it has gone very wrong somehow.
I've spent hours researching it, and checking my process, and I see no mistakes.
(Also there is no possibility that there were no alkaloids in the pods as, as I said, I got high with a single pod!)

Sources:
I mainly followed this process by mongler
http://www.rollitup.org/t/morphine-extraction.117185/page-2

I also referred to:
https://erowid.org/plants/poppy/poppy_article2.shtml
https://opiophilia.blogspot.com/2012/12/how-heroin-is-made.html
https://en.wikipedia.org/wiki/Calcium_morphenate
Theoretical Organic Chemistry by Julius Cohen

I would really appreciate any help you guys could offer, and hopefully this will help enlighten others as well.

Thank you!

Peace

 

[Solipsis]

I think at pH 8 you would have converted only about half your morphine to the freebase as it is quite near the pKa, of that freebase most would crash out of solution since it is only sparingly soluble in water... heating this may have been pretty bad for it if it was lying on the bottom of your container and may possibly explain the sludge/gunk; even if the temperature of the solution was safe, it would require constant stirring to keep the precipitate from getting the full power of the heat.

Did you use a transparent container to see what's going on in there during the process?

Still doesn't explain what happened to the rest of the protonated morphine, I don't know how unstable it is when heated.. Also even damaged alkaloids should still be bitter I would think...

And finally: you are supposed to take your sodium morphenate solution and treat it with a weak acid to crash out the freebase morphine.

 

[MeAndMissEmma]

I think at pH 8 you would have converted only about half your morphine to the freebase as it is quite near the pKa, of that freebase most would crash out of solution since it is only sparingly soluble in water... heating this may have been pretty bad for it if it was lying on the bottom of your container and may possibly explain the sludge/gunk; even if the temperature of the solution was safe, it would require constant stirring to keep the precipitate from getting the full power of the heat.

Did you use a transparent container to see what's going on in there during the process?

Still doesn't explain what happened to the rest of the protonated morphine, I don't know how unstable it is when heated.. Also even damaged alkaloids should still be bitter I would think...

And finally: you are supposed to take your sodium morphenate solution and treat it with a weak acid to crash out the freebase morphine.

Thanks for the reply

Yes, I agree; the "increase the pH to 8" was the one dubious part of that procedure that I followed.
I did stir it regularly, the only way I could justify this was that maybe, at 70C, even freebase morphine would be fully dissolved, however, as the concentration increased, yes, it may have precipitated out.

No unfortunately not. I used glass containers for every other stage though, so that I could see if any precipitates formed.

Yes, I wonder what the decomposition products of alkaloids are, does it break up into the elements, or just form a slightly different compound?

In stage 13, I added hydrochloric acid to the sodium morphenate solution to reduce the pH to 9.1
Is there any particular reason that a weak acid should be used? I added 36% HCl directly to the solution in drops until the pH was right.

I've noticed that calcium hydroxide is usually used as a base, and ammonium chloride as an acid, in the "industrial" processes.
Since ammonium chloride is only weakly acidic, and it evolves ammonia upon neutralisation, this would seem to be less than ideal, so maybe it is just because it is cheaper and easier to handle, perhaps, than mineral acids?

I am thinking of trying it again, but this time doing a basic extraction at pH 12, to directly form sodium morphenate, thereby skipping a stage (although I did try a basic extraction a while ago, which I didn't mention here because I didn't do it right, and it seemed to extract a lot more of the unwanted oily/waxy stuff than the acid extraction did)

 

[mokele]

Hi,

This is going to be a long and detailed post, but I will try to be as clear as possible.
Hopefully this will help others, as there isn't a great deal of useful information out there regarding the process of extracting morphine from dried poppy pods.

I have done a lot of research on this topic, looked at various threads on this forum and others, and referred to the Merck index, before coming to what seemed like a good extraction procedure.
I have reasonable chemistry knowledge, but not a lot about organic chemistry.

I got 1KG of dried poppy (papaver somniferum giganteum) pods. Once the seeds were removed, the pods weighed 379G (A lot of seeds!).
To put this in perspective, the seeds removed from the pods filled a 2L jar.
Most of the pods were brown and dry, although some were green and not fully dried.
Some of the pods had black patches (I believe this shows high opium content, it isn't mold)

First, however, I made poppy tea:
I ground up a single pod (and I hadn't yet got a coffee grinder, so I ground it manually, and I didn't do it very well; It was still quite coarse)
I added the powdered pod to about 500mL of water and heated it to ~60C for half an hour, stirring frequently.
Thereafter, I filtered the solution, allowed it to cool, and then drank 2/3 of it.
Aside from the unpleasant "dry poppy" taste, the solution was distinctly bitter (I love bitter tastes)
After about half an hour, I began to feel the familiar effects of morphine, and within an hour I felt quite high (although it felt like a small dose, I have a very low tolerance), my pupils were small, etc, the usual effects.
Note: I woke up with a headache for three days after, and I felt like shit.
I've never felt this before, even after coming down from numerous days of morphine use, I theorise this could be due to the presence of other undesirable alkaloids, and this is what lead me to attempt to extract the pure morphine from the pods, a process which proved very frustrating.

So, considering that the level of "intoxication" (can't think of a better word) seemed roughly similar to a 10mg dose of morphine (yes, very low tolerance) and considering that I only drank 2/3 of the solution, also taking into account the rushed and imperfect extraction procedure, it would be safe to make a conservative estimate of 20 - 25mg of morphine per pod.

There were around 100 pods in 1KG that I got, so that works out to 2 - 2.5G of morphine, so probably about 5G of alkaloids in total. Quite a lot!



So here is the extraction procedure I carried out:

1)
Ground up all the pods in a coffee grinder, until I had a quite fine light-brown powder, a little coarser than flour.

2)
Mixed the powdered pods up with about 3L of water, acidified with hydrochloric acid, adjusted to a pH of 2. (I used pure 36% hydrochloric/muriatic acid, not diluted/impure stuff).
I did not use any heat during the extraction, as morphine (and the other opium alkaloids) are highly soluble in acid, in this case by the formation of alkaloid hydrochloride salts, so I thought that using heat would be unnecessary to extract most of the alkaloids.
I left the solution at room temperature for around 18h, stirring regularly for a good portion of that time.

Note: Perhaps another extraction method, such as using alcohol or heat, could have extracted a little more morphine, but I figured I would get >90% this way.

3)
Strained the solution through a cloth

4)
Filtered the strained solution through lab filter papers to remove any fine particles.
I was left with a light brown - amber solution, about 3L of it!

5)
Adjusted the pH to 8, because morphine hyrochloride is much less inert to heat that morphine base, so I have read, so heating it in acidic solution may damage the molecule.
I used pure sodium hydroxide to increase the pH.

6)
Concentrated the solution to a more manageable volume
To concentrate it, I heated the solution in a double-boiler set-up, to about 70C, and concentrated it down to around 500mL, stirring regularly. This took around 20 hours.

I have read that, although it is ideal to keep the temperature at 70 - 80C, higher temperatures will not result in a great loss in potency.

Now I was left with a much darker, black-coffee-colored solution.

7)
Reduced the pH back to 2, as this more concentrated solution would no longer be able to hold all of the impurities already extracted, however all of the alkaloid salts would stay in solution.

8 )
Left the re-acidified solution overnight in the fridge to allow any impurities to precipitate.

9)
The next day, I filtered out the precipitate, it was a brown waxy sludge, which I dried out and kept (As this was my first extraction attempt, I kept all of the waste products from each stage, in case I needed to carry out another extraction on it)
This dried material seemed exactly like opium, it deliquesced quickly upon cooling and being exposed to air, and adopted a waxy tar-like consistency, however it would contain little or no alkaloids as they would still be in solution.

10)
Increased the pH to 12, again with sodium hydroxide.
This should have reacted with the morphine to form soluble sodium morphenate, while leaving the other alkaloids unreacted and causing them to precipitate out.

11)
Left the solution in the refridgerator overnight again to allow the precipitate to form.

12)
The next day, I filtered out this precipitate. This time is was not waxy, but rather a light-brown powder when dried, with some sparkling crystals visible. This I assumed was a mixture of the other opium alkaloids, and it weighed around 5G, which seemed about right.

13)
Reduced the pH of the filtered solution to 9.1

14)
Left the solution overnight in the refridgerator to, in theory, precipitate the morphine base.
But nothing formed! The solution was still clear the next day, no sign of any precipitate. I checked the pH, and it was still 9.1, and I left it a bit longer, but still nothing formed.

So, just as an experiment, I reduced the pH further to 7.0, still nothing.

So now we get to the puzzling part, I went back and checked the light-brown precipitate obtained in step 12, thinking that maybe the morphine had been precipitated with those. I rinsed the powder with water, and then dried it again, to remove any salt or sodium hydroxide that might be present.
This did not result in much loss in weight, as the powder seems to be insoluble in water.
However, this powder seemed to contain no alkaloids, as it did not taste bitter atall, just an odd acidic taste.
Just to make sure, though, I then dissolved this powder in dilute hydrochloric acid, stirring frequently, the idea behind this was to react any alkaloids present to form alkaloid hydrochlorides.
After a few hours of stirring, I filtered out the insoluble matter (maybe meconic acid) and dried the solution.
I was left with about 3.6G of brown powder, again with some crystals visible.
This, I thought, must be a mixture of alkaloid salts, perhaps including morphine due to some mistake I may have made.
But it was not! It had absolutely no bitter taste whatsoever, just that very odd acidic taste (I think this powder may be meconic acid). Just to make sure, I ate about 100mg of it (maybe a bad idea to eat unknown compounds, but I knew that it could not contain anything dangerous, even if it were pure morphine, 100mg would be safe), and no narcotic effects were felt. Not even any nausea that might have been associated with thebaine, for example. No ill effects resulted either, thankfully.

So where was the morphine hiding?
I then went back to the waxy precipitate I had obtained earlier, and confirmed (guess how), that this neither had any bitter taste, nor narcotic properties.
Therefore, the morphine must still be in solution!
Again, wrong it seems, as the solution had no bitter taste (although it was very unpleasant due to the presence of a lot of sodium chloride), and besides, how could the alkaloids still be dissolved at a pH of 7 - 9? No alkaloids are soluble at this pH.

So the only other place the morphine could be is still in the poppy straw, right?
So I tested this theory, I made some poppy tea with some of the straw. The solution obtained was very light colored (as, it seems, everything had already been extracted from it), and it had no bitter taste, and guess what, no narcotic nature!


I am really puzzled by this, as I have not lost anything in the procedure, yet morphine, and indeed none of the alkaloids, are anywhere to be seen, the morphine fairy has taken them...

The materials I used:
Pure sodium hydroxide (powder)
36% hydrochloric acid
Calibrated digital pH meter
Lab filter papers

The only other theory I had was that, maybe, the alkaloids had been destroyed by the heat, but this seems almost impossible, considering that I kept it at a safe temperature.

Does anyone have any suggestions/experience with this?
I really don't understand it, this should have been a simple process yet it has gone very wrong somehow.
I've spent hours researching it, and checking my process, and I see no mistakes.
(Also there is no possibility that there were no alkaloids in the pods as, as I said, I got high with a single pod!)

Sources:
I mainly followed this process by mongler
http://www.rollitup.org/t/morphine-extraction.117185/page-2

I also referred to:
https://erowid.org/plants/poppy/poppy_article2.shtml
https://opiophilia.blogspot.com/2012/12/how-heroin-is-made.html
https://en.wikipedia.org/wiki/Calcium_morphenate
Theoretical Organic Chemistry by Julius Cohen

I would really appreciate any help you guys could offer, and hopefully this will help enlighten others as well.

Thank you!

Peace

Try calcium hydroxide instead of NaOH to form the calcium morphenate.The Problem is the fats in water extract.i heard the Pharma comp.use a new method called water threshing but havent looked it up.You should really get the book Oxy from Otto Snow,great recipe in there for exactly that and beware of low alkaloid strains planted for seeds,try to get high potency strains like tazzies or Izmir poppy bush.seeds used to be Online from Canada but our DEA friends closed them :-( But search the Net,You should get lucky and try that recipe,no ether or other extremly volatile solvent needed,but still take care.
Mo

 

[Solipsis]

Ca(OH)2 is more typical and might have more suitable properties but I doubt that makes such a world of difference. Other than that you make a vague/puzzling point^.

Not sure if it works to go straight to base, not sure if you have an extraction funnel or how big but you might have to concentrate your solution at a low pH (evap and possibly filter any gunk) and extract with non-polar solvents to get the fatty shit out, then basifying to the morphenate and crashing it out with a weak acid. Don't know what would be wrong with that but it doesn't seem particularly wise to deviate from the standard methods. And also even if you have a funnel, that kind of work can be even more tricky and laborous than the normal method which is straight to the point, or it would seem.

Maybe just try again but keep much better track of your morphine + minor bonus alkaloids and avoid anything that kills them / find alternatives. Also, maybe try a smaller batch first until you get a grip on it so that you are not wasting as much product to get the hang of it.

P.S. extraction seems pointless unless you use it to esterify the morphine alkaloid mix after like crude not-so-tarry black tar prop dope. I wanted to try that but ended up eating all my opium until i could work up the motivation.. fucken opiates..

 

[MeAndMissEmma]

Ca(OH)2 is more typical and might have more suitable properties but I doubt that makes such a world of difference. Other than that you make a vague/puzzling point^.

Not sure if it works to go straight to base, not sure if you have an extraction funnel or how big but you might have to concentrate your solution at a low pH (evap and possibly filter any gunk) and extract with non-polar solvents to get the fatty shit out, then basifying to the morphenate and crashing it out with a weak acid. Don't know what would be wrong with that but it doesn't seem particularly wise to deviate from the standard methods. And also even if you have a funnel, that kind of work can be even more tricky and laborous than the normal method which is straight to the point, or it would seem.

Maybe just try again but keep much better track of your morphine + minor bonus alkaloids and avoid anything that kills them / find alternatives. Also, maybe try a smaller batch first until you get a grip on it so that you are not wasting as much product to get the hang of it.

P.S. extraction seems pointless unless you use it to esterify the morphine alkaloid mix after like crude not-so-tarry black tar prop dope. I wanted to try that but ended up eating all my opium until i could work up the motivation.. fucken opiates..

Yes. I notice that no one has even mentioned "sodium morphenate" anywhere, however Wikipedia says: "Calcium morphenate is the intermediate in various latex and poppy-straw methods of morphine production, more rarely sodium morphenate takes its place."

Also, the Merck Index says (I don't have it with me so this may not be an exact quote): "freely soluble in solutions of fixed alkali hydroxides"

Haha. Vague and puzzling. That is about the most accurate way you could put it.

In my first extraction attempt (the one that I didn't do right), I used xylene, shook it up a lot, and then removed the layer from the water once it seperated.
This didn't seem to do much, and the xylene turned yellowish, however I couldn't figure out how to get rid of the last traces of xylene, it seemed to have dissolved in the water a little (maybe it is 0.000001% miscible?), and the smell just wouldn't disappear. I tried boiling it off, but that didn't work for some reason. Not that it matters, the amount is so small anyway.

No I don't have one of those funnels, although if I can get this procedure done I will certainly invest in one if it'd help. Haha.


Yes, I think I will try it again, I was initially using the whole kilogram to reduce losses, but it seems that that backfired!! Lol

"P.S. extraction seems pointless unless you use it to esterify the morphine alkaloid mix after like crude not-so-tarry black tar prop dope." -
I'm not sure I follow you there

Haha. Opiates. Gotta love 'em!
I just want to do it to reduce tons of pods into a small amount of powder, really, it doesn't matter too much if it is an alkaloid mixture.
I could just extract the "opium" and keep that, but it tastes so horrible, I don't think smoking it would be much better. XD

Thanks for your suggestions, I'll give it another go

 

[Solipsis]

idk, might be because you aren't using a funnel that separation was so hard... for emulsion type shit you could add salt though, or alternatively you could just roughly extract an excess of the watery layer that has the xylene blobs to at least get rid of the xylene/ non-polar, then if it is really meaningful extract the aqueous layer back from another container that offers more accuracy.

Poppies are supposed to mostly contain morphine as meaningful alkaloid, the long duration is perhaps due to competitive inhibition delaying the breakdown of the morphine... anyway, like I said there is little to be gained from this extraction IMO - what are you trying to achieve with it?
Avoid the bad taste of the tea? Yeah if you're struggling so hard I would just rather see about some reduced tea or extracting the opium and making something with it that lets you skip the eating/chewing etc which indeed is bitter. Just something you can glugglugglug down nearly as well as some alkaloid powder. Waxy shit is hard to pulverize but if you'd focus your effort on doing that all it would take is some large sized capsules to down that pulver.

Extractions are pretty cool especially if you learn, can afford to waste the materials etc... but it's different if all you really want is to get the goods and down em.

 

[MeAndMissEmma]

idk, might be because you aren't using a funnel that separation was so hard... for emulsion type shit you could add salt though, or alternatively you could just roughly extract an excess of the watery layer that has the xylene blobs to at least get rid of the xylene/ non-polar, then if it is really meaningful extract the aqueous layer back from another container that offers more accuracy.

Poppies are supposed to mostly contain morphine as meaningful alkaloid, the long duration is perhaps due to competitive inhibition delaying the breakdown of the morphine... anyway, like I said there is little to be gained from this extraction IMO - what are you trying to achieve with it?
Avoid the bad taste of the tea? Yeah if you're struggling so hard I would just rather see about some reduced tea or extracting the opium and making something with it that lets you skip the eating/chewing etc which indeed is bitter. Just something you can glugglugglug down nearly as well as some alkaloid powder. Waxy shit is hard to pulverize but if you'd focus your effort on doing that all it would take is some large sized capsules to down that pulver.

Extractions are pretty cool especially if you learn, can afford to waste the materials etc... but it's different if all you really want is to get the goods and down em.

Add salt. Yes that is a good idea, I think I read that in one of the extraction methods actually.

Yes, it is quite odd. It was certainly much less pleasant than morphine alone, but maybe that is something to do with me, rather than the actual substance.

Well, I have a source of pods pretty cheap, and reliable, not sure why they are so cheap, but when I got them, they were all covered in a thin layer of mold, so not much use for decorative purposes! Maybe that is why. Anyway, that is one reason, to avoid ingesting too much mold. 8)
It wipes off of the surface though, so I don't see this being too much of a problem
hint: Maybe this is why I felt so crappy for days afterwards.
Anyway, as far as I can tell, all the alkaloids are still there, and it's three times cheaper, and from a much less dodgy source, than any others that I can find, so mold doesn't really matter if I'm getting pure alkaloids from it (Tell me if I'm wrong here, I know that certain types of mold can be pretty toxic)

Well the tea is quite unpleasant, although I actually like bitter stuff (I think ever since I drank codeine solution, I've associated bitterness with happiness, so anything bitter is nice).

Yes, capsules is a good idea. The "opium" is hard and brittle when hot, but it quickly deliquesces and becomes waxy when it has cooled, so maybe it could be ground up just after drying.

To be honest, aside from the above reason, it just seems very appealing to have smokable morphine freebase also that is another reason, morphine is much better smoked due to the low oral bioavailability

Thanks again mon ami

 

[sekio]

If you go through all those steps and your pH testing technique is legit, then the obvious answer is your pods don't contain any/enough alkaloids to be worthwhile.

The process you describe is similar enough to e.g. USP/patent methods to isolate alkaloids from poppy straw/opium. No need to use lime (Ca(OH)₂), sodium hydroxide works too. Morphine should be stable enough to withstand boiling as a concentration method too.

 

[Solipsis]

The pods were tested though with good results if you read, so if they are actually weak / inactive when the extraction intermediate is sampled then the maths would seem to be off on how much you need to take of that to feel it.

As for the mold: cut that loose anyway, and be careful not to just extract any mycotoxins from a mold rendering the whole thing pointless - so don't extract on the moldy parts. Highly doubtful the mycotoxins would have similar physical properties but still...

Feeling bad for days from mold should feel different from coming down off of poppy tea, though poppy tea apparently does produce quite the long withdrawals if you do get those. I just wouldn't be too frugal when cutting off the mold.

 

[MeAndMissEmma]

Yes, maybe when the opium alkaloids are combined, the result is more potent? Seems vaguely possible, but I doubt it would be orders of magnitude.

Right. Yeah it felt pretty much like opiate withdrawals; headaches, irritability "you don't really know why, but you wanna justify rippin' someone's head off" sort of feeling. Lol.

In the book Theoretical Organic Chemistry by Julius B Cohen it says, and I quote:

"Morphine is a colourless crystalline compound, which melts at 230C and decomposes at the same time. It is very slightly soluble in water, is without smell; it has a bitter taste, and is a strong narcotic. It has an alkaline reaction, and is a tertiary monacid base. Morphine may be distinguished from many of the alkaloids by its solubility in caustic alkalis"

Then it goes on to describe the process of extracting the alkaloids from opium:

"In order to seperate the alkaloids, the opium is extracted with hot water and boiled with milk of lime, which dissolves the bases, but precipitates the meconic acid. The liquid is filtered from the insoluble calcium meconate, and the filtrate is boiled with ammonium chloride until ammonia ceases to be evolved, whereby the lime is converted into calcium chloride and the morphine is precipitated together with the other alkaloids"


I'm not sure what help this is, but a few things strike me as interesting:

This is about the only explicit reference to calcium meconate you will find anywhere.

It seems to suggest that the solution of lime and the alkaloids can be allowed to cool before filtration (doesn't say it has to be done while hot), and yet this extraction is supposed to extract all of the alkaloids, not only morphine.

Not sure what to make of that, because none of the alkaloids except morphine should be soluble in a cool alkaline solution, so they would precipitate out along with the calcium meconate too!

As a side note, this book is pretty interesting, it has a lot of stuff that is hard to find nowadays.

https://archive.org/details/theoreticalorgan00coherich
Morphine stuff is at page 582

 

[adder]

Perhaps try to further reduce the volume of your final solution and see if anything precipitates. At this point that's the only thing you can do, I guess. It is puzzling that you did not get any precipitate given that the narcotic effect was there with the tea. You may also try adding solid ammonium chloride to salt out morphine.

 

[MeAndMissEmma]

Hi guys,

A slight update.

I had kept the powdered poppy straw left over from the extraction, figuring it would still contain quite a bit of solution (turned out it did, the powder originally weighed 400g, but even after straining and squeezing as much solution out of it after the extraction, it weighed 1200g)

So I thought I'd do an "experiment" (really just an excuse to get high), I made poppy tea with some of this already extracted poppy straw, I used about 16 pods worth (figuring that almost all of the alkaloids would have already been extracted).
This was a bit on the heavy side, it seems.
I drank about half of the solution, slowly over a period of hours, (I may be stupid, but not so much as to drink it all at once :D)
And it definitely worked. Felt the usual positive effects, very talkative, happy, blissful, however with a lot of negative effects, nausea, weakness, complete loss of taste and smell, slight itchiness, twitching and trembling (not sure why this happens).


As time went by I felt more and more nauseous, and ended up lying in bed for hours (which was pretty good, just listening to music blissfully) but as soon as I moved, waves of horrible sickness. And I still feel sick a day later.
Okay I'm getting a bit off topic, but, basically, my point is, that maybe the extraction process was not that effective at all. From my estimation I'd say I took 50 - 100mg of morphine (any less wouldn't make me feel so sick, I don't think), so I'm thinking maybe multiple extractions are required, maybe a very rough estimate this would suggest that somewhere between 30% and 80% of the alkaloids are still in the poppy straw.

P.S. I realise that this also contained dilute hydrochloric acid, but that didn't seem to cause any trouble, because it seemed to have mostly been neutralised by the alkaloid bases, maybe. Certainly didn't taste very acidic.

This is what I will try next time, a double extraction.
*Closes eyes and lies down*

Thanks for all your suggestions guys :D

 

[adder]

Yes, you're right one extraction may not be enough even if you're using acidic solution, especially with poppy straw which will absorb a lot of the aqueous solution of extracted alkaloids. In the industry 2-4 extractions are usually done for opium with the undissolved and filtered out residue from the previous extraction being pressed and treated with another portion of water. The clandestine method of the so-called "kompot"/"Polish heroin" production, which is basically an acetylated concentrated extract of poppy straw, involves extracting poppy straw several times consecutively as well, each time producing a weaker batch (with the colour changing from dark brown/burgundy brown to pale yellow), but supposedly up to the 4th batch there is still some opioid effect. As an interesting side note, to get alkaloids out of the aqueous solution (brown-coloured extract of poppy straw) ion-exchange resin is used.

Anyway, here's an interesting article from 1950, even if out of purely theoretical scientific perspective, by Barbier on his method of the extraction and separation of opium alkaloids on an industrial scale. He also shortly discusses older methods.

 

[MeAndMissEmma]

Yes, you're right one extraction may not be enough even if you're using acidic solution, especially with poppy straw which will absorb a lot of the aqueous solution of extracted alkaloids. In the industry 2-4 extractions are usually done for opium with the undissolved and filtered out residue from the previous extraction being pressed and treated with another portion of water. The clandestine method of the so-called "kompot"/"Polish heroin" production, which is basically an acetylated concentrated extract of poppy straw, involves extracting poppy straw several times consecutively as well, each time producing a weaker batch (with the colour changing from dark brown/burgundy brown to pale yellow), but supposedly up to the 4th batch there is still some opioid effect. As an interesting side note, to get alkaloids out of the aqueous solution (brown-coloured extract of poppy straw) ion-exchange resin is used.

Anyway, here's an interesting article from 1950, even if out of purely theoretical scientific perspective, by Barbier on his method of the extraction and separation of opium alkaloids on an industrial scale. He also shortly discusses older methods.

Yes, it soaks up a lot of water... I added about 2L, and it just seemed to rehydrate and expand greatly in volume, so I needed to add about 3L or more, so that it would be reasonably liquid.

Oooh. An ion exchange resin, that is interesting. I've just been looking it up. Wow. I wasn't expecting that it was usually injected. O.O

Thanks a lot! That article is really interesting. This struck me:

"The opium is exhausted with cold water and the resultant liquor concentrated to a syrupy consistency. It is then precipitated hot with powdered sodium carbonate and heated as long as ammonia is given off"

I noticed that, during my dodgy first extraction process (the dodgy one I did ages ago, which failed too), there was a strong smell of ammonia evolved when I added sodium carbonate.
I wonder what reaction was happening there? I hadn't added any ammonia or ammonium compounds beforehand.

"I found that 125 kilograms of morphine base had disappeared in this way." - Ouch! A lifetime supply :D

Update:
I have extracted the poppy straw with boiling water (throwing caution to the wind) for a few hours and filtered it, and it is now being concentrated.
I have not increased the pH to 8 this time, but rather left it at 2.5, I think morphine hydrochloride should be stable enough, and this eliminates any complications associated with that grey area of solubility at an almost neutral pH of 8.
The plan is to concentrate it down to a much smaller amount, perhaps around 100mL or less, and then leave it overnight in the refridgerator for any sludge to form, then filter it out.
Finally, I will raise the pH to 9.1 and leave it overnight for (hopefully) all of the alkaloids to precipitate. The morphine can then be separated from this mixture later by basification and formation of sodium morphenate.
I am going to try to separate the alkaloid mixture first, though, thereby avoiding doing too many stages at once. Haha. Lest it vanishes again.


P.S. Slightly off topic:
Does anyone else find that morphine, taken orally, is about the most unaddictive substance imaginable?
For me, whether it is poppy tea, morphine solution, or tablets, the ill effects are so long-lasting and nauseating, that the thought of taking any more is very undesirable, for at least a week afterwards until the memory fades.
(I once took about 5 times my intended dose by accident, and I did not get any higher, but the ill effects were just much stronger and awful)
I bet it is much better smoked, though! Let's hope this works.

Thanks again, I will let you know if this extraction results in anything :D

 

[DotChem]

avoid adjusting the pH as much as possible.. here is the problem: any time you adjust the pH by using NaOH to increase or HCl to decrease the pH you are generating salt (Sodium Chloride) according to classical chemistry: acid+base --> salt + water in this case HCl + NaOH --> H2O + NaCl. By adjusting the pH - either way (NaOH to increase or HCl to decrease) your are increasing the concentration of salt NaCl (cumulatively) and pushing out (salting out even reasonably water soluble ionic compounds like sodium morphenate that you are are trying to selectively extract. You ended up basically trying to extract the alkaloids you want in BRINE solution not Water!! So I think somewhere along the way you basically salt out all the alkaloids you are aiming at including ones that would be expect to be in solution by virtue of them being charged at the pH you are aiming at.. The use of Calcium hydroxide may help overcome this problem since the by-product of pH changing in this case would be Calcium Chloride CaCl2 (deicing salt used on roads). The hydrate is less soluble than NaCl so it wont salt-out your alkaloids as much as NaCl would..next time, try tasting (just tiny bit on tongue) the solution before and after going through pH adjustment(s) and notice and record the "salty" taste...that will tell you whether you are dealing with a Briny solution or now... just an opinion.. but who knows?

 

[spacejunk]

Does anyone else find that morphine, taken orally, is about the most unaddictive substance imaginable?
For me, whether it is poppy tea, morphine solution, or tablets, the ill effects are so long-lasting and nauseating, that the thought of taking any more is very undesirable, for at least a week afterwards until the memory fades

No.

I think i did feel this way when i started fooling around with opiates a long time ago.
Gave me hangovers to begin with, and i didn't think i could do it every day.

...sadly i disproved that theory, and ended up needing it every day.
Interesting you don't like the taste of pod tea, because i always liked it - but then again i associated the taste with the effects, which i always very fond of.
I have to stay away from that stuff nowadays...

 

[MeAndMissEmma]

No. I think i did feel this way when i started fooling around with opiates a long time ago. Gave me hangovers to begin with, and i didn't think i could do it every day. ...sadly i disproved that theory, and ended up needing it every day. Interesting you don't like the taste of pod tea, because i always liked it - but then again i associated the taste with the effects, which i always very fond of. I have to stay away from that stuff nowadays...

Ahh interesting. I tend to find that I get cravings for codeine the next day but not with morphine. Maybe this is because codeine gives a stronger rush when taken orally. Codeine is pretty strange for me though, sometimes it feels great and other times, with the same dose, I feel no euphoria at all and end up getting frustrated and miserable, whereas morphine always has the required effect :D The taste isn't too bad, I like the bitterness, just not so sure about the rest. Haha

 

[MeAndMissEmma]

avoid adjusting the pH as much as possible.. here is the problem: any time you adjust the pH by using NaOH to increase or HCl to decrease the pH you are generating salt (Sodium Chloride) according to classical chemistry: acid+base --> salt + water in this case HCl + NaOH --> H2O + NaCl. By adjusting the pH - either way (NaOH to increase or HCl to decrease) your are increasing the concentration of salt NaCl (cumulatively) and pushing out (salting out even reasonably water soluble ionic compounds like sodium morphenate that you are are trying to selectively extract. You ended up basically trying to extract the alkaloids you want in BRINE solution not Water!! So I think somewhere along the way you basically salt out all the alkaloids you are aiming at including ones that would be expect to be in solution by virtue of them being charged at the pH you are aiming at.. The use of Calcium hydroxide may help overcome this problem since the by-product of pH changing in this case would be Calcium Chloride CaCl2 (deicing salt used on roads). The hydrate is less soluble than NaCl so it wont salt-out your alkaloids as much as NaCl would..next time, try tasting (just tiny bit on tongue) the solution before and after going through pH adjustment(s) and notice and record the "salty" taste...that will tell you whether you are dealing with a Briny solution or now... just an opinion.. but who knows?

That is an interesting theory, I hadn't thought that salt would affect the extraction.
Yes you are right, it does get very salty.
I have tried the extraction process a little differently this time, and yielded nothing.
The morphine may still be in the solution but it contains a ton of salt so I can't drink it

This time I did this:

1) Did a second extraction on the poppy straw by boiling (almost) in dilute HCl for a few hours
2) Strained the solution and dissolved the opium-like substance from the previous extraction in it
3) Concentrated the solution to around 100mL, leaving the solution's pH at 2.5
4) Filtered the solution to remove the sludge (this took numerous days)
5) Increased the pH to 12 and refridgerated overnight to precipitate stuff
6) Filtered the precipitate and dried it
7) The precipitate is a brown, slightly waxy, crystalline substance
8 ) Decreased the pH to 9.1 and refridgerated overnight to precipitate morphine
9) Nothing at all! Not even a cloudiness
10) Concentrated the solution even further to around 15mL
11) Continued from 4 again, still nothing!

The solution remaining may still contain morphine, however it seems unlikely, also it is too salty now to 'test" it

As for the precipitate obtained in stage 7, this was added to water and filtered to remove any traces of sodium hydroxide and salt.
What remained was pretty much insoluble
It has no bitter taste, well it has no taste at all really
I tried heating it and condensing the vapour, it seemed to consist only of water vapour, no solids seemed to condense.
So I think that this may be meconic acid or something, certainly has no narcotic effect.

So, my current, seemingly most plausible theory, is that the "sludge" in stage 4 contains most of the alkaloids, and this is where they go missing. I can't really explain how this is possible though, as they should always be soluble in an acid solution, right?

Is it possible that the alkaloids would, somehow, be insoluble in a solution of pH 2.5?

 

[Prescottdave]

Calcium morphanate is the way I have read is the route by which this should be done and that would be the end product. Using muratic acid to acidify a water based solution to a PH of 2 seems way overkill. Couldn't acetic acid be used instead for steps like this.