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

[MeAndMissEmma]

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.

Yes, calcium (or sodium) morphenate should be an intermediate product, but not the end product I don't think as it maybe only exists in solution.
(Don't have any evidence of that, but I suspect it is probably unstable. Also, it only exists in a basic solution, and it is soluble, so it would be difficult to separate from the dissolved base)


That is an interesting point, maybe my next step should be to try an alkaline extraction instead of an acid one

 

[Prescottdave]

This link looks like the way to go from poppy pod putty. Acids and basses involved include acetic acid/white vinager and sodium carbonate as well as NaoH in the middle of the extraction. I think many chemists back in the day worked with raw opium making the process much simpler when trying to precipitate a mixed alkaloid extraction minus the papervine and nicotine. Having a very strong starting product makes precipitating alkaloids much more straight forward.

I would just stick to poppy pod tea or collecting raw opium or pods. Or making pod putty then soaking it in acetic acid for 2-3 days stirring and then filtering the solution and evaporating it back to hopefully a much stronger putty for oral use. If I lived someplace P soms grew all over then I would be in heaven.

Here in the southwest they are a bit less common then Washington or certain other countries though people still can grow huge fields. Take certain parts of AZ. They used to farm poppies out in yuma per the now defunct business. The easiest time I had growing poppies was actually when I lived in a high mountain part of AZ. You could start them in march and harvest them by the end of may or mid june. Took a huge clay type flower bed container and grew a small patch to try and get some seeds adapted to the hotter climate. Stupid neighbors stole all of the 20 or so pods. Man did the poppies love the AZ weather during those months.
http://www.bluelight.org/vb/threads/362596-Pure-Morphine-From-Poppy-Pods

 

[MeAndMissEmma]

This link looks like the way to go from poppy pod putty. Acids and basses involved include acetic acid/white vinager and sodium carbonate as well as NaoH in the middle of the extraction. I think many chemists back in the day worked with raw opium making the process much simpler when trying to precipitate a mixed alkaloid extraction minus the papervine and nicotine. Having a very strong starting product makes precipitating alkaloids much more straight forward.

I would just stick to poppy pod tea or collecting raw opium or pods. Or making pod putty then soaking it in acetic acid for 2-3 days stirring and then filtering the solution and evaporating it back to hopefully a much stronger putty for oral use. If I lived someplace P soms grew all over then I would be in heaven.

Here in the southwest they are a bit less common then Washington or certain other countries though people still can grow huge fields. Take certain parts of AZ. They used to farm poppies out in yuma per the now defunct business. The easiest time I had growing poppies was actually when I lived in a high mountain part of AZ. You could start them in march and harvest them by the end of may or mid june. Took a huge clay type flower bed container and grew a small patch to try and get some seeds adapted to the hotter climate. Stupid neighbors stole all of the 20 or so pods. Man did the poppies love the AZ weather during those months.
http://www.bluelight.org/vb/threads/362596-Pure-Morphine-From-Poppy-Pods

Thanks for the link, I don't think I had seen one that before :D
Interesting how acetic acid is often used, maybe due to the low toxicity?
Yes, where I live there aren't a lot of opium poppies growing, but there are a few.
Was going to plant some but it got a bit late in the year haha.
In heaven. I know right.

You mean legally grow huge fields or...?
Oh that is interesting, they used to be grown for opium there?
I'm thinking of raiding some of the poppies growing around here, I'm surprised no one else has yet.
They aren't really big enough yet, but it is finding that perfect balance between allowing them to ripen, and waiting too long and someone else having picked them.



I have been reflecting on the extraction process, and I have thought of one other thing that might be significant:

When I did the extraction, I used acid (about 70mL of 36% hydrochloric acid) , then filtered it, then basified.
However, this is producing a lot of salt (I calculate around 40g!), going from pH 2 to pH 12.
Perhaps this could be salting out the morphine or altering the solubility of it and the other alkaloids?
An alternative method here would be to evaporate the solution after filtration, this will get rid of most of the acid, and then dissolve it again, thereby reducing the amount of base required to reach pH 12, and miniminising the amount of salt dissolved.
This could explain why it is easier to do the extraction with opium, because it elimenates the acid extraction stage altogether.

 

[adder]

Basic extraction with ethanol or isopropanol is worth a try IMO, the solubility of alkaloids in neutral or charged form will be better than in water. Take a look at this patent. Alternatively, try getting alkaloids out of the acidified solution with an ion-exchange resin, it's puzzling where the alkaloids go, this way you might find out if the extraction of straw itself works alright as alkaloid recovery this way is typically very high. Sulfonated polystyrene cationic exchange resins typically used to deionize water serve well for this purpose.

 

[MeAndMissEmma]

Basic extraction with ethanol or isopropanol is worth a try IMO, the solubility of alkaloids in neutral or charged form will be better than in water. Take a look at this patent. Alternatively, try getting alkaloids out of the acidified solution with an ion-exchange resin, it's puzzling where the alkaloids go, this way you might find out if the extraction of straw itself works alright as alkaloid recovery this way is typically very high. Sulfonated polystyrene cationic exchange resins typically used to deionize water serve well for this purpose.

This is probably a silly question, but what does basified alcohol actually mean?
I have seen some extraction techniques referring to alcohol basified to a pH of 11...
Doesn't pH only apply to aqueous solutions...
Does this mean, a solution of base at pH 11, mixed with alcohol?

The ion-exchange resin looks like a good idea!
I have been reading about it, so the resin is added to the opium solution, allowed to react with all of the alkaloid ions, and then filtered out.
The resin is then treated with an alkaline solution (ammonia is preferable because it is a gas, so easily separated, I suppose) to displace the alkaloids out again.
Is this about right?
Will definitely look into trying this when I order more pods.
The resin seems to be sold in large amounts on eBay, like kilograms of it, do you know where it might be procured in a smaller quantity?

Thanks for the suggestion

 

[mokele]

I guess for that ion-exchange to work You will need the amounts,concentrations,etc.
Once tried to understand the chemistry behind Desomorph.production,which was invented by a russian chem.student who just came from rehab!
Page was in russian,Google translation
-bleech-?,my polish gf tried to translate but got stuck all the time with words
like “farunk“.
Page is pulled off web anyhow,would have loved to know where they fucked up..or p.didnt use clean....!
If you get that ion-exchange to work,
I salute you!
In my country,close to ex East.Block,we used to have Czechs with little bottles of just that,few dared try,HIV was just coming,but i watched a guy try it,hit the ground with spike still in,also 2young guys were found dead in a Bus with backpack full of these bottles.
Better get a bag

 

[adder]

This is probably a silly question, but what does basified alcohol actually mean?
I have seen some extraction techniques referring to alcohol basified to a pH of 11...
Doesn't pH only apply to aqueous solutions...
Does this mean, a solution of base at pH 11, mixed with alcohol?

The ion-exchange resin looks like a good idea!
I have been reading about it, so the resin is added to the opium solution, allowed to react with all of the alkaloid ions, and then filtered out.
The resin is then treated with an alkaline solution (ammonia is preferable because it is a gas, so easily separated, I suppose) to displace the alkaloids out again.
Is this about right?
Will definitely look into trying this when I order more pods.
The resin seems to be sold in large amounts on eBay, like kilograms of it, do you know where it might be procured in a smaller quantity?

Thanks for the suggestion

Basified alcohol is alcohol with base added to generate alcoholic solution of RO(-), in this case you add NaOH or KOH and actually generate a mixture of RO(-) and HO(-) with some water generated as a result of alcohol deprotonation.

As for ion-exchange resin, you will probably need anywhere from 0.2-1.0 kg of resin per 1kg of poppy straw to be extracted, general clandestine procedure for extraction and acetylation of the extract that I know of, though I'm not speaking from practice, use 0.5-1.5 kg per 1 kg of straw. The right quantity obviously depends on the resin used, generally you want a strong cationic exchange resin. Chemisorption takes place from acidified solution (typically 10% acetic acid soln is used to acidify) and morphine is freed with aqueous ammonia solution, but the literature says 4M HCl as well as 1M NaOH works well for this purpose (source).

It's hard to say if it's feasible to obtain pure or almost pure morphine starting with 1 kg of straw, the scale you're working at seems to be very important here.

 

[MeAndMissEmma]

Ahh! Amazingly I think I understand that.
Thanks for clearing that up.
So alcohol loses the hydrogen from the hydroxyl group, forming a negative alkoxide ion, RO-, which forms a sodium or potassium alkoxide and the hydrogen forms water upon reaction with the hydroxyl group.

ROH + Na+ (OH)- > RO- Na+ + H2O

I didn't actually know sodium ethoxide was a thing until just now.

Ahh. That sounds doable, unfortunately the link doesn't work for some reason, I will try it again later. Gives some sort of "Requested resource could not be loaded" error.

Okay. There is one thing that is confusing me about the concept of ion-exchange, perhaps I am looking at it wrongly...
It seems like a displacement reaction, where the resin, which consists of sulfonate anions and sodium cations, has a weak affinity for the sodium ion so it exchanges it with the alkaloid ions in this case.

Sodium sulfonate + Morphine hydrochloride > Morphine sulfonate + Sodium chloride

However, if the sulfonate ion has a stronger affinity for morphine than it does for sodium (thereby allowing the exchange to take place) how will the reaction be reversed when the resin is added to sodium hydroxide?
Is it due to the high concentration of sodium hydroxide that the exchange takes place even though there is a weaker affinity for sodium?

I found this which seemed to clear up 90% of the confusion, though.
It lists the order of affinities which is interesting.

This stuff looks like the right kind, and it is for sale in small quantities (1L = 840G so that should be just about enough according to your source)
BTW, I actually only have 400G of straw, the pods weigh 1KG including the seeds. Hah.
The Merck index states that dried pods contain up to 0.5% morphine (look up "poppy capsules")...
I wonder if they meant with or without seeds?
If they meant the latter then there goes 60% of my projected morphine yield. Oops!

 

[adder]

That article you linked to pretty much summarizes the mechanism of ion-exchange with ion-exchange resins. Using poppy alkaloid extraction as an example:

1. After activation/regeneration of the resin with a strong acid, it has H(+) ions bound to -SO3(-), so essentially it's a polymeric arenesulfonic acid.

2. When you put the resin into the solution of morphine sulfate or acetate or some other salt, the resin exchanges H(+) ions with protonated morphine ions. Why this works has to do with the difference in the affinity of different ions. I'm not really sure why, for instance, Ca(2+) ions would have higher affinity to -SO3(-) than Na(+), or NH4(+) higher than H(+). But I suppose alkaloids have high affinity for polystyrene sulfonate resins due to additional interactions of polymeric chains of the resin with hydrophobic moeities in alkaloids.

3. Recovery or elution of morphine (along with other alkaloids + some impurities) from the resin can be done either with acid or base. With base you basically deprotonate morphine-H(+) and release it as a freebase or morphenate depending on the pH. With acid excess acid (like 4M HCl) flushes out morphine-H(+) from the resin.

Anyway, the extraction from 400 g of poppy straw may not be feasible unless you want to end up with something like Polish heroin which could perhaps be taken rectally, with intravenous injection being out of the question in my opinion, nevertheless that's the main route it was/still is used despite very low purity.

 

[MeAndMissEmma]

Thanks for the explanation mon ami!

I'm actually currently trying to learn a little more organic chemistry, it is quite interesting (not to mention useful), it is my dream to be able to look at some complex molecule and have even a vague idea of what sort of compound it is or what kind of chemistry could be used to alter it or add a functional group here or there.
A lot of stuff to remember, that is what I struggle with.

So if one uses an acid to recover the morphine one is going to end up with a dissolved salt... Well that would be okay actually, because the HCl could then be evaporated off.
Using sodium hydroxide, one would have to precipitate the alkaloids from the solution I should think (perhaps that is why ammonia is preferred, it can be evaporated, leaving nothing behind but the alkaloids)

Yes, I am going to give it a try... After all, if it works, I could get more pods and do it in a higher quantity.

Funny you should mention rectal administration... Probably too much information here but, in the name of science *wink*, I just tried that ROA with concentrated poppy tea (used 8g of pods).

And I discovered something interesting on the way;
Using multiple extractions is definitely necessary, as the powdered straw seems to hold onto a lot of water once it is filtered, even if it is pressed.
For the first extraction I used 160mL of almost-boiling water (quite convinced the theory of alkaloid decomposition is greatly exagerated and compensated for by the increased solubility in boiling water)

After force-filtering using a 100mL syringe with a circle of filter paper (much quicker than letting it drip through without pressure) I was left with less than half of the solution.
Exerting considerable force on the syringe only got a little more solution out of the poppy straw, and about half of the water stayed in the straw (I was left with 90mL of solution)
So, a single extraction will probably only extract ~25% of the alkaloids (assuming 50% of the alkaloids are dissolved into the water on the first pass, and 50% of the water stays absorbed in the straw)

I did two more extractions, and the third one still had a bitter taste, then reduced it to about 100mL (sounds like a lot of solution to plug but it is actually quite fun. Definitely TMI)

So the plan, with the 400g of straw, is going to be something along the lines of three extractions with almost-boiling dilute hydrochloric acid, for numerous hours. I'm sure nothing will escape that!

I wonder if I should just use plain water for the straw extraction, and then acidify it before using the resin.
I've never used acidified water for making poppy tea and there has never been any problem, but then again the solution is much more dilute.
Maybe multiple extractions with water alone would be better as it would take fewer impurities with it. Then again maybe not.

Anyway, this ROA seems to be a LOT better than drinking the stuff, no nausea and no unpleasant solution to drink!

It took a lot longer to come on than I had expected (about an hour) and there was no rush, but this could be due to my failure to acidify the solution (The pH was already acid, around 5, however maybe the alkaloids aren't fully in meconate form at this pH)

I am not sure whether or not it is more intense, however it feels a lot better due to the lack of nausea, a big breakthrough (even with a low dose, the nausea I experience is usually so bad that I can't move or even breathe deeply without waves of horrible queasiness).

Next time I should acidify the solution with a few moles of hydrochloric acid, just to make it come on a little faster.

Yes I agree, IVing anything like that seems horrific.
Opiates seem to be unusually easy for me to deal with, in the past I've had access to a lot of morphine, but I've never really been tempted to use it frequently, the memory of the experience, and the knowledge that I will use it again, seems to be enough to keep me from taking it too often.

On the other hand, if I have any weed around, I can't resist the urge to smoke it, and I wonder why because I don't even like it... Oh and the withdrawals from weed are a lot worse than coming down from opiates (not worse than opiate withdrawals, but worse than coming down after a single use)
Welcome to the Twilight Zone!

Anyway, please forgive me for rambling on... Opiates make me talk endlessly about stuff that is endlessly fascinating to me now, but probably boring as hell to anyone who isn't high too.

If I manage to get some reasonably pure morphine, I would like to try converting some to dihydromorphinone, just for fun... The process looks unbelievably simple, but maybe I am missing something.
https://erowid.org/archive/rhodium/chemistry/dihydromorphinones.html



Thanks again for your help, I am going to get some of that resin and give it a try

 

[Prescottdave]

70 ml of hydrochloric acid is extremely dangerous. I think that may be an error as 10 drops of 35% muriatic acid brings 2 cups of water down to a PH of about 2-4. I think you may be better off avoiding extraction teks and just stick to some safer methods of ingestion.

 

[Prescottdave]

Thanks for the link, I don't think I had seen one that before :D
Interesting how acetic acid is often used, maybe due to the low toxicity?
Yes, where I live there aren't a lot of opium poppies growing, but there are a few.
Was going to plant some but it got a bit late in the year haha.
In heaven. I know right.

You mean legally grow huge fields or...?
Oh that is interesting, they used to be grown for opium there?
I'm thinking of raiding some of the poppies growing around here, I'm surprised no one else has yet.
They aren't really big enough yet, but it is finding that perfect balance between allowing them to ripen, and waiting too long and someone else having picked them.



I have been reflecting on the extraction process, and I have thought of one other thing that might be significant:

When I did the extraction, I used acid (about 70mL of 36% hydrochloric acid) , then filtered it, then basified.
However, this is producing a lot of salt (I calculate around 40g!), going from pH 2 to pH 12.
Perhaps this could be salting out the morphine or altering the solubility of it and the other alkaloids?
An alternative method here would be to evaporate the solution after filtration, this will get rid of most of the acid, and then dissolve it again, thereby reducing the amount of base required to reach pH 12, and miniminising the amount of salt dissolved.
This could explain why it is easier to do the extraction with opium, because it elimenates the acid extraction stage altogether.

Do not attempt this.

 

[adder]

70 ml of hydrochloric acid is extremely dangerous. I think that may be an error as 10 drops of 35% muriatic acid brings 2 cups of water down to a PH of about 2-4. I think you may be better off avoiding extraction teks and just stick to some safer methods of ingestion.

Working with concentrated acids and bases requires special attention and care, I agree, but you're overreacting a bit, I think. 1M HCl solution has a pH of 0 and you're not going to get burnt if you spill it on your hands and wash it away with running water shortly after.

70 mL of conc. HCl is not that much if you consider the volume of diluted solution. I dump 1 L of conc. HCl into a 10L bucket filled at 3/4 with water to make an acidic bath (for glass cleaning), which roughly gives a 5% solution.

 

[clubcard]

Correct me if I am wrong, Adder, but in Papaver somniferum, morphine meconide is the common ester. I know UK opiates are all derived from poppy straw (used to be grown in India) and poppy straw is controlled. Being a weak acid, a weaker base and an easier to handle acid (citric?) might be safer? I don't know if that is just here. I do know that desomorphine is obtained with a much higher yield if the RP & I are replaced with another reducing/deprotecting system where the HI concentration can be controlled (22% for example) by slow addition of the reducing agent. Of course, the stuff is still a very fast acting compound and not one I would want to see. I've read that it is the RP partially changing into another allotrope that is responsible for a lot of the damage.

I think we have both tried a lot of compounds in this class and it is hard not to 'collect them all' but then again, not much fun for a long time. Don't forget, if you come over, I will sort out the paperwork (couldn't PM you).

 

[draculic acid69]

Firstly you need to make a tea of the plant material then do it again extract plant material at least twice with water at a warm to hot but not boiling temperature.dont use acid it is COMPLETELY unnecessary.all the morphine is already in a water soluble form and should not fukd with yet.just water is adequate.it extracts the alkaloids just fine.if you add acid it's just something to get rid of later.and after forming your sodium morpheme you need to add ammonium chloride NOT hydrochloric acid.the p.h. does not need to be lowered as it is the OPPOSITE of what you need to do.you probably still have a solution of sodium morphenate and lots of sodium chloride from all the unnecessary acid and caustic soda.once you add the sodium hydroxide to the tea to make sodium morphenate then add ammonium chloride then your morphine settles out of solution.ammonium chloride is not an acid and hydrochloric acid is not an acceptable substitute.this is one reason why you didn't get anything.

You've taken a few different extraction methods and chopped and changed them to come up with the process you tried.heres where you went wrong:
1:you didn't extract the plant material well enough with only room temperature water.making a tea on the stove will be more effective.always extract at least two times.when heating two to three times should be adequate.any more is overkill.
2: you added acid.this is pointless at this point.water on its own works fine and acid doesn't dissolve more or work better than water.
3: you made sodium morphenate instead of calcium morphenate.the sodium morphenate is probably a lot more soluble than the calcium one.this is a source of problems.
4: you added hydrochloric acid acid to the sodium morphenate instead of ammonium chloride.

If you'd followed one extraction technique instead of mixing parts of the homebake and poppy straw extraction you would have got a result.

 

[Iloveflowers]

Calcium hydroxide then ammonium chloride