Question about acid-base extraction with Hydrochloric acid and Dimethyl Ether

[Limpet_Chicken]

You can just get solid caustic soda from B&Q or homebase, and make your own solutions. Its always best to by NaOH solid and make up your own.

If a sample DOESN'T release NH3, when treated, then it is most certainly not ammonium chloride. If it does, ammonium chloride is present, but that doesn't preclude a mixture. There are of course, opioid testing reagents, which can be used to determine if it is a mixture. Thankfully, even if you struggle getting it out (I'll see what I can find out about selective solvents for removing it), ammonium chloride isn't toxic. Actually they make a really nice salted liquorice, I think its norwegian, possibly finnish or swedish, called salmiak, that is salted with both NaCl and NH4Cl, its really tasty.

One thing you could try, is adding a soluble silver salt, to remove the chloride ions, as silver has a strong affinity for halide ions, which form silver halides, which are insoluble in water. Filter off the silver chloride precipitate (of course, don't discard it, after all, it has silver in there, save it up and smelt it down when convenient in quantity). And then acid/base using something mild like sodium bicarbonate or carbonate, sodium bicarbonate can be had from pharmacies, don't use 'baking powder' as that can have all manner of crud in it like rice flour, but the BP grade bicarbonate can be relied on as being quite safe, of course.

Unless you were to use a soluble silver salt of a nontoxic, biologically compatible counterion, for binding any chloride ion. Be aware not to store silver salts and ammonia solution, decompose it immediately, because the combination, which forms more rapidly the stronger the ammonia solution, forms silver nitride, which is highly sensitive and violently explosive. No practical use as an explosive, since it can't be isolated in enough of a quantity for anyone to make a bomb with it, it'd detonate from being touched to manipulate it, or even from internal stresses in a crystal if it was anything but tiny, or under it's own weight in the solid if in more than miniscule quantities.

 

[RedHat]

I was reading through this document, which explains how heroin is produced overseas, explaining how its converted from opium to morphine, then to heroin base, then to heroin hydrochloride in the last couple steps.

On page 9, it explains how they convert: brown heroin base => white heroin base => white heroin hydrochloride

The paragraphs I'm referring to are:

Purification of the brown heroin base
The brown heroin base was dissolved in diluted hydrochloric acid. The solution
had a pH value of 7-8. Because not all of the heroin base had dissolved, the
solution was filtered through a cloth. Activated carbon was then stirred into the
solution, and the liquid was allowed to stand for 30 minutes. Then the activated
carbon was filtered out using a cloth. Because the solution was not yet clear,
it was filtered a second time, using a paper filter.

Precipitation and isolation of the white heroin base
Then, the heroin base was precipitated using a diluted ammonia solution. The
pH value was 12.
The white heroin base was filtered through a cloth.

Conversion of the heroin base to heroin hydrochloride
The white heroin base was dissolved in a mixture containing hydrochloric acid
and a small amount of acetone. The heroin solution was then filtered through a
paper filter into a metal bowl and evaporated on a water bath. The white
heroin hydrochloride precipitated.

Jekyl Anhydride, I get why you were asking why the process outlined in my first post basically re-converted the base back into a base, and my assumption is that the article was written about purifying some type of heroin (either #3 or #4) that may contain cuts.

So it seems safe to me to basically skip all the steps before whichever step is supposed to yield heroin base. But pick up from there, reproducing the steps as best as I can (they even include the pH values :-O! )

What do you guys think??

 

[RedHat]

I haven't updated this in a while, but I believe I have the process down pretty well. Its been a while since I've been able to test it out (since I get #3 via Silk Road, which is hit or miss, and in my case, its much more "miss" than "hit" lately).

I've done an insane amount of research on this, including going over the existing documents on the web, and I'm like 95% sure I know exactly what needs to be done. I was thinking about documenting it (in depth), and posting a How-To somewhere (and somehow prune all data that would link back to me...).

Some of the confusion in the previous posts on this (primarily regarding why the process involves converting a base to a base) is mostly because Heroin #3 is packaged and sold right after the morphine is converted to heroin base, but before the heroin base is cleaned up using activated carbon and chloroform.

Heres a rough outline of the steps I have down thus far (not super well in depth)

1. Re-Purify the heroin #3 base
   1. Mix the heroin base in distilled water
   2. Add HCl to the distilled water in increments, mixing and testing the pH after each addition. Stop once the pH reaches ~7
   3. Remove all solid particulate matter (centrifuge, vacuum filter, whatever); move the solution to a separatory funnel
   4. Add chloroform to the mixture (1.5mL of chloroform for every 1g of H base), swirl it around;
   5. Separate out the chloroform layer (which should now contain some colored impurities)
   6. Add activated carbon; stir it up well; filter out carbon;
   7. Should now have a clear solution which contains the Heroin base
2. Rrecipitation and isolation of white heroin base
   1. Add ammonium hydroxide to the solution, one drop at a time; continue until the precipitation stops
   2. Mix the solution until it appears homogeneous
   3. Isolate the white heroin base via vacuum filtration
   4. Dry the solid substance in a steam bath
   5. Should now have a white solid substance, which is white heroin base
3. Recrystallization of the base
   1. This is just a typical recrystallization process using Ethyl Alcohol. Google it if needed
4. Conversion of recrystallized base to heroin hydrochloride
   1. Mix ethyl alcohol, ether and HCl to a boiling flask (exact amounts in my documentation)
   2. Heat the mixture (not quite to boiling)
   3. Dissolve the recrystallized base to the heated solution
   4. Slowly add HCl to the solution while stirring
   5. Test the solution to ensure the concentrations are adequate (theres a couple different ways to test it)
   6. Slowly add ethyl alcohol to the mixture, then ether
   7. When the crystals begin to form, add the remaining ether
   8. Let it chill for about an hour
   9. Filter the mixture via vacuum filtration
   10. Deposit the filtered substance in an evaporation dish, allow it to dry
   11. This should yield purified heroin hydrochloride

Like I said, the above is just a very very short summary of the steps I have laid out, and not all of them have been tested yet. But I have the exact amount of chemicals needed, the exact pH levels that should be reached for each step (and even more important, why those pH numbers are what they are), etc. If it all ends up working well, then ill find a way to safely share my knowledge!

 

[Jekyl Anhydride]

1. Re-Purify the heroin #3 base
   
2. Mix the heroin base in distilled water (although base won't mix with water and will just clump & precipitate unless that's the intended goal for cut removal only)
3. Add HCl to the distilled water in increments, mixing and testing the pH after each addition. Stop once the pH reaches ~7
   
4. Should now have a clear solution which contains the Heroin base (but also some H HCl from the addition of acid)

Hey RedHat,

Glad to see you came back and are as motivated as before. I was hoping you would, even if current circumstances leave me unable to devote as much time as I'd like assisting with more of the write up.

For now I just wanted to suggest saving all used solvents, even ones that are supposed to only contain waste or non active cuts, as a few things might require refining to prevent some significant losses.

This (these) step(s) stick out, as acidifying with HCl will create a mix of hydrochloride salts and bases mixing the H up between the polar & non polar solvents.

*Re-Purify the heroin #3 base

* Mix the heroin base in distilled water
*Add HCl to the distilled water in increments, mixing and testing the pH after each addition. Stop once the pH reaches ~7

Could you explain why this is performed and what bringing things to a neutral pH will achieve?

 

[RedHat]

Hey RedHat,Glad to see you came back and are as motivated as before.

Yep! I actually really enjoy figuring this kinda stuff out, learning about chemistry, which I completely neglected to do in high school.

For now I just wanted to suggest saving all used solvents, even ones that are supposed to only contain waste or non active cuts, as a few things might require refining to prevent some significant losses.

Indeed. I actually didn't get that much chloroform or ether primarily because solvents can be recycled. It may occasionally be necessary to clean the solvents, but they're completely recyclable.

This (these) step(s) stick out, as acidifying with HCl will create a mix of hydrochloride salts and bases mixing the H up between the polar & non polar solvents.

*Re-Purify the heroin #3 base

* Mix the heroin base in distilled water
*Add HCl to the distilled water in increments, mixing and testing the pH after each addition. Stop once the pH reaches ~7

Could you explain why this is performed and what bringing things to a neutral pH will achieve?

Sure. Obviously the heroin in its powdered base form isn't at all soluble in water, adding HCl to it will fix that, just as adding citric acid to it when you're cooking it up is necessary. As HCl is added, the hydrogen atoms will attach themselves to the nitrogen atoms within the heroin molecules. When all of the heroin has been neutralized (if thats the right word?), the pH should be >= 7. Adding more HCl will lower the pH level since the hydrogen atoms don't have anything to bond to.
Also, out of all of the documents I've found online that contain this process, only one of them actually include what the pH should be, and it also says "pH value of 7-8".

As to why the above process needs to be done, that would be because the powdered base isn't soluble in water at all, which is required for quite a bit of the steps afterwords. Or am I not understanding your question?

Hopefully I answered your question adequately.

P.S. The steps you're referring to were based off of steps found in the Documentation of a heroin manufacturing process in Afghanistan document, the past section on page 9, titled "Purification of the brown heroin base".

The brown heroin base was dissolved in diluted hydrochloric acid. The solution had a pH value of 7-8...

Keep in mind though that the process I summarized isn't 100% based off of the above pdf. Theres a couple others that involve some additional steps that purify it further, or use chemicals I would rather use. But the steps you specifically referred to are in the above pdf.

 

[Jekyl Anhydride]

I was going to mention that to salt it all you need to get the pH down to the 5's as commercial H is 4.8 from your other thread. Not that the UNODC didn't put together some good info but nobody who salts #3 does so at pH 7-8. If you read the PDF it mentions that not all of it will be converted.

 

[RedHat]

I was going to mention that to salt it all you need to get the pH down to the 5's as commercial H is 4.8 from your other thread. Not that the UNODC didn't put together some good info but nobody who salts #3 does so at pH 7-8. If you read the PDF it mentions that not all of it will be converted.

Right, commercial H is 4.8, but the step were talking about isn't for the final product, its an intermediate step. If the goal is to neutralize the base completely, why would you want the pH to get lower than 7? From what I understand, that means that all the base is neutralized, and there are available hydrogen ions, making it an acid.

I'll try both out and see which yields either higher quality or greater quantity.

Edit: I believe what were looking for is the "equivalence point", which will be obvious if I graph out the titration curve. Something I'll try out asap

 

[Jekyl Anhydride]

I was looking at this from the experience that sometimes a bit of excess is required to get and keep everything water soluble. The UNODC procedure was more for Kilograms vs small batch runs that the average user would be doing.

This is from the chemist on the HH site:

*Add a dilute solution of HCl dropwise while stirring with a glass rod. Monitor the pH closely. As the acid is being added, the diacetyl morphine base is being neutralized and converted into the water-soluble hydrochloride salt form.

*When all the solid material has just dissolved, stop adding the HCl. I found that this takes place around pH 5-6.
Note: If one tries to bring the pH all of the way up to 7, the free base alkaloid precipitates back out requiring addition of more HCl.

 

[RedHat]

I was looking at this from the experience that sometimes a bit of excess is required to get and keep everything water soluble. The UNODC procedure was more for Kilograms vs small batch runs that the average user would be doing.

This is from the chemist on the HH site:

I'm familiar with the document you're referring to, its one of the primary data sources I used, however the If one tries to bring the pH all of the way up to 7, the free base alkaloid precipitates back out requiring addition of more HCl part you're specifically referring to definitely slipped my mind! I shall change the pH listed in my docs from 7 to 5-6. Thanks!

 

[RedHat]

@Jekyl Anhydride I've looked into this a little more, and I actually think I was right with the pH needing to be around 7-8. The quote you shared was from the Heroin Purification Again document on Heroin Helper. Not only is the step you're quoting from a different stage in the overall purification process, but it looks like the overall process is actually different from what I'm using here.

The "Documentation of a heroin manufacturing process in Afghanistan" document is more in line with the process I'm using (and the origin from a lot of my documentation). And that does state that the pH should be about 7 or 8.

 

[Jekyl Anhydride]

If you can keep it all of it a salt at pH 7-8 please share how. Regardless of the purification stage, I've never been able to get anywhere near all of it in to a salt with out dropping nearly 2 points below neutral. The UNDOC description was an observation vs a step by step guide.

 

[RedHat]

If you can keep it all of it a salt at pH 7-8 please share how. Regardless of the purification stage, I've never been able to get anywhere near all of it in to a salt with out dropping nearly 2 points below neutral. The UNDOC description was an observation vs a step by step guide.

Ok so lets make sure were on the same page - When you say "I've never been able to get anywhere near all of it in to a salt with out dropping nearly 2 points below neutral", were you performing an acid-base reaction to further refine heroin #3 (heroin base) into heroin #4 (heroin hydrochloride) (similar to the Purifying Heroin article on Heroin Helper)? Or were you purifying some heroin that was already in the hydrochloride form? (similar to the other heroin purification article on Heroin Helper)

If its the latter, then thats actually a different process/technique than what I'm using.

I've done a lot of research on the subject (not "heroin purification" specifically, but acid-base related chemistry), and nearly everything I've read states that you need to fully protonate the base by adding the acid, and that once its fully protonated, the pH should be ~ 7. Also, this step isn't supposed to yield a salt. The step converting the solution to its final salt form is much later in the process.

The document that contains the quote If one tries to bring the pH all of the way up to 7, the free base alkaloid precipitates back out requiring addition of more HCl, isn't referring to the protonation step in an acid-base reaction.

P.S. I'm definitely having one of those "Fuck me! Why didn't I pay attention in HS chemistry class?!" moments. /facepalm

 

[RedHat]

Something I just found - I've been thinking the whole time that if the heroin base (or any base, really) is fully protonated with the acid (in my case, HCl), then the pH should be 7 (makes total sense to me..)

But reading the Wikipedia page for Neutralization says (at the end of the first paragraph):

In a reaction in water, neutralization results in there being no excess of hydrogen or hydroxide ions present in the
solution. The pH of the neutralized solution depends on the acid strength of the reactants. Neutralization
is used in many applications.

So I suppose I may be wrong... Well, looks like I have some more research to do.

 

[RedHat]

Up until now, I was under the impression that using too much acid in an acid-base reaction would require one to counteract the drop in pH by adding more of the base (which, in regards to refining heroin base into heroin hydrochloride, would mean a lower overall purity in the final product). @Jekyl Anhydride, this is actually the reason that I question your logic behind protonating the solution until the solution reaches a pH of 5 or 6.

However, I have a Chemistry Stack Exchagne thread open on the topic of using a "diluted" HCl solution in an acid-base reaction and just how diluted it should be. One of the users just left the below comment:

There's nearly never any harm in adding too much HCl, because any extra acid is retained in the aqueous layer, which you are going to remove anyway. For most purposes you therefore only need to do some maths: count how many moles of base you used, and hence the volume of HCl you need to add. If (for whatever reason) you really needed to monitor the pH, though, you could use pH paper to make sure the pH is around 7, as you suggested.

So, according to that logic, as long as the pH is at or below 7, it should be fine.

 

[RedHat]

Mix with ice cold water, then separate with your Buchner funnel, if you notice some crap in the catch flask then rinse a little more over it. You might pull out cuts like diphenhydramine, as that's used in the southeast states a lot.

I'm curious about that purity test, hopefully you get coffee colored results.

I know this is a late reply, but I thought you might find this interesting. Regarding the results from the purity test kit - It seems that the colors associated to the purity levels aren't as consistent as one would hope for... lol. Take a look. https://d.pr/i/yScygw

 

[Limpet_Chicken]

Not true in the case of a labile group present like an ester, esters are sensitive to both acid and base, and are easily cleaved by either.

 

[RedHat]

Not true in the case of a labile group present like an ester, esters are sensitive to both acid and base, and are easily cleaved by either.

Was that a reply to the last post by me? Or to an earlier post?

 

[fairnymph]

I was looking at this from the experience that sometimes a bit of excess is required to get and keep everything water soluble. The UNODC procedure was more for Kilograms vs small batch runs that the average user would be doing.

This is from the chemist on the HH site:

This has certainly been my personal experience (also using dutch #3). I go down to pH 4-5. Working right now on perfecting a purification process with limited equipment/solvents. I will add to this thread as I progress.