Org Prep Daily

August 2, 2012

Shake and pray

Filed under: lab destruction, procedures — milkshake @ 6:16 pm

There is a pop-chem procedure on YouTube that I find astonishing – it beats the Diet Coke and Mentos trick hands down:

A guy loads NaOH dry solid pellets, about 1 inch high, into a plastic bottle, and adds about 2-3 inch thick layer of dry ammonium nitrate granules. Then he fills the bottle with ethyl ether and adds a good chunk of lithium metal foil. He screws the cap on and swirls the mix around. God have mercy.

This man is not building a home-made ANFO for roadside bombing. It is not going to be a Molotov cocktail enhanced with a metal/oxidizer, or perhaps a crude rocket. He is making a batch of meth by the Shake and Bake method. As he ads a pack of ground pseudoephedrine pills, he squirts in a small amount of water, caps the bottle and starts shaking real fast. The water initiates a vigorous and pretty much uncontrollable reaction of the lithium metal with ammonium nitrate. The solids in ether gradually liquify and become a bottom layer sludge – this all is accompanied by evolution of  copious amounts of ammonia and hydrogen. So he shakes this thing by hand and he periodically vents the ammonia by loosening the cap  when the plastic bottle bulges up too much. Eventually the reaction slows down, the majority of lithium metal gets dissolved and the leftover lithium pieces floating on top of ether attain a bronze/copper hue, this marks the completion of the reduction. The ether layer is decanted into a small plastic bag, saturated with HCl gas (evolved from another soda bottle with sulfuric acid and NaCl) and the hydrochloride salt crashes out and is collected on coffee filter and dried. The yield is about 1-2 grams of a hilbilly-grade crank in form of a white powder, from one large pack of pseudoephedrine pills, about 2 hours start to finish. No glassware anywhere.

The method does not scale – attempts at running bigger batches end in self-immolation. A common error is adding too much water at the beginning, which leads to uncontrollable takeoff:  the whole ether/ammonia/NaOH/NH4NO3/Li brew squirts out. One can try and keep the lid on an a bulging soda bottle by a sheer force but as the Li metal floats on top and fast reaction makes the chunks of lithium pretty hot,  they tend to burrow through the plastic wall and an impressive stream of flaming goodness rushes out with them, delivering bright red and yellow-colored ether flames accelerated by ammonium nitrate and lithium metal all over the place. As one skin graft patient observed “I haven’t seen stuff burning this fast before”.

The Shake and Bake meth is a twist on the classic method using Li metal with anhydrous liquid ammonia/ether. The outdoor storage ammonia tanks are now getting watched and additives are introduced into agriculture-grade NH3(l) so as to ruin its usefulness for dissolved metal reduction. Hence the soda bottle modification for ammonia generation in situ. No need to go to fields, now you can cook in the safety of your home…

Note: It would be easy for a manufacturer to add some organic soluble iron compound like Fe(acac)3 or ferrocene to the ether-based starter fluid  and likewise a small pinch of FeSO4 to the ammonium nitrate in cold packs and lye/drain opener. A finely divided iron promptly decomposes Li metal solution in ammonia to lithium amide and so it would make these materials useless for home brewing.

32 Comments »

  1. Where does the “home hobbyist” get lithium foil and Et2O?

    Comment by Joe Q. — August 2, 2012 @ 11:35 pm

  2. lithium batteries and and starter fluid

    Comment by milkshake — August 3, 2012 @ 3:50 am

  3. is there perhaps a video of the actual procedure anywhere? just, um, curious.

    Comment by subnaught — August 6, 2012 @ 3:04 am

    • there are actually several Youtube videos – I saw one particularly frightening: Li metal repeatedly bursting into flames in contact with ammonium nitrate layer while being immersed in ether, then going out (by bouncing up into ether layer where there is apparently less oxygen), this all in a 2L thin wall plastic soda bottle. I did not want to provide a link to such a completely suicidal video procedure, even with an appropriate commentary.

      Comment by milkshake — August 6, 2012 @ 11:36 am

  4. As dangerous as that procedure is, it’s kind of ingenious, particularly to be robust enough for various people to use without really measuring reagents and with questionable starting materials. I would think that there is a very narrow window of water concentration for the thing to work, too much and the lithium is quenched (most likely violently), not enough and the ammonium nitrate and sodium hydroxide don’t react and/or the intermediate anion from pseudoepedrine is not protonated. Having seen it I can understand how it would work, but I never would have assumed it was viable otherwise.

    Watching those videos I am also dumbfounded that they shake the crap out of the reaction and even invert the bottle at times. I’d be terrified of the aqueous salt sludge coming into direct contact with the lithium (if we are looking at the same videos, that is when the brief fire occurs). If you could keep those layers physically separated you could have at least some small hope of avoiding self-immolation, otherwise good luck.

    Comment by Mike S. — August 8, 2012 @ 1:27 am

    • I don’t think ‘ingenious’ is the correct term; perhaps ‘mental’ would be more appropriate. I feel sorry for anyone attempting to make meth (the worst drug imho), especially by one of these methods – they must be absolutely desperate!

      Comment by Gnown — August 9, 2012 @ 9:27 pm

      • There is an impressively bleak movie “Winter’s Bone” on Netflix, about a family of a rural meth cook trying to locate their missing dad. It has a great acting, it is non-sentimental and has a happy end (of a very grim kind).
        Yes I think these people are desperate – and they don’t know any better.

        Comment by milkshake — August 9, 2012 @ 9:47 pm

  5. what is the alternative for CCL4 for NBS reactions? Free radical brominations.

    Comment by A!@yahoo.com — August 8, 2012 @ 10:28 am

    • I heard people run this very successfully in 1,2-dichloroethane at 60-80C, with react mix irradiation using visible light (200W construction site flood lamp bought at Home Depot for something like 15 USD). Also, please use old NBS, not recrystallized one – a trace of decomposition-related impurity (Br2, HBr) sometimes helps the reaction.

      Comment by milkshake — August 8, 2012 @ 11:47 am

      • I have used this method many times – it gives excellent results. Get the lamp just close enough so the mixture barely refluxes; use boiling stones and an air condensor.

        Comment by Russ — August 8, 2012 @ 6:20 pm

        • Also see J Chem Ed using benzotrifluoride (i.e. trifluorotoluene) as solvent for this rxn. A little greener than the chlorinated solvent approach.

          “A Substitute for “Bromine in Carbon Tetrachloride””, Journal of Chemical Education, Vol. 82 No. 1 January 2005

          Comment by psl — August 13, 2012 @ 8:05 pm

          • ok, I just have to say, you win the internets for quoting a Scientific Journal in an article about making Meth…

            Comment by Puella Nivis — May 9, 2013 @ 4:23 pm

      • Yes indeed, I have done this reaction with the setup just as you describe using NIS (to perform an iodolactonization) as well as NBS, both work fine. I did several runs: putting a reflux condenser on top was too cumbersome and the cooling lines got a little melty from the lamp. I found that running it in a sealed tube was most convenient and the heat from the lamp was plenty hot to get it up to the boiling point of DCE without an oil bath. Here is a link to an old tenderbutton post I wrote about it (login: tender, password: button). http://archive.tenderbutton.com/?p=256

        Comment by dylan — August 14, 2012 @ 10:09 pm

        • sorry for not mentioning the source in my comment – Tenderbutton was most likely the place where I saw it the first time.

          Comment by milkshake — August 15, 2012 @ 2:00 am

    • chlorobenzene (PhCl) is also used quite often, I have seen a publication in Organic Process Research & Development

      Comment by Alexey — August 16, 2012 @ 4:07 pm

  6. Thanks a lot. I will let you know the outcome of my trial.

    Comment by A!@yahoo.com — August 9, 2012 @ 9:32 pm

  7. In case someone missed the reverse reaction. BTW thanks, Google, for the “did you mean ‘conversion of pseudoephedrine to methamphetamine’ ‘now showing results for conversion of pseudoephedrine to methamphetamine'” When a bunch of G-men come knocking on my door, I’m going to have a hard time explaining this one.

    Also, whenever I am reminded of the fact that high school dropouts can do successful organic transformations using stolen garbage yet my carefully set up reactions in quality glassware with fine reagents turn to brown muck, I get a little frustrated.

    Comment by Bob Honclbrif — August 10, 2012 @ 4:13 pm

  8. Milkshake, I read your post about job interviews (in the archives from 2006), and I have to say it was extremely informative! However, I’d like to know if the process would be the same for an MS fresh out of school — would they require you to present your MS research, are they more likely to ask dumb HR questions, are they still going to take an entire day to interview you? I imagine this probably varies greatly from company to company, but any insights would be much appreciated!

    Comment by student — August 21, 2012 @ 1:52 am

    • Hi, best luck with your job search. Please keep in mind that not everyone interviewing you will be professional interviewer – they could be just as awkward and nervous as you. Also, if you get several one-on-one meetings, from all these meetings only one or two will be really important – the interview with your immediate boss (who is hiring person into his group so you really need to impress him) and typically also the boss of the chemistry dept who likes to watch over the new hires. The role of HR is often a formality but you should not annoy her (even if she is asking those dumb questions).
      You probably will need to present something from your research. For MS position everyone understands it is not as a major project as with a PhD candidate but you will still need to be able to talk about what you have been doing in the lab in a reasonable intelligent fashion. So try to put it into a coherent story – what was the purpose and what exactly was wanted, how you went about it, what kind of problems cropped up and how you dealt with them and what was the outcome of that project and what other interesting things happen. You need to clearly differentiate what was your work, what were your contributions and improvements you came up with, and what were the results of other group members and how they relate to your work/

      Comment by milkshake — August 21, 2012 @ 12:13 pm

  9. Thank you milkshake. Ironically enough I feel that my MS project would make for a more interesting story than my BS project simply because it required a lot of troubleshooting since the chemistry was very picky about the substrates, whereas the BS project was pretty much smooth sailing from day one and it would just be “yeah this worked and that also worked, here’s 4 tables worth of examples” (both MS and BS projects were methodology based). That reminds me, in my research summary I talked about both my MS and BS projects, but because my BS project has since been published, I want to focus my presentation entirely on my MS project, but I don’t know if that would be frowned upon since they might expect me to elaborate on my BS project if I put that in my research summary. Or maybe I could just say “in the interest of time I’ll only be talking about my MS project, but I have brought some reprints of the published work from my BS project and would be more than happy to discuss any specific questions”

    Comment by student — August 21, 2012 @ 12:44 pm

    • It depends on you, you can certainly give a talk about two unrelated projects. It does not matter whether some of it was published already – in fact it looks good when you include the reference to your paper somewhere on your slides. You can prepare more slides than necessary and put few extras past the end (in case you get asked about those details, you can then pull those addendum-like slides). Remember, the purpose of this presentation is not to give a conference-presentation level talk. It is to show you in the most positive light and invite a good discussion where you can impress your potential employers even further

      Comment by milkshake — August 21, 2012 @ 3:17 pm

      • Milkshake, what would you say is the average salary range for an MS associate at a large-ish pharma? I’ve tried doing my own research (ha) but it seems to be all over the place, it’d be nice to have an insider’s perspective. (you can email me if you prefer, many thanks)

        Comment by student — August 29, 2012 @ 8:07 pm

  10. I wonder if ferrocene is stable in the presence of lithium metal, or does it cause the decomposition to lithium amide in ammonium in the same manner as FeCl3? Reason I ask is because ferrocene is benign to engines, it is used as an anti-knock agent in many formulations.

    Comment by opsomath — September 11, 2012 @ 2:03 pm

  11. Links, or it didn’t happen!

    Comment by KemKat — September 16, 2012 @ 4:41 am

  12. The original Shake n’ Bake method was developed by someone on The Hive over a decade ago. I read an analysis of the mechanism of the reaction a while back out of shear interest and although it may see like a remodification of a Birch reduction, it actually might proceed through a Li complex that does the reduction and leaves the copper colored lithium at the end. From my understanding, that doesn’t happen in the Li/NH3 reduction method, but I can’t speak from any sort of experience.

    Comment by ChemicalEnthusiast — February 20, 2013 @ 9:38 am

  13. your note at the end might have been useful here: https://www.innocentive.com/ar/challenge/9933386

    Comment by anon — October 21, 2013 @ 12:57 pm

    • Thank you – I am aware of this Innocentive Challenge and I was actually thinking about submitting a solution but in the end I got lazy. First, adding Fe-based compounds into pills with pseudo is not a new idea, there are patents describing just that (ferrocene works great for example), the problem here is to use exclusively additives that are listed on the GRAS (generally recognized as safe) list of ingredients approved for use in pills. It could be done. Second problem is that Innocentive challenge asks for some lab actually performing experiments to prove that all possible meth cook alternatives would be thwarted by this modification (I don’t have my own lab, or a pill press, or a license to work with class II substances – and I am definitely not suicidal to do “shake and bake”). The reward for purely theoretic proposal is much lower.

      Besides, this is a wrong approach, far more effective and cheaper would be to add trace of iron to cold packs ammonium nitrate and the ether starter fluid. I think the manufacturers of starter fluid and cold packs are unwilling to do something about the problem on their own because they profit from the misuse of their products. They would have to be forced by a some kind of regulation. And anyway, most of the meth in US comes from cartel labs in Mexico and they buy Chinese-made pseudo in pure substance form, fighting redneck garage cooks is not the most important thing to do IMHO.

      Also I have sketchy experience with Innocentive – their challenge problems are often worded in such a way that the they are nearly impossible to satisfy, which leaves lots of wiggle room to not to pay anybody. Also, the author of the challenge gets to read a pooled input from several hundred solvers, but has to pay only one award – if he feels like it. Innocentive takes its cut from the Challenge regardless of what happens. The system is prone to rip-offs.

      Comment by milkshake — October 21, 2013 @ 2:01 pm

  14. Looking at the reaction on paper I do not think the water is even necessary if the correct molar masses are used. To me this only seems to increase the danger level exponentially. Granted, if the heat can be adjusted then the reaction can be better controlled. This could be done even in a soda bottle without any special equipment, but even controlling the heat of the reduction one would not want to add water. I mean why? What is it supposed to do? It does not have any chemical effect. I don’t get that part, unless people think it is starting the reaction. It really isn’t. Doing the reaction described in this article would probably work if the correct masses were used, but the product would likely be of a very low grade, IF anything is gotten at all. It will work but incorrect quantities of the various agents would likely just make the whole thing fail miserably. Various washes could be performed to increase the quality of such a reaction, both pre and post reaction procedures. I mean seriously? Dumping crushed pseudoephedrine into the mix? Does anyone have any idea the fillers that are in that crap? This will affect the reaction in some way I’m sure. To do this reaction properly, although I am not experienced as I’ve never attempted to do anything this crazy, I can think of at least 3 more chemicals that would be needed. Maybe even more than that. Not for the reaction itself of course, as that is relatively simple in chemical terms considering the similarity of the molecules that are being converted into methamphetamine, and in fact this method is relatively interesting. Granted it has been known for a long time though in science. This reduction needs high pressure, and although soda bottles are rated at a high enough PSI for the reaction to properly occur, as has been pointed out an uncontrolled reaction can quickly escalate into something dangerous. If anyone is dumb enough to try this, for goodness sake don’t put freaking water into the bottle with the Lithium. And another thing…You would not put the crushed pills in at the same time. That would probably make the product inferior as well I would think. I personally don’t care what people do. If someone wants to do it, they should at least have proper information. One shouldn’t half-ass anything, even if I don’t agree with what they’re doing. If people wish to ruin their lives, that is their business. Nobody should be able to tell someone else what they can or can not put into their body.

    Something that some people are overlooking is the following: you think that because all these harmful chemicals go into the mix that all of these harmful chemicals are going into one’s body. This is NOT the case by any means. It is chemistry. All that is occurring here is a molecular shift. A reaction, in this case a reduction. The final product is not going to contain these toxic chemicals. It could be argued that methamphetamine is a toxic chemical, but really it is not. The effects of long-term use are bad of course, and it is addictive because of its similarity to dopamine and the way it binds to receptor sites, and all of this is known…But saying that putting this substance into your body is akin to drinking acetone or sulfuric acid is just ludicrous and downright laughable.

    Comment by JiggyPotamus — June 9, 2014 @ 4:14 am

    • dude, you must be high as a kite. Please go away kindly, reddit is a better forum for your rambling – I won’t have any more of it here

      Comment by milkshake — June 9, 2014 @ 10:56 am

  15. You know where the shake a bake receipts for meth originated? Let me give you a hint: he won a Nobel Prize in Chemistry and is still alive today

    Comment by Frank — July 15, 2014 @ 12:20 am

    • Shake and Bake dates to the “Anarchist cookbook”, which from what I heard is a collection of dangerous and unreliable crap. Please what makes you think that Sharpless (or EJC) had anything to do with this?

      Comment by milkshake — July 15, 2014 @ 1:14 pm


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