The Vespiary

The Hive => Stimulants => Topic started by: elfspice on May 02, 2004, 04:32:00 AM

Title: removing iodoephedrine
Post by: elfspice on May 02, 2004, 04:32:00 AM: I was just looking at some info about halogen groups from haloalkanes, and it said that a hydroxide can remove it.

Iodoephedrine is crappy. nobody wants it. Is there any reason why a reflux in conc NaOH to impure reaction material wouldn't remove all those iodoephedrines, leaving them as ephedrine again, which can be then separated via distillation to be able to be re-reacted.

Could it bee that this is why kerplunking improves the effects?
Title: ReX Improves but does not eliminate
Post by: ChemoSabe on May 02, 2004, 05:33:00 AM: Swim's buddy had never had much luck de-iodomething as opposed to de-iodoephedrining which he's not attempted at all.

ReXing always improves Iodoed meth but has never really cleared it up fully.

Mostly clueless about the iodoephedrine.
Title: google "hydroxide haloalkane reaction"
Post by: elfspice on May 02, 2004, 10:24:00 AM: Since the hydroxyl is attached, not on the benzene, but on the aliphatic saturated carbon chain, it should react much similarly to the haloalkane:

http://www.chemguide.co.uk/mechanisms/nucsub/hydroxide.html (http://www.chemguide.co.uk/mechanisms/nucsub/hydroxide.html)

That would mean refluxing the reaction with alcohol and base added (probably equal volume to the reaction fluid) - add the base first of course to neutralise the hydriodic acid. Should only take about half an hour, and the result will be no iodocrap.

This would make it very worth the effort of using simple distillation to use the different boiling points of the ephedrine and meth, as there would be no iodoephedrine left after the sodium hydroxide gives it's OH to the iodoephedrine, and steals the iodine.
Title: haloephedrine to aziridine
Post by: Rhodium on May 02, 2004, 02:31:00 PM: Treatment with base cyclizes haloephedrines to the corresponding aziridine:
Post 483374 (https://www.thevespiary.org/talk/index.php?topic=8340.msg48337400#msg48337400)
(Rhodium: "Synthesis of the required aziridine", Stimulants)

You need some kind of reductive removal. An atmospherical hydrogenation reduces both haloephedrines and aziridines to meth:
Post 483349 (https://www.thevespiary.org/talk/index.php?topic=8340.msg48334900#msg48334900)
(Rhodium: ""Ephedrine Aziridine" Reduction to Meth", Stimulants)
Title: Iodoephedrine as impurity from a HI reduction...
Post by: Organikum on May 02, 2004, 03:22:00 PM: Iodoephedrine as impurity from a HI reduction is a urban myth.

Why is everybody so sure to have iodoephedrine? The forensic vultures never have been able to detect this impurity in street meth - in difference to chloroephedrine which is actually an impurity in meth made by catalytic hydrogenation pathways. (after my best of knowledge).

If iodoephedrine would be a common impurity we would face shitloads of goverment financed studies on the dangers of this compound (see chloroephedrine).

You may have crap in your post-reaction, you may have iodine compounds there maybee, but I bet you dont have iodoephedrine.

How to get rid of the shit?
Steamdistill. First steamdistill the still acidic post reaction mixture - add water and boil it away fast - this will remove all iodine which might be left and a lot of other steamvolantile crap. Then basify and steamdistill the meth-base out.
Thats it.

ORG
Title: Basic workup cyclizes it
Post by: Rhodium on May 02, 2004, 05:42:00 PM: If iodoephedrine has been freebased (which happens in nearly all workups) it will cyclize to an aziridine - and that toxic substance has been detected in all forensic studies I have read to date.
Title: Any guess for how long iodoephedrine/aziridine
Post by: Osmium on May 02, 2004, 06:32:00 PM: Any guess for how long iodoephedrine/aziridine will survive under GC conditions?
Title: Nevertheless there will be no iodoephedrine in
Post by: Organikum on May 02, 2004, 06:34:00 PM: Nevertheless there will be no iodoephedrine in the product but an aziridine. The posts above all talk about the removal of an non-existant impurity - agreed?

So it would be right to talk about the removal of aziridines, wouldnt it?

I want to add that I have an differing opinion onto the way aziridines and other impurities come into existance, but I dont want to start to argue about this again now and here :)

We agree that there is no fucking iodoephedrine present - why is another question. So there is no need to talk about its removal - yes?

My question: Will aziridines go through an double steamdistillation - acidic/basic conditions as described?

PS: Even ephedrine is known to get easily reduced to methamphetamine under GC conditions, so iodoephedrine wont have the slightest chance to stay this treatment. But the same is true for chloroephedrine and GC is not the only anylytical method available I guess. If it would be all those chloroephedrine articles would never have been written.
Plain academical question.
Title: Impurities in HI/P Methamphetamine
Post by: Rhodium on May 02, 2004, 09:38:00 PM: Investigation of the impurities found in methamphetamine synthesized from pseudoephedrine by reduction with hydriodic acid and red phosphorus
K. L. Windahl, et. al.
Forens. Sci. Int. 76, 97-114 (1995) (https://www.thevespiary.org/rhodium/Rhodium/chemistry/meth.hi-p.impurities.html)
(https://www.thevespiary.org/rhodium/Rhodium/chemistry/meth.hi-p.impurities.html)
Title: Also I believe to be able to interpret this...
Post by: Organikum on May 02, 2004, 11:15:00 PM: Also I believe to be able to interpret this heap of diagrams halfway for my own, I wont dare to post this interpretation.

Might you Rhodium please interpret this for us non-chemists?

There is at least one clear sentence in the article: No aziridines were found at the end of the reaction. I couldnt find anything representing iodoephedrine in the data for the regular finished reaction product - but maybee I just couldnt recognize it?
At start it is told "hurrah! we discovered two new impurities!" but it seems the amounts are not very big - small enough to raise the question if the boys have cleaned their instruments well enough.......
But thats what I read there. And I am no chemist.

ADDON: And what is this fuzz all about please? I told iodoephedrine is a myth and Rhodium "all iodoephedrine converted to aziridines by basic workup" - yes? So there is no iodoephedrine. And thats all I told. In addition I suggested a workup method which is even supported by Osmium - oh yeah! Acidic/basic steamdistillation. Something wrong with this?

Sorry, no offense intended and not to be misunderstood, but I feel very confused and misunderstood here. Damn. Whats fucking wrong about it?
Title: hmmm...
Post by: elfspice on May 02, 2004, 11:24:00 PM: interesting...

so this means if one were to deliberately make the halo-ephedrine (beta position substitution) that it would form the aziridine after being turned into the halo-ephedrine... and this would not be reduced to meth via HI.

useless...

i now hate hydriodic acid
Title: Nonsense. Aziridines are very well reduced to...
Post by: Organikum on May 02, 2004, 11:34:00 PM: Nonsense. Aziridines are very well reduced to meth by HI. The authors of the article state that they found lots of aziridines during the reaction in progress but none after the reaction was finished.
This says that one possible way for the reaction to take place is through the intermediate formation of aziridines which get reduced to meth lateron. This is an argument for the long reflux as reaction scheme.
Nobody says this is the one and only way this reduction can take place - it is very well named in the article "a possible reaction sequence".
Title: Elfspices Ker plunk Q
Post by: ChemoSabe on May 03, 2004, 01:47:00 AM: I woulnd't say for certain but your initial kerplunk question may have had some validity. Back when swim's buddy was doing the hot 1 hour cooks the ker plunk always seemed to do wonders for both yeilds and overall quality. It seems to not affect LWRs as markedly but I'm assuming this is due to the completeness and cleanliness of the LWR.
Title: kerplunking
Post by: elfspice on May 03, 2004, 03:07:00 AM: Alrighty rooty

KERPLUNK KERPLUNK you should all kerplunk, lwr or not.

you know something i now have worked out a new synthetic modality.

the kerplunk... If i were to say, how could one reduce cyclicisation from basification so that it were not able to immediately cyclicise... what is the difference compared to the basification workup and this idea of diluting with alcohol to help hold the stuff in... what would help prevent the aziridine forming, which i can see, although it is a very unstable 3 member ring, it has to be reduced to release it. It doesn't have to be strong mind you.

Would sodium react with aziridine in the desied way? I have to have a close look at the structure's hydrogen counts to see if the hydrogen could be donated directly by the....

D'OH of course, what is a birch reduction?

the use of sodium metal (or other group one metals) to withdraw the extra hydrogen from ammonium and donate it to a hydroxyl group so as to saturate it's bonds and dehydrate it.

The page i linked to, which obviously nobody actually read, showed a diagram which clearly showed that the re-hydroxylation process caused by a hydroxide reacting with the halogen, and this OBVIOUSLY is going to liberate sodium in an active form if it enters a low hydration enviroment, if only for a moment as the substitution occurs that puts the hydroxide on the site of the halogen and the halogen forms an ion with the sodium.

Looking at the chemical dynamics involved in the kerplunk process, i propose an alternative method, which quite possibly could in fact be an alternative reduction method, based on Phase Transfer Catalysis.

This kerplunking thing involves the salt sodium iodide (the result of adding sodium hydroxide to the iodine laden reaction mixture) being present, so there would have to be this salt in the environment. The reaction requires the participation of hydroxides, so there has to be an excess of sodium hydroxide to the reaction. Here is a proposed reaction mechanism, not really taking into account the mechanism, just to illustrate how the presence of water and the nonpolar phase contribute to this:

Na+OH- + H+I- + methamphetamine-OH --PTC reflux--> Methamphetamine + Na+OH- + I- + H2O ---> methamphetamine + Na+OH- + H+I- + OH-

This reaction is driven forward primarily by heat which increases molecular kinetics, and the fact of the phase boundary which permits freebase ephedrine to expose it's water soluble one and only part, it's hydroxyl, to the polar phase.

At the phase boundary, the ephedrine is reduced to iodmeth, which is then immediately cyclicised to the aziridine, which then can go further to be reacted with the sodium ion at the phase boundary to decyclicise, possibly taking the hydrogens from the nonpolar solvent, unsaturating it. A-La birch reduction, except done as PTC.

This is such a simple experiment that I think it would be worth seeing if say, 240mg, a single 240 pill, were subjected to this treatment directly, without even addressing the gaks or anything. If the ingestion of the acid/base extracted product of this experiment gave noticable or more than noticable activity, this is a route of synthesis that should be pursued. proper ratios of the NaI and NaOH will be established, lengths of reaction time etc etc.

This reaction is so beautiful in its elegance and simplicity, that even if with maximum optimisation it only yields 50%, this is an acceptable situation because of the fact that no difficult chemicals are required, just a refluxing setup that can handle strong alkali.
Title: I would surmise that Orgy's solution would work
Post by: dwarfer on May 06, 2004, 10:43:00 PM: As the salt, boil snot out of it.

Base, adn then GENtLY steam over the esier to transfer
meth.

You can effect a reasonably decent separation of metha from unreacted precursor this way:

so I THNINK (likely maybe) it would work similarly with
GENTLE steamingconditions..
Title: If you did the reduction right in the first...
Post by: amalgum on May 06, 2004, 11:56:00 PM: If you did the reduction right in the first place, why would you even be worried about iodoephedrine?
Title: Right Way? What's that?
Post by: wareami on May 07, 2004, 02:48:00 AM: ;D
>If you did the reduction right in the first place, why would you even be worried about iodoephedrine?

What a novel idea! 8)
The problem with that suggestion is that for years the completion parameters weren't set correctly that would allow for the removal/conversion of the aziridines and other by-products.
The first sign of conversion/completion was enough to call it done and pull it.
Also there has been some longstanding misconception which has since been solved, surrounding hydration and temp, both of which have an equal consideration when a bee needs to say to the rxn...(and the MethGodz)
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000504278-stulovesthis.gif)
Who's Yer Daddy???

This still doesn't address the needs of those attempting to pioneer new ways for the good of the collective.
It's very easy to tell most the right way to do it, but the slightest deviation from that instruction will result in questions such as the one above..._{Nooo....not who's yer daddy?}...what to do with excess iodo-sides present in the end-result. :P
I think it's evident that they simply need to be cooked off.
But that isn't an easy proposal once the work-UP is complete.
One would have to test some known Iodo endresult then keplunk and retest to see if it converts/oxidizes them.

Elfspice: I curiously await to hear of any new breakthroughs along the lines proposed.
Title: Re: Removing iodoephedrine
Post by: java on May 07, 2004, 05:32:00 PM: Assuming... we're talking about C6H5-CH(I)-CH(NHCH3)-CH3, then to me , I've always had to struggle to make the Haloephedrine ( chloroephedrine) and hydrogenated with Pd to convert to meth, something that iodoephedrine would do much easier since it's an easier leaving group. As for the aziride impurities, I once read an article from a forensic report where they just heated the meth in a warm oven for ten minutes and the azirides were no more. .........my two cents as I see it....java
Title: Are you perhaps referring to a GC-MS?
Post by: Rhodium on May 07, 2004, 06:14:00 PM: As for the aziride impurities, I once read an article from a forensic report where they just heated the meth in a warm oven for ten minutes and the azirides were no more.

That sounds like bull to me - where would the aziridines go?
Title: Hmmmm...
Post by: wareami on May 07, 2004, 09:07:00 PM: Java: With all due respect regarding the question to that forensic report, I must agree with Rhodium.
For what possible reason would a forensic team, through the process of analysis, try to refine or purify a specimen that would, you would think, be regarded as collected evidence.
Just puzzles me. ::)
Not that I question that you read it, but maybe misinterpretted...
Again...with all due respect.

And in an attempt to keep with the kerplunking theory, and heat....my belief has always been grounded on the principal that cooking longer either reduces or oxidizes aziridines or iodo impurities.
I was of the belief originally that oxidation of the free iodine through treating the post-rxn solution with the addition of Na₂S₂O₃-
5H₂O would effectively deal with iodo-side impurities.
I now feel that is not the case.
Yes it removes free iodine, but not the more complex aziridines or other necessary intermediates created during the reduction process.
Those necessary components created will go onto the building of a purer meth specimen if allowed to run the course to completion through longer cooking...IMHO

This leads me to believe that elfspice and chemosabe, et.al...may be onto something by looking more into the mechanics behind kerplunking that uses heat as a catalyst of sorts in bringing the product past some of the worst gaak encapsulators.
Those inhibitors can be viewed as impurities as well since they survived the rxn.
Just thinking...
Title: Look ware, I wasn't trying to attack you ...
Post by: amalgum on May 07, 2004, 10:58:00 PM: Look ware, I wasn't trying to attack you personally or anybody for that matter. SWIM never had a problem with reduction in the past once he got the hang of it. He has analyzed his own product everytime with tlc and mp tests, and granted his tlc technique is not that great, but iodo impurities are no longer a problem. Your also right about how you can tell people what to do but they are still not going to do it exactly right. Well, thats their bad. The literature on how to do it properly is out there for the taking, it is up to each individual chemist to make it work for himself or herself, thats what SWIM did and is sure thats what you did and several other people on this board. Besides they will get a lot more from it if they learn to tweak the rxn themselves, as then it becomes a learning experience. It's all science and technology, not mystical "meth gods".
Title: Re: removal of azirides
Post by: java on May 07, 2004, 11:56:00 PM: Rhodium, and fellow Bee's.....Well how about that I did misread the article , sorry about that I'm wrong and all I can do is provide the article that led me astray ,or should say misread.....I just don't know how I got aziridine mixed up ..must be gray matter failure ...........java

Title: The Use of Heat to Eliminate Dimethyl Sulfone from Amphetamine and Methamphetamine Hydrochloride Samples
Author: Morales-R
Source: MICROGRAM; 1999; V32 (1); January; P10
Abstract: It is frequently the case that samples of methamphetamine hydrochloride or amphetamine hydrochloride are mixed exclusively with dimethyl sulphone. It was found that, when attempts were made to identify the methamphetamine/amphetamine salt in the presence of dimethyl sulphone, the dimethyl sulphone interfered with the IR spectrum. In order to isolate the controlled substances from the dimethyl sulphone, therefore, the sample was heated in a convection oven for 10 minutes at a temperature of 115C. As the sample was heated, the dimethyl sulphone sublimated, leaving behind the methamphetamine hydrochloride or amphetamine hydrochloride. If this process does not work, then heating the sample for a further 10 minutes should solve the problem.
Title: Ooooops....
Post by: wareami on May 08, 2004, 05:03:00 AM: amalgum: Apologies if I gave the impression of coming off from a defensive angle.
I know your statement wasn't intended to offend or beelittle anybee.
I was simply pointing out a flaw in that kind of suggestion, as it should bee a well accepted fact, if it weren't for the overlooked mechanics of the RP/HI, or the variables being discussed such as the ones in this thread.
I hope you know that my choice to use that statement as an example, is no ill reflection personally or toward the many useful contributions from SWIM's corner in past.
Looking back, I can see ware I may have given the impression I was being defensive.
Had you elaborated some more in that reply I wouldn't have felt the need to pipe-UP with my reply using your statement as an example! :)
No offense...okies?

java: Thanx for clearing that UP! Something just struck me as odd considering what's been disclosed in the past from forensicko's :P reports.
After some long thought however, prior to posting, I did consider that from a prosecutory standpoint, it would be easily understood why a forensic team might try to fudge the potency analysis for leverage in building an otherwise weak case. But we all know they wouldn't stoop that low now would they? :o

Methylsulfonylmethane...aka...Dimethyl Sulfone, MSM

That little peace is very enlightening though and something that Ibee's never had to deal with but sees it addressed from time to time here on the board by those plagued by it's presence in streetgear!
So that's all there is to ridding it?
Many bees should be jumping for joy, as I've seen many ways suggested to deal with it's removal, but never so easily.
Maybe I just missed it since it's not an area of concern in Ibee's circle!
Title: No pobs wareami 8-) SWIM guesses he should...
Post by: amalgum on May 08, 2004, 11:29:00 PM: No pobs wareami 8)

SWIM guesses he should have looked at it from the newbee side of things, as it would be better for their health to learn how to get rid of side things like iodo shit and aziridines. SWIM didn't mean to appear cocky.