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Author: Subject: NH4NO3 rendition of psuedo-Birch reduction
chemrox
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[*] posted on 26-9-2010 at 12:21
NH4NO3 rendition of psuedo-Birch reduction


Watching a TV show on the scurge of meth in middle america I ran across the "one-pot" or "shake & bake" reduction of ephedrine. I did a brief search and found the method detailed in something called the Clandestine Chemist's Notebook: http://www.scribd.com/doc/35411/The-Clandestine-Chemists-Not...
It seems that reduction of the hydroxyl can be accomplished using Li and NH4NO3. Maybe the Li-(NH3)x complex is formed as the reaction proceeds. I haven't dome a true literature search yet. I'm not sure what the search terms should be but I will try tonight. If this is a synthetically useful reduction for reducing things like aryl halides I'd like to know about it.




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wink.gif posted on 4-10-2010 at 08:36


it's called lithium bronze i think that's too strong a reducing enviroment for the substrate you have in mind (tertiary benzylic alcohols) will snip it right off.

that looks like a recipie for chemical ashixiation,burns, expolsions.
who wrote this shit?

[Edited on 4-10-2010 by jon]

[Edited on 4-10-2010 by jon]
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chemrox
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[*] posted on 4-10-2010 at 09:22


I ran across it on the telly, I searched acs and couldn't find a word about it. I tried NH4NO3 & Lithium & reduction and various permutations. So since you've at least heard of it, how does it work and is it a worthwhile reduction? If so for what? If it's too harsh a reducing environment why are the cooks using it? If the cooks are using it why can't I find anything in the legit literature? (I haven't looked in the abstracts yet). The reason for my curiosity is the potential application to other reductions. NH4NO3 is cheap! Li metal is not terribly expensive either. Handling would be more convenient than in typical Birch or modified Birch conditions. btw did you mean asphyxiation? Tell us about it, please. Is their a paper or two?

(there was a thread on this the FSE didn't find for me: http://www.sciencemadness.org/talk/viewthread.php?tid=12727)

[Edited on 4-10-2010 by chemrox]




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[*] posted on 4-10-2010 at 10:21


There has been some work done on lithium bronze by me and others.
I believe the cooks use it because it uses readily available materials. In my opinion it looks pretty inconvenient and there are other well documented procedures which work better. If there was one thing I liked about lithium bronze it was the complex itself, it looks like copper colored mercury absolutely beautiful! Other than that it was a pain in the but to work with as it had a habit of sticking to glass.

here are some links you may like.

http://www.sciencemadness.org/talk/viewthread.php?tid=13161

http://www.sciencemadness.org/talk/viewthread.php?tid=13563#...

http://en.wikipedia.org/wiki/Birch_reduction
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jon
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[*] posted on 4-10-2010 at 21:33


well chemrox if you wanted to dehalogenate what i think you wanted to it would reduce the tertiary alcohol also.
btw how did the other process turn out???


[Edited on 5-10-2010 by jon]

[Edited on 5-10-2010 by jon]

[Edited on 5-10-2010 by jon]

[Edited on 5-10-2010 by jon]

[Edited on 5-10-2010 by jon]
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Sedit
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[*] posted on 5-10-2010 at 18:14


This process I hear of a while back from cooks themselfs and unable to believe in blind faith I decided to research it which lead to my Li[NH3]4 complex thread. This is not NH3NO3 + Li but a matter of using NH3NO3 + NaOH to produce the NH3 which is feed into an Et2O solution with stirring to yeild Li[NH3]x complex which in itself is basicly a form of Lithium alloy with Ammonia, of all things, to yeild a compound with a pretty great reducing potential.

While researching I came across many text detailing how the reaction proceeds even if the Ammonia is not a liquid but as a gas as well unlike in a traditional birch reduction. It appears that the complex forms and behaves exactly the same yet it has a much higher electron density as the "bronze" complex. Most required the use of a NH3 ballon or a slow steady stream of Ammonia.

I do have reservations on it however in that you are now dealing with a biphasic reaction whereas in the traditional birch it is a single phase. Attempts to reduce MeBn proved in short order that rapid stirring is a must and I would bet the farm that arylhalides would prove just as much if not more difficult. Papers have stated simular or above normal yeilds but the time factor should be increased by a factor of hours. Please to not attempt to produce amphetamines from this route else you may create some sort of unidentified poision that would contaminate your product and possibly leave you feeling ill for days after.


[edit]
Chemrox could you please post the page number of the reaction spoke of in the link so that I dont have to read thru all that shit? I want to view the correct section to see how they word what they say but have little interest in reading the rest thanks.

[Edited on 6-10-2010 by Sedit]





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[*] posted on 5-10-2010 at 18:34


Quote:
Please to not attempt to produce amphetamines from this route else you may create some sort of unidentified poision that would contaminate your product and possibly leave you feeling ill for days after.


Or blow yourself and your surroundings to hell, assuming you go "shake and bake" style. Can't count how many times I've seen articles about people being horrifically burned by this, hotel windows blown out, etc. Some people even do this while driving - thought texting at the wheel was bad?! :o




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[*] posted on 5-10-2010 at 18:38


Well I was referencing making the "bronze" complex and reacting that with Ephedrine which would not have the desired outcome without some sort of chromography of some sorts. The typical Shake and Bake style is pretty much a problem waiting to happen although I could see some potential in forms of birch reductions that could afford to be abit sloppy and lose large amounts of the yeilds in the process.




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[*] posted on 5-10-2010 at 18:42


I do agree with what you said though, side reactions and the potentially toxic products that follow are a real risk that not many "cooks" consider. All sorts of strange things happen with organic chemistry!



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[*] posted on 5-10-2010 at 18:54


Sorry to sidetrack this thread into such a topic but my main concern that cooks don't consider is that Ephedrines are an amine which also desires to complex with the Lithium in a simular fashion so if there is unreacted Lithium it would react with the starting materials or the products themselfs creating something that a flame test of the reactions products would produce a red coloration signaling something is wrong. Dimmerization of any amine in the presence of Lithium would pose a real problem and if this reaction became popular in pop drug culture there would be serious issues with toxicity and deaths. All in all the warning "Cooks do not try this at home" should be posted on all these half assed TeKs at the very lest.

Chemrox had it right when speaking of attempting Arylhalide reduction which I feel would be the greatest potential of this complex other then basic benzene ring reductions.





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[*] posted on 5-10-2010 at 23:01


better they called it urea/Li reduction - no one would blow himself my mixing them, but heating of urea would also produce ammonia gas
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[*] posted on 6-10-2010 at 14:25


@Sedit: Please post the refs you were talking about having read. I searched ACS and no joy but was probably using the wrong search terms. As I understand what you're saying the ammonium nitrate has to be mixed with NaOH as well as Li metal. In a proper lab how would the reagent be made? Please post a good ref or two. I'm assuming the academic refs do not discuss amphetamines which are of no interest here. CRX



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[*] posted on 6-10-2010 at 16:15


I have to see if I still have them since my computer crashed and my website storing all my files had to be removed due to copywrite issues but I know they are posted somewhere. I believe in the reference request thread at thevespiary you will find a couple of them detailing the birch reduction without the use of liquid NH3.

You misunderstood what I said as well chemrox. The reaction is just like a birch except gas NH3 in a non polar solvent is used instead of liquid NH3. Read the reference posted in the Lithium complex thread it is wounderful in understanding the formation of the complex and electron density.

[Edited on 7-10-2010 by Sedit]





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[*] posted on 6-10-2010 at 16:41


I believe a forensics journal has a paper where they tried it out and it worked. Sounds pretty horrifying. Who really uses those expensive little batteries anyways.

Actually it sounds better than upturning a BBQ tank and using the boiling propane to condense the ammonia :o

Now I am curious: where does the water go? Does the excess Li destroy it or does the ether keep it away?




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chemrox
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[*] posted on 6-10-2010 at 20:31


Forget the crude shit the meth cooks do. Why isn't this published if it works? It seems like a simple enough procedure if some speed freak can do it in a parking lot.



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chemrox
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[*] posted on 6-10-2010 at 20:47
mechanism study


This might shed some light on how the NH4+ might be subbed for NH3

Attachment: Metal-Ammonia Reduction of Cycloalkanones. A Revised Mechanism.pdf (885kB)
This file has been downloaded 2207 times





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[*] posted on 7-10-2010 at 08:07


Quote: Originally posted by chemrox  
Forget the crude shit the meth cooks do. Why isn't this published if it works? It seems like a simple enough procedure if some speed freak can do it in a parking lot.

What are you talking about? There are hundreds of articles on Birch reductions and its variations. This is not a new reaction. It is as much published as Britney's tits. Just because some dumbass suicidal cook got enough brains to realize that lithium floats on hydrocarbon solvents and that these do not dissolve water, it does not mean anybody with half brain would use something as ineffective and primitive like that as some serious method for any reduction in any even remotely serious lab. Besides, dechlorinations are way more simple to do by hydrogenation rather than using Birch conditions.
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[*] posted on 29-2-2016 at 09:40


Quote: Originally posted by Sedit  
Please to not attempt to produce amphetamines from this route else you may create some sort of unidentified poision that would contaminate your product and possibly leave you feeling ill for days after.
The typical Shake and Bake style is pretty much a problem waiting to happen... but my main concern that cooks don't consider is that Ephedrines are an amine which also desires to complex with the Lithium in a simular fashion so if there is unreacted Lithium it would react with the starting materials or the products themselfs creating something that a flame test of the reactions products would produce a red coloration signaling something is wrong. Dimmerization of any amine in the presence of Lithium would pose a real problem and if this reaction became popular in pop drug culture there would be serious issues with toxicity and deaths. All in all the warning "Cooks do not try this at home" should be posted on all these half assed TeKs at the very lest.

Quote: Originally posted by madscientist  
I do agree with what you said though, side reactions and the potentially toxic products that follow are a real risk that not many "cooks" consider. All sorts of strange things happen with organic chemistry!


Guys are you trying to spread some hard anti drug propaganda?
Toxic mysterious products? Just wow.

How you can have something mysterious when you make hydrochloride salt?
It`s pure hydrochloride.
Everything else is in solvents.
Right?I think so (99,99% sure)...
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[*] posted on 5-3-2016 at 00:13
Li/NaOH/NH4NO3/C7H7BrMg


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[*] posted on 5-3-2016 at 00:15
wowy


whoever was dumb enough to try it eventually got really good at it, and i wish the hive was around to kick this tek around the world a bit. No info on it besides what personal nightmares were had,,,,that turned into white/sparkly ,kick in the arse goodness
:P

[Edited on 3/5/2016 by (UH) Stacked]
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[*] posted on 5-3-2016 at 11:19


Ammonium nitrate, hexane, lithium and sodium hydroxide work EXCEEDINGLY well to reduce psuedoephedrine when done properly. "Shake-and-bake".

None of this is a mystery, rednecks in Ar-Kin-Saw been doing it for years.




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