Possible improvements and streamlining of teks.

[dalpat077]

Well here's the culmination and most important of today's contributions.

I've a collection of teks. that I'd like for those in the know to take a look at with a possible view to streamlining them. They appear to be all over the place (to begin with) and certainly deviate from standard procedures and, in one or two cases, are pretty innovative for small scale extractions (for those prepared to muck about with Coca teabags or Coca powder anyway).

In looking at these things and spending a lot of time on this: I cannot help but wonder if a new set of qualified eyes couldn't improve and streamline (again: new pair of qualified eyes could maybe be of benefit). Just for fun and as examples: I've found two papers where warm or boiling methanol is purported to be more efficient (and obviously quicker) and have also found a paper dealing with microwave extraction under pressure (the latter though, I'm figuring, more for analysis and testing purposes i.e. impractical for production on any scale).

I also cannot help but wonder if these teks. are being over complicated. And while there's some commonality between them: there's also some differences that are of concern (or, to be more precise, that I don't understand).

Anybody prepared to lend a helping hand here and give their professional opinions (none of this stuff is anything new though i.e. been floating around for decades so far as I can tell).

I will upload the teks. into a single compressed file for download if that's acceptable. Done.

CETEK.zip

drive.google.com

 

[sekio]

Extraction of cocaine is not that difficult, of course many methods can be used to extract cocaine, but the classic method is described thusly
1. Mix coca leaves with a small amount of water, and add lime (calcium hydroxide) as a base
2. extract that mixture with nonpolar solvent (usually something like kerosene)
3, kerosene solution of crude cocaine base precipitated with sulfuric acid to produce crude cocaine sulfate
4. cocaine sulfate treated with potassium permanganate (oxidizes cinnamoylcocaine and other unsaturated impurities) <-- strictly optional
5. purified cocaine sulfate treated with alkali & extracted with nonpolar (chloroform, DCM) to produce cocaine base
6. cocaine base dissolved in e.g. acetone and treated with HCl (either as gas or as aqueous HCl)... cocaine HCl precipitates

yield is between 0.5% and 1% usually
less if you have stroed the leaves improperly, or if you expose cocaine to alkali+water too long

 

[dalpat077]

Amazingly I have the same document (Paco) i.e. just didn't bother to include it in my little collection.

Here's what I'd like to know though (the below from ye olde trusted Rhodium archive):

"a. Direct Leaf-to-Base Laboratories

In a recently developed and currently quite common variant, both solvent and acid extraction laboratories are being extended to production of coke base. In this alternate, coca paste is never isolated; rather, the unoxidized agua rica solution recovered from back-extracting the kerosene solution is filtered, adjusted (if desired) to higher pH with acarbonate or bicarbonate salt, and then treated directly with the potassium permanganate solution. This is a short-cut technique directly converting coca leaf to coke base, and offers several advantages to the clandestine operators:

1. There is a net savings of whatever inorganic base is being used to precipitate coca paste and the sulfuric acid required to reconstitute the agua rica;
2. The previously described difficulties associated with the poor shelf-life of coca paste are avoided (coke base is much more stable than coca paste); and
3. The operators save a lot of time.

Coke base generally varies from 80 to 95% cocaine. Since potassium permanganate oxidation tends to remove both the cinnamoylcocaines and other colored impurities typically found in coca paste, the appearance of coke base is usually much lighter, varying from light tan to white; in addition, it has a drier, more mobile (free-flowing) consistency versus coca paste."

Are these teks. implementing the above or going the longer route? I've been trying to figure out, from them, the branching out point (as is shown in the Rhodium document diagrams) i.e. where the isolation of coca paste is skipped (because that seems like a waste of time and effort and can result in a loss in yield or worse).

What floats my boat is the way one of the dudes times the oxidation process though i.e. seems to take some guesswork (and I dare I say "art") out of the process anyway. Then again: see below paragraph.

What strikes me though insofar as these homegrown teks. are concerned is that they seem to be specifically tailored to the Coca tea and Coca powder fraternity. I've spent years (off and on) checking this shit out and I don't see people running around in the jungle with pipettes and beakers and separation funnels and the like (nor ice buckets come to think of it) i.e. they just seem to toss the shit together (unless that's all based on such a thing known as "experience" of course). Most hitech thing I've seen is microwaving the end product (brick) in order to expedite the final drying process.

 

[sekio]

I don't see people running around in the jungle with pipettes and beakers and separation funnels and the like (nor ice buckets come to think of it) i.e. they just seem to toss the shit together (unless that's all based on such a thing known as "experience" of course). Most hitech thing I've seen is microwaving the end product (brick) in order to expedite the final drying process.

Reminds me of a Hammilton's Pharmacopeia episode where he goes to South Africa to look at the endemic methaqualone abuse still happening there. He meets this guy who acts as a "cook" to make crude methaqualone, and it is surprising how little if any this man knows about what he is doing. All he knows is what to physically look for, rough quantities to add of what reagents, the time needed, what pH to adjust the solution to to allow for the methaqualone to precipitate, how to crudely work up the material by collecting it in pillowcases and letting it drain in the sun...
The same happened with clandestine PCP labs. There are whole generations of "cooks" who never set foot on a post-secondary school and could never read a chemical name without hesitating, that have a closely guarded recipe that they follow, because it's reliable enough to work. Mechanisms, yields, checking purity, hell even basic "sanity checks" like checking for the level of cyanide present in the final product are not things that happen.

One such manifestation is termed the “The Bucket Method” (Scheme 37).109 Following instructions seized from a clandestine PCP laboratory by the United States Drug Enforcement Administration (DEA), the starting materials are first divided into two buckets, Bucket A and Bucket B; to Bucket A are added cyclohexanone (206) and Na₂S₂O₅ (209, which can generate NaHSO₄ in situ when exposed to water), while piperidine (210) and an alkali cyanide salt are added to Bucket B. Addition of the contents of Bucket A to those of Bucket B (or vice versa) yields masked iminium species PCC (207). In a third bucket, Bucket C, bromobenzene (211) is added to magnesium turnings to generate PhMgBr. This Grignard reagent is then added to a solution of PCC in naphtha to give PCP (166). Because such processes can readily produce large batches of PCP, the DEA stringently monitors several related compounds, such as piperidine and potassium cyanide.

You can have total morons do good chemistry if the process is documented and tested well.

Are these teks. implementing the above or going the longer route? I've been trying to figure out, from them, the branching out point (as is shown in the Rhodium document diagrams) i.e. where the isolation of coca paste is skipped (because that seems like a waste of time and effort and can result in a loss in yield or worse).

There's a chart in the document.

The process I described above seems to be the "direct to base" version. I would recommend this, the acid-first method seems iffy.

The older process would have taken the cocaine sulfate produced from the extraction of the kerosene, and converted it back to the freebase so that it could be stored (?) or possibly the acid->base flipping provides some sort of purification? Either way, it's not strictly needed, as evidenced by the emergence of a better method. The recipe I wrote a few posts up already has this optimization.

This is the "correct" way to produce cocaine.hcl from the freebase.

 

[dalpat077]

Yip. Those are the exact diagrams to which I was referring.

As for the first paragraph: that's my point. There's an amusing little passage in the Cocaine Handbook i.e. something along the lines of some Colombian cook taking a look at a lab. setup and looking puzzled and saying that all you need are three buckets and two bed sheets (and David Lee and his partner promptly then booked into a hotel and stole the bed sheets)! And that's pretty much what I've seen over the years in my research. That's why I'm saying these teks. seem to have been worked out for the tea and powder fraternity i.e. not scale production (to be clear to the authorities: relax i.e. I'm not talking about metric tons here)!

 

[sekio]

Cocaine Handbook

I actually am not fond of that book, it's beyond outdated and has hokey bullshit like "bleach tests" and "burn tests"... fuck man, we can send samples out to be analyzed with GCMS or whatever, for an affordable fee these days.
It's a period piece but let's be straight, it's almost 40 years old. ("revised" ed in 1983, 2021-1983=38 ) So it's information on cocaine must all be from more than 40 years ago. Would you trust a doctor who refused to modernize his medicine beyond 1983? I sure wouldn't. He would probably tell me cannabis is going to render me sterile, etc.

The thing that grates me, is that so many people in my city who use, sell ,or handle more than trivial amounts of cocaine, but have no clue that it's actually quite water sensitive.
So you'll have guys that store paper "flaps" with cocaine HCl in their center console for weeks, guys that carry cocaine "on their person" (crotch it) or even just in a sweaty hand for too long, people who store multiple grams in half sealed cheapo Ziploc bags...
It was the strangest shit, because in many of the cases I analyzed, there were rarely any cutting agents visible on GC,, but still sometimes it was like 30% cocaine, 70% benzoylecgonine
Eventually I had my cocaine-supplying friends start giving me samples in sealed bags, suddenly the purity is way higher???

Curiously, if you want reliable cocaine, buying crack is the way to go sometimes
Because of the very nature of crack production (alkaline environment), benzoylecgonine loses its HCl, but also loses a carboxylic acid proton, and now it's a super polar water soluble salt... it doesn't end up in the precipitated cocaine base.
Believe it or not this is one of the street's approved metric for quality of cocaine batches - how much it "cooks back", they say. If you have ideal chemistry, you get 303.4/339.8 = ~89.3% mass yield. That is, 100 grams of cocaine hydrochloride ("powder cocaine"), treated with bicarbonate, under totally ideal circumstances will produce 89.3 grams of freebase "crack" cocaine. This yield is decreased depending on any of several reasons. One is if many common cutting agents are added (most of them - salt, sugar, etc - don't behave like cocaine does and hence can be separated with ease, but apparently levamisole, which is an alkaloid with a solid freebase form, became popular because it would undergo the same solubility changes due to pH, was cheap to get (livestock dewormer, baby), possibly acted as a prodrug for the powerful stimulant aminorex, etc.
Another reason yield can drop is if the cocaine was exposed to some combination of excessive moisture and at least some heat. Cocaine is super hygroscopic (absorbs ambient moisture) so the combination of a bunch of water, plus some heat, results in rapid hydrolysis, mostly to benzoylecgonine.
The process is, theoretically, reversible, but mostly as an academic exercise rather than anything anyone actually does.
So, encourage your cocaine dealers to store their stash with desiccants, and wrap the flaps up too.
Crack dealers need not apply, they can store crack rocks in their mouth or wherever, without too much hydrolysis at all.

 

[dalpat077]

Obviously I read the above with interest and meant to comment yesterday but didn't get around to it.

It's interesting (to me) how it's possible to go backwards i.e. from HCL (back to) freebase (NOT Crack).

Back in the day I used the water, ammonia, and ether route no problem (although the yield always being formal and quantifiable notification of just how badly you were getting screwed over of course).

And which, of course now, has given rise to some questions or ideas (soon to appear on one of these other threads).

 

[dalpat077]

Oh. By the way. I re-read these posts often to make sure I’ve not missed anything and then cross reference to whatever new stuff I’ve come across.

Just realised I actually have a tek. courtesy of none other than the DEA as to how to separate out Levamisole. Not of any use to me nor would it ever be applicable to me either and certainly way above my pay grade. Possible nevertheless (once again, as usual, requiring a proper laboratory and equipment of course).

And which reminds me. The DEA is late with its 2020 Drug Assessment Threat Report for some reason. Always makes for good research and information from both sides of the aisle! More than anything though: pretty keen to see the effects that the pandemic has had on the status quo of the industry.

 

[G_Chem]

I actually am not fond of that book, it's beyond outdated and has hokey bullshit like "bleach tests" and "burn tests"... fuck man, we can send samples out to be analyzed with GCMS or whatever, for an affordable fee these days.
It's a period piece but let's be straight, it's almost 40 years old. ("revised" ed in 1983, 2021-1983=38 ) So it's information on cocaine must all be from more than 40 years ago. Would you trust a doctor who refused to modernize his medicine beyond 1983? I sure wouldn't. He would probably tell me cannabis is going to render me sterile, etc.

The thing that grates me, is that so many people in my city who use, sell ,or handle more than trivial amounts of cocaine, but have no clue that it's actually quite water sensitive.
So you'll have guys that store paper "flaps" with cocaine HCl in their center console for weeks, guys that carry cocaine "on their person" (crotch it) or even just in a sweaty hand for too long, people who store multiple grams in half sealed cheapo Ziploc bags...
It was the strangest shit, because in many of the cases I analyzed, there were rarely any cutting agents visible on GC,, but still sometimes it was like 30% cocaine, 70% benzoylecgonine
Eventually I had my cocaine-supplying friends start giving me samples in sealed bags, suddenly the purity is way higher???

Curiously, if you want reliable cocaine, buying crack is the way to go sometimes
Because of the very nature of crack production (alkaline environment), benzoylecgonine loses its HCl, but also loses a carboxylic acid proton, and now it's a super polar water soluble salt... it doesn't end up in the precipitated cocaine base.
Believe it or not this is one of the street's approved metric for quality of cocaine batches - how much it "cooks back", they say. If you have ideal chemistry, you get 303.4/339.8 = ~89.3% mass yield. That is, 100 grams of cocaine hydrochloride ("powder cocaine"), treated with bicarbonate, under totally ideal circumstances will produce 89.3 grams of freebase "crack" cocaine. This yield is decreased depending on any of several reasons. One is if many common cutting agents are added (most of them - salt, sugar, etc - don't behave like cocaine does and hence can be separated with ease, but apparently levamisole, which is an alkaloid with a solid freebase form, became popular because it would undergo the same solubility changes due to pH, was cheap to get (livestock dewormer, baby), possibly acted as a prodrug for the powerful stimulant aminorex, etc.
Another reason yield can drop is if the cocaine was exposed to some combination of excessive moisture and at least some heat. Cocaine is super hygroscopic (absorbs ambient moisture) so the combination of a bunch of water, plus some heat, results in rapid hydrolysis, mostly to benzoylecgonine.
The process is, theoretically, reversible, but mostly as an academic exercise rather than anything anyone actually does.
So, encourage your cocaine dealers to store their stash with desiccants, and wrap the flaps up too.
Crack dealers need not apply, they can store crack rocks in their mouth or wherever, without too much hydrolysis at all.

I learned something here. So benzoylecgonine can be washed out with hot water washes then, that’s nice...

The times I’ve made my own freebase I’d take distilled water and boil it in the microwave then immediately drop it on to the freebase in a vial. After 3-4 washes itd turn into snowflake looking crystals, that would blow your head off.

-GC