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Zdocs - Tips Urushibara Style Amphetamine
Zdocs - Tips Urushibara Style Amphetamine
Zdocs - Tips Urushibara Style Amphetamine
First of all many thanks go to CHEM_GUY for his continuous urging of the Hive community to try
Urushibara Nickel reduction on phenylnitropene. This reduction turned out to be easier than any
so far encountered. This is not based on any of the excellent references pertaining to
Urushibara that have been mentioned on the hive, only chem_guys postings!
Procedure:
Dissolve 4.0g Nickel Chloride hydrate (light green crystals) in 75 ml 95% ethanol w/ mag stirring
and warming to 50'C. After salt is dissolved remove stir bar and add 1ml water and 1ml conc.
HCl. [1] While solution at 50'C slowly add 5g regular Reynolds wrap torn up into .25 x 1.0in strips
in 1g portions with manual stirring. The aluminum will SLOWLY react with the nickel salt forming
the metal Ni(s) through metathesis as a dark grey chunky powder which settles to the bottom.
A gentle effervescence of hydrogen occurs during reaction. Add aluminum at a rate that
maintains a steady effervescence and keeps temperature roughly in the 50' range. Note this
may take up to two hours!
At the end of Al addition all green color from nickel salt should be discharged. If any color
remains add another gram of aluminum and wait for soln to clear.
At this point Urishubara nickel catalyst is prepared and ready for reduction. Dissolve 5g pure
phenyl nitropropene in 50ml Ethanol and add to nickel soln. [2] Now slowly add 3ml conc. HCl
[3] and 1 gram shredded aluminum w/ manual stirring. Aluminum will slowly dissolve with a more
vigorous effervescence of hydrogen than the first step. Maintaining good stirring with a glass
stirring rod is essential in beginning. Attempted magnetic stirring will result in frustration because
nickel is ferromagnetic and will stick to stirbar preventing surface area exposure necessary for
reduction. After aluminum is dissolved add three more milliliters HCl and one more gram Al.
Repeat adding acid and Al until 10 grams Al and about 30ml HCl has been added. Aluminum
reacts slowly. Expect addition to take about six hours, longer if temp falls below 50�C.
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Constant stirring towards end is not necessary, just give mix a good stir occasionally.
After all aluminum is added and mostly decomposed slowly pour in a soln of 30g NaOH in 100ml
H20 with careful stirring. Wear goggles and be careful! Base neutralization is highly exothermic!
In 30 minutes all aluminum sludge will solvate into bottom aqueous layer and a nice orange
alcohol layer reeking of amine will settle out on top. Nickel is not dissolved by the NaOH so it will
remain floating around between the two layers but this does not present a major problem. After
all, it�s not poisonous like mercury or anything! Now decant off the top orange organic layer
and distill off alcohol down to a orange stinky syrup completely different smelling than the P2NP.
Dissolve these goodies in acetone and slowly add sulfuric acid to precipitate the amine sulfate.
Voila!!!!!! about 3 grams light yellow amphetamine sulfate.
[1] Addition of water and acid found to be necessary to initiate rctn. btw NiCl2 and Al.
[2] When nitropropene was added to NiCl2 soln before conversion to Ni powder was complete
some polymerization occurred greatly reducing yield. It seems essential to add P2NP to rxn after
Ni is fully precipitated.
[3] Use of Sulfuric acid produced inferior results causing polymerization of P2NP to red tar
Increasing Yield: Use overhead mechanical stirring to keep nickel catalyst better suspended
during reduction. Re-extract aqueous NaOH/Al layer w/ toluene and work up in standard
manner. Use larger amount of nickel catalyst and more aluminum for hydrogen generation.
Thanks too to CHEM_GUY for enlightening the Hive to the benefits of Urushibara, and for
answering my dolt-like questions regarding same offline!
From "The Journal of the American Chemical Soceity", yr 1987, Vol 109,
pages 3459-3461
..."
[1] Adv, Organomet. Chem. 1986, 25, 73. (b) Modern Syth. Methods 1986,
4, 1. (c) Ultrasound: Its Chemical, Physical and Boilogical Effects
1987. (d) J Chem. Ed. 1986, 63, 427. (e) Ultrasonics 1985, 23, 157.
[2] J. Am. Chem. Soc. 1983, 105, 5781. (b) J. Am. Chem. Soc. 1983,
105, 6042. (c) High Energy Processes in Organomettalic Chemistry,
American Chemical Society 1987, p 191.
[4] Ultrsonics 1987, 25, 40. (b) Tetrahedron Lett. 1986, 27, 3149.
(c) J. Org. Chem. 1985, 50, 910, 5761. (d) J. Amer. Chem. Soc. 1980,
102, 7926.
[5] Angew. Chem., Intl. Ed. Engl. 1983, 22, 728. (b) J. Am. Chem. Soc.
1984, 106, 6856.
[6] Ultrasonics 1987, 25, 45. (b) J. Lab. Pract. 1984, 33, 13 and
references therein.
[7] Tetrahedron Lett. 1986, 27, 415. (b) J. Am. Oil Chem. Soc. 1983,
60, 1257. (c) Chim. Ind. (Milan 1968, 50, 314.
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[12] All sonications were performed with a Heat Systems-Ultrasonics
W375 cell disruptor with a titanium immersion horn at acoustic
intensties of ~50 W/cm^2 at 20KHz, as described elesewher in
detail [2]. Irradiation in a low-intenstity ultrasonic cleaning bath
does give hydrogenation, but at greatly reduced rates. Hydrogenation
reactions were carried out at 273 K under 1 atm of H2. In a typical
reaction, 1 g of Ni powder (200 mesh, EM Science, Cherry Hill, NJ
08034) was added to a 10% solution of alkene in octane. ...
Did you take the Ni preceptitated with the Al and wash it before the addition of the nitro- and
the conc. HCl?
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Also I assume you are using 36% (by weight or 12 M) HCl.
I know you mentioned regular reynolds wrap, but purely out of curiosity does the Al thickness
have the same relationship to the RXN that it does with Al/Hg reductions? ei can the RXN be
slowed or speeded up by varying foil thicknesses?
What are the pitfalls a novice chemist might anticipate in pursuing this route?
If there really was a God, I would have been forwarded to Hell a long time ago.
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Ritter Re: Urushibara Style Amphetamine Bookmark
(Stranger)
07-25-00 21:02 Chem_guy:
No 32946 Oops, forgot to mention activation of catalyst! Add this between first and second paragraph:
Precipitated Nickel powder was added to 100ml 20% NaOH soln and manually stirred at 60'C for
30 min. Excess NaOH is decanted and nickel is washed with 5 x100ml aliquots of distilled water
to remove excess base.
The 1st paragraph ends with ppt Ni in EtOH soln. Does one have to filter off the Ni or could one
also pour the 20% NaOH directly into the EtOH ? If it has to be filtered, what would be the best
way to do so ?
--psyloxy--
Yield was 60+%. (closer to 50% after clean up) Way cool for the 1st kick at the can. I am
impressed! Its all OTC!
Question though. could methanol be substituted for the ethanol? Be easier to control
temperature that way.
BTW - FOAF found that temp increased with stirring as did hydrogen evolution (causing beaker
to foam over). something to keep an eye on.
Also to avoid Ni at interface while separating layers toss a magnetic stir bar in and stir with the
NaOH douse. All the Nickel will stick to it, then you simply transfer the stirbar w/ nickel to beaker
of HCl and stir to regenerate your NiCl2(H20)6. (takes a couple days though) Probably a little Al
goes over to, Oh well.
Curious though, there is a white precipitate in the HCl as well, is this Aluminum Chloride? Be
sweet if Alumninum Chloride isn't H2O soluble cuz it'll make seaprating the Ni easier.
Just gone.
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Lem Re: Urushibara Style Amphetamine Bookmark
(Newbee)
01-25-01 20:53 LOL!
No 169343 Chemicals!?!?!? WE DON'T NEED NO STINKING CHEMICALS!!!!!
He who makes a beast of himself gets rid of the pain of being a man.
Antibody2 add it directly to the nickel after decanting the ... Bookmark
(Rehabilitated)
06-09-02 15:55 add it directly to the nickel after decanting the activation solution. Your rxn will get very viscous
No 319114 as it progresses, requiring the addition of more EtOH. It wouldn't hurt your rxn to bring your
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No 319114 as it progresses, requiring the addition of more EtOH. It wouldn't hurt your rxn to bring your
volume up to 125mls EtOH. You will still end up with a viscous slush at the end. If you look on
Rhodiums page you will see my variation of this same rxn for TMA-2. Check solvent volumes
there.
happy redxns
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