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Phenylpiperidine Opioids - how low can you go?

polymath said:
Even if one batch in 10 contains something really toxic like WP, it's going to cause a lot of damage...

The extraction of morphine-like alkaloids may not work in the same way as with amphetamines, as they are also soluble to alkaline solutions because of the phenol -OH, and it seems that morphine freebase is not soluble to petroleum ether (but is soluble to some other nonpolar solvents). Maybe it's some misunderstanding about how it should be purified by extraction.

Actually, looking at solubility data, codeine freebase isn't soluble in pet ether either, and I think that must have been the real reason why my own codeine extraction didn't do the trick as I expected...
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I'm certainly not pushing desomorphine as a drug of abuse. I'm trying to work out if their is a simple, reliable way to remove the species that apparently causing the tremendous damage. Nobody making in in their kitchen is going to extract desomorphine into chloroform, wash back into hydrochloric acid and distil of said acid to arrive at samples that only contain compounds with a basic nitrogen. It may be argued that the 'expert samples' aren't krokodil but whatever the term, if 3M H2O2 will oxidise the species to -PO4 3- so people aren't being destroyed then all to the good.

That people ARE prepared to destroy themselves so quickly while looking at others going down the same path then it's safe to say that it's in the subjective class of Diconal/Ketogan/Levo-Dromoran i.e. both opioid and NMDA activity. The difference is, while the others last 6-8 hours, desomorphine lasts just 1 hour. That much euphoria with such brevity isn't going to be dependence-forming, it's going to be compelling. I realize that Russian HR is in it's early days but they repeatedly say that psychological addiction can occur after 1-2 shots.

I note the Swiss experience with Permonid describes it as being:

+ 'faster acting and more effective than morphine'

but

- 'relatively more severe respiratory depression produced at equianalgesic doses, as well as a high incidence of other side effects such as hypotension and urinary retention, were felt to outweigh any potential advantages'

I don't know of the experiences of others but some pretty large Swiss trials using morphine to substitute diamorphine showed that beyond a certain (equipotent) dose, users were unable to differentiate the two drugs. Safe to say that I WOULD know if it was a joint opioid/NMDA antagonist; people hooked on that rush used to mix methadone wet-amps & cyclizine aka (Valoid™) travel sickness medication. We saw a lot of strange things at Lifeline in the 80s. Since I like pills & will vap or snort rather than inject pure material... I wasn't quite dragged in.

Realistically, it can happen in any nation where codeine is [P] or lower.

I will bet $1 that officially or not, Poland is now the home of Krokodil.
 
quite sure desomorphine lasts longer than 1 hour,more like 3 hours,still shorter than morphine
 
My admittedly old copy of The Merck Index lists duration as 60 minutes. At the much larger doses taken by regular users, it's 60-100 minutes according to most Russian HR sites. Don't forget, Krokodil can actually contain 6-deoxymorphine & 6-methyldesomorphine as well or even JUST be one of the 3. You have to look at the metabolic fate of them all. Seven different CPY450 metabolise the nominal parent (desomorphine) it and unlike levorphanol (in which norlevorphanol is the NMDA antagonist thus part of it's analgesic action), the C-ring of desomorphine is hydroxylated and N-oxidation competes with N-demethylation. Gluconation rapidly occurs in all of these species. On the other hand, some samples ONLY had 6-deoxymorphine in them which means that the C-ring isn't up for grabs.

There has been on and off sightings of the stuff around Europe, mainly in ex-patriot Russian & Ukrainian communities. I'm not pretty certain that it is phosphorous species that are responsible. The solubility of the different forms of P (WP,RP & BP) is diverse. From what I can see, the 'cooks' seem to add a little more I2 (in MeOH or EtOH as far as I can tell) until the product doesn't reduce it in an attempt to remove it but clearly the hugely elevated levels of P in the bodies of users fits the classic signs of chronic P poisoning.

It's tricky getting concrete data on ANY aspect of the stuff since the people making it to use themselves are in great peril BUT the 'expert samples' I have referenced had no P species in them at all. We know H2O2 will certainly oxidize P but the -PO2 & -PO3 species haven't been well studied for chronic toxicity. The LD50 of their monobasic salts is high by all accounts but IF it was solely P that is responsible, I'm going to stick my neck out and say that H2O2 is worth looking into more closely. 3M isn't about to explode if you heat it. The question is, how quick and how hot? Nobody is going to sit for more than a few score seconds, so it's then a case of working out if it IS a HR strategy.




OT - I find it ironic that commercial dextromethorphan synthesis relies on a chiral catalyst (otherwise you would need to remove 50% of the product - a Class A/CIII/Schedule 1 drug) and the plant would look like MacFarlan Smith's works in Edinburgh. Basically, you work in a prison-like environment. It would be at once funny and terrible if someone sent them the mis-labelled catalyst....
 
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Of the three commonly known allotropes of phosphorus, if elemental P IS the cause of krokodil toxicity, it can only really be the white allotrope, red phosphorus is insoluble in almost everything (IIRC it is soluble in PBr3, I seem to recall Schlenk's phosphorus/scarlet phosphorus being produced via crystallization of RP from PBr3, but thats a bit..out there), and black phosphorus is pretty unreactive, behaving more like graphite than other forms of P, also rather hard to make.

WP on the other hand, I can believe it. Although what is somewhat odd, is that I read of no reports of paralysis, or parkinsonian type effects. These were the primary effects, physical pain aside, from a low-level (acute) exposure, was in my school days, and caused no end of difficulty afterwards, had been doing a microscale distillation under inert gas to purify WP prepared via heating RP, and some of it spat, caught me on the forearm, and there definitely seemed to be neurotoxic type effects, due to transdermal absorption of however much actually entered my system, the most noticeable symptoms were severe parkinsonian-like tremor and shaking on trying to move the affected arm, and muscle weakness close to paralysis.

Never heard of either as a result of krokodil use.
 
IIRC [P4] is soluble in PBr3
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Oh boy, just what we need, can I buy a 200L drum of 10% sol'n?

Even if soluble hypophosphite / phosphite / alkylphosphate salts are present shouldn't a trivial basification and solvent extraction do wonders to purify it? Even a rapid filtration over silica should bind salts like HPO22- ? Why add H2O2 when you know they'll fuck the measurements on that too and end up with humongous, white scars along all major veins & on their hands?
 
clubcard said:
My admittedly old copy of The Merck Index lists duration as 60 minutes. At the much larger doses taken by regular users, it's 60-100 minutes according to most Russian HR sites. Don't forget, Krokodil can actually contain 6-deoxymorphine & 6-methyldesomorphine as well or even JUST be one of the 3. You have to look at the metabolic fate of them all. Seven different CPY450 metabolise the nominal parent (desomorphine) it and unlike levorphanol (in which norlevorphanol is the NMDA antagonist thus part of it's analgesic action), the C-ring of desomorphine is hydroxylated and N-oxidation competes with N-demethylation. Gluconation rapidly occurs in all of these species. On the other hand, some samples ONLY had 6-deoxymorphine in them which means that the C-ring isn't up for grabs.

There has been on and off sightings of the stuff around Europe, mainly in ex-patriot Russian & Ukrainian communities. I'm not pretty certain that it is phosphorous species that are responsible. The solubility of the different forms of P (WP,RP & BP) is diverse. From what I can see, the 'cooks' seem to add a little more I2 (in MeOH or EtOH as far as I can tell) until the product doesn't reduce it in an attempt to remove it but clearly the hugely elevated levels of P in the bodies of users fits the classic signs of chronic P poisoning.

It's tricky getting concrete data on ANY aspect of the stuff since the people making it to use themselves are in great peril BUT the 'expert samples' I have referenced had no P species in them at all. We know H2O2 will certainly oxidize P but the -PO2 & -PO3 species haven't been well studied for chronic toxicity. The LD50 of their monobasic salts is high by all accounts but IF it was solely P that is responsible, I'm going to stick my neck out and say that H2O2 is worth looking into more closely. 3M isn't about to explode if you heat it. The question is, how quick and how hot? Nobody is going to sit for more than a few score seconds, so it's then a case of working out if it IS a HR strategy.




OT - I find it ironic that commercial dextromethorphan synthesis relies on a chiral catalyst (otherwise you would need to remove 50% of the product - a Class A/CIII/Schedule 1 drug) and the plant would look like MacFarlan Smith's works in Edinburgh. Basically, you work in a prison-like environment. It would be at once funny and terrible if someone sent them the mis-labelled catalyst....
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any data available for these 2 compounds(6-deoxymorphine and 6-methyldesomorphine).Are these active on their own to a significant degree,and do those two share the pharmacological traits of desomorphine,having a short duration and being very fast acting.Also any guess on potency(x Morphine)?
 
At least, H2O2 would be also just as easily removed, due to the catalytic effects of several transition metal oxides, such as MnO2. Or catalase, from animal liver, etc.

And 200l? bloody christ...I cannot imagine what you are up to, but I'm not sure if I want to know.

Couldn't manage 200l, but smaller quantities, wouldn't be a problem. Would have to make the PBr3, but RP and Br2 are to hand..
 
That would be a terrible waste in terms of expense, and practicality. Granted the fumes from the PBr3 would make a wide area pretty unpleasant to be caught with your pants down in a vietcong tunnel, but the solubility of WP isn't huge in that solvent, it's sufficient to allow crystallization of Schlenk's phosphorus, but WP is only soluble to around some 10%, if one were to want to carpet-bomb a wide area, then a very low altitude airburst charge of phosphorus-saturated CS2 would get more of the munition to target, or simply disperse solid WP with an explosive charge, as in military incendiary rounds of modern day use.

But that much PBr3 would be awfully expensive, to carry sufficient white phosphorus to make a military-scale mess of a target.

And it is pretty efficient on it's own, without anything to dissolve it. Low melting point, and sticks to targets and keeps burning until it either burns itself out, or burns out the other side of the target, leaving acid in it's wake, and if the target doesn't get roasted, they end up poisoned, it REALLY doesn't take much to cause toxic effects. Been there, nastily surprised by it, so no need for solvent, it only takes a piece of WP a few mm in diameter and a couple of mm thick to cause pretty nasty, somewhat lasting effects.

Although a pretty passable napalm can be made with styrofoam and any reasonably viscous, flammable solvent that will dissolve it.

Not that I've got any particular desire to make use of it, buggering about as a kid, sure, but not these days:p

And either then, or now, I'd far sooner keep my RP, WP (don't as of yet have any sample of black, scarlet, violet or blue P, Hittorf's violet phosphorus is probably next on my list for experimentation, since the original preparation is probably the simplest of the more unusual allotropes, one route being heating white phosphorus in molten lead for 24-48 hours, then dissolving away the lead with HNO3 followed by boiling in concentrated HCl, the other being more difficult, requiring rather precise temperature regulation in an evacuated tube, held for many days in an electronic tube furnace, with a temperature differential, that being the difficult bit, then probably the scarlet allotrope, since that just requires exposing a CS2 solution of WP to light for a prolonged time. Everything I've ever read about black P makes it sound damn tricky to prepare, and the blue form I'm not entirely sure whether it can be prepared in bulk, everything I read on it suggests growth as a monolayer by molecular beam epitaxy, or growth as a few layers, that said, I've seen reference to exfoliation to prepare phosphorene, the P homolog of graphene, and one cannot exactly strip layers off a mono-layer of atoms, so it might be more interesting even so,
 
Look, BBr3 does NOT result in higher yields. I mean some of those samples had >90% of dessomorphine, 6-methyldesomorpine & 6-deoxymorphine in them. Yes, if you MUST have desomorphine then you can go down the (old) patent route... but the new patents just use HBr. Why make it hard? HI at the correct concentration and with the right rate-accelerant is also in the patents. I would expect 10% mol equivalent of Aliquat-336 to futher increase the yield based on... yet more patents. I might add that if I make a reference, I presume everyone trees that reference.

I'm talking about the real world. It's been amply demonstrated that amateurs are making it and sekio is most likely right in that it's WP to blame. Now consider the fact that the Russian experience talks about residences being rendered uninhabitable by the smell. A garlic smell, to be specific (search in Russian). An environment with WP floating about is NOT good for anyone regardless of if they actually use the stuff. WP is certainly oxidised by H2O2 so if it's placed in the cooker, it may be of great benefit. Obviously I need to check that but if this stuff IS turning up, better to give people the chance to decide to change. At the moment it's a one way street - people with the self-destruct button firmly taped down.

Krokodil users will NOT A/B the product. Mechanical losses make it really inefficient. They reuse the petrol or whatever it is they use to extract the C but consider all of the species left in the mix after the reaction. Any extraction solvent will have to be dumped or cleaned each time. BTW - BP is slightly soluble in water and if people are whacking the stuff up every 2-3 hours, how long will it take to reach toxic levels? P doesn't display clean allotropy, especially in hot, acidic conditions.

Ironically, it's a Russian paper that tackles the subject in the simplest manner. DOI: 10.1134/S0036024417100028

After all, isn't BL supposed to be about HR?
 
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That garlic smell, thats a dead giveaway.

And probably a dead junkie to go with it. Was reading a paper earlier where the street procedures were replicated and analyzed via GC/MS, and apparently the preparation after synthesis often extends to 'bring the PH up a bit by adding fag ashes, filter gross particulates and IV.

No wonder it's rotting people. Makes me think of a sort of globally-distributed phossy jaw.
And one thing I've noticed about WP, is that small amounts, often don't reach sufficient a degree of self-heating when exposed to air to become pyrophoric.

Had a bit of a cockup last year, where an alembic shattered, while being used to heat the red allotrope under a current of dry argon, distilling off white phosphorus, catching it under iced water.

The thing got too hot, and first cracked slightly, before going off in a huge fireball moments later. Made quite the mess of my back garden lawn to say the very least.

Small pieces (1cm or slightly less) will ignite, but if it's finely divided or as a thin layer on a nonflammable surface, an oxide layer forms that seems to protect a layer of white phosphorus for quite some time, bits of that alembic still smoked and gave off that characteristic garlic odour when the orange layer covering the surface was scratched, and that, was on pieces of shattered glass found months later.
 
After all, isn't BL supposed to be about HR?
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Well yeah, but at some point one has to draw the line in the sand. Can you do a pop bottle Birch reaction to make meth? Uh, yeah. Is it a smart or safe thing to do? Nope. Would I publish a "safe" method to do so? Nope. Because one small alteration could result in a flaming Gatorade bottle of kerosene and ephedrine melting onto one's skin.

There are Better Ways to do chemistry than cutting every corner possible in service of a drug.
 
sekio said:
There are Better Ways to do chemistry than cutting every corner possible in service of a drug.
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I totally agree but HR only works if people buy into it. I'm familiar with handing out brown-bags, naloxone & information. I don't see us handing out glassware & reagents or indeed dealing with used solvents. Sin-bins yes, solvents no.
We can only hope for additive HR and 3vol H2O2 is something Exchange Supplies CAN do.
 
Handing out glassware? I wish=D

But the likes of used solvent disposal, that'd just be a real shitty idea. It'd only be a matter of 'how soon' not 'if' some bugger dumps a ten year old bottle of ether, dioxane or THF that'll blow the place to hell the moment it hits the bottom of a bin.

3% H2O2 though, is non-threatening enough that they could give it out, hell its avalable OTC even here in this chemophobic shithole often known as the UK.

That said, anything with the word 'peroxide' in it's name is not entirely unlikely to trigger a terrorist-related panic. Including such concentrations as are OTC (up to 9% in pharmacies here),
 
On DMT-Nexus there was some thread about using cooking oils as a nonpolar solvent in extraction... This may be safer than flammable hydrocarbon solvents or the carcinogenic chlorinated hydrocarbons, but there's the problem that any saponification of the oil in contact with alkali could produce an emulsion that is difficult to break. Such oils are also more viscous than ordinary solvents, possibly mechanically worsening the contact between phases upon shaking. Haven't tried this with any amine, but it's quite obvious that CNS active alkaloids should be soluble in biological fats to some extent, at least enough to pass the blood-brain barrier.
 
I don't know how the UK deals with solvents but in 2001 I bought a stack of DCM in The Neterlands just before the price doubled. Their law meant the seller had to take back & dispose of dirty solvents and it is evidently expensive. Be honest - ANYONE in the UK can get everything to make Krokodil but the prices don't add up UNLESS given the low yield BUT I note the Polish shops sometimes stock pseudoephedrine & codeine containing meds that are OTC in the nation they are from. If someone just asked for a palette of the stuff - it's the wholesalers bringing it in and since they allow 30mg/500 paracetamol for ?2 then SOMEONE is goint to catch on.

Being in a position to respond to TicTac data fast with Exchange Supplies already up to speed, we can get the information to local HR groups in days rather than months and the sterile 3vol H2O2 to replace deionized water ready then we can get the plan in place, have a D&D News article published and hopefully stem the tide of destroyed bodies for long enough to go forward with 1-2-1 meetings with clients.

Of course, people asking for the H2O2 will be as depressing as seeing people you know moving from orange tops to green tops or blue tops. That point when you feel that this client won't last. Still, it would be worse if people were reusing or sharing pins. It can be a laugh but it's not a fun job. Stnill, people DO stop and getting them onto juice or bup the day they make the decision is the important thing. If it takes weeks, the majority change their mind... an chance lost.

Working on the methadone bus was much better.

Glassware is cheap but I don't see us getting funded. I think the most expensive thing I own is a porcelain 450mm Buchner funnel (1.5l). Plastic and metal ones suck.
 
Cooking oil? *shudders* what a nasty thought. The saponification part would fuck it up IMO. Hell, a lot of those high boiling, low flammability aliphatic alkane type solvents, stoddard solvent, heavy-duty cleaning solvent are terrible in practice, unless you need something to stick an alkali metal under for a bit, I do use cooking oil in my thiele tube, but IMO that is far removed from actually using it in chemistry since it's only in contact with the outside of a microcapillary tube and a thermometer plus an elastic band or wire tie.

And do you really want to have to vac-strip something like corn or olive oil? I don't. IMO if one cannot be careful enough to handle solvents which present only a flammability risk (E.g naphtha fractions, toluene, xylene, alcohols etc.) or flammability/ingestion toxicity such as MeOH, then you need not be in a lab to begin with.

I mean, sooner or later, unless doing only plant A/B extractions, you ARE going to come across something that presents much greater than a simple flammability hazard if inclined to do any serious chemistry. Hell, even what we think of as the entry level sort of cooking, such as nitroethane/benzaldehyde>P2NP, it's very common to use Al/Hg by beginners, and mercuric chloride is a LOT worse than most any solvents, Even I2/phosphorous reagent or RP based reduction of pseudoephedrine involves the intermediacy of PI3, Or potentially even phosphine if someone buggers it up with phosphorous or hypo acid. And doing it via the Birch instead of a Nagai reduction, involves handling anhydrous NH3 in liquid form, or else handling ether (I prefer the latter, it takes longer, but bubbling anhydrous gaseous ammonia through anhydrous diethyl ethereal suspension of fine lithium pieces will get the job done,)

The likes of acyl, alkyl halides, phosphorus tri/pentahalides, SOCl2 are essentials in any decent lab IMO, and if one cannot handle running a simple P2NP>amphetamine or pseudo>meth synthesis without resorting to that bastardized birch in a pop bottle monstrosity, then all hell is going to break loose when one comes to need to alkylate/acylate/chlorinate something.

And god help the poor bastard who can't handle solvents any worse than cooking oil when they find out they need something like hydrazine, azides, WP, or some godawful borane derivative that both stinks like a rotting dairy farm, wants nothing better than to rip your face off, and is pyrophoric to boot.
 
I'm not really saying that the cooking oil extraction is a serious idea, but it wouldn't be the first thing to sound really dumb on first encounter but still work to some extent. And I have handled things like liquid Br2, chlorosulfonic acid and red fuming >90% nitric acid in the lab. Something where cooking oil could actually be worth a try is the finding of a high-boiling solvent for tryptophan decarboxylation.
 
Cooking oil's have a BP inconveniently high and petroleum ether isn't exactly hard to acquire. DCM is the solvent for codeine freebase but not a phenol-baring derivative. Ethanol & isopropanol are fine. Throw in ethanolic or isopropanolic HCl solution and and equal volume of petroleum. 3 hours @ 0C will result in the product crashing out... filter and you have pure product... but that needs a lot of messing around and quite a loss of kit and as I said, the people DIYing Krokodil aren't about to do THAT. I suspect that is how the 'expert samples' were cleaned but who knows. The Russians are amazingly inventive in their DIY chemistry. Using acetylsalisylic acid to convet M to H is one example.

I HOPE nobody is going to do such dubious things.

However you look at it, it only makes sense to make krokodil for your own (self destructive) use.
 
Hey, since you are familiar with RFNA, you might answer me a quick question.

While RFNA needs the containers to be vented regularly to dispose of NOx gases that build up due to decomposing N2O4, does WFNA require the same treatment?

Instinct tells me it shouldn't, but always better to find out what can go wrong before it actually does.

Br2 isn't so bad IMO, but that stink...it was most aptly named IMO. It's the BrCl that comes off of the most expedient preparation (alkali metal bromide in saturated solution, gassed with Cl2), that is problematic IMO. Never actually had a problematic run-in with the stuff, but being a gaseous, more reactive version of ICl doesn't give me the warm fuzzies, considering the propensity of the latter to start fires, bugger up gas mask fittings (not the most ideal situation for that to happen, distilling the stuff) and considering the toxicity.

IIRC it isn't just the boiling point of the solvent that is responsible for the decarboxylation. It seems like an alkene present is important, IIRC weren't traces of cyclohexene in cyclohexane found to promote the decarboxylation? similar for carvone, etc.?
 
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