Author Topic: Urushibara failure  (Read 217 times)

Impossible

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Urushibara failure
« on: May 19, 2013, 04:02:44 AM »
The exact procedure from:
http://www.erowid.org/archive/rhodium/chemistry/amph.urushibara.html
was followed with the exception of substituting Al powder for foil.  The addition of 3ml HCl and 1g Al gave no reaction whatsoever, after an additional 6ml HCl and 2g Al were added over the course of 2 hours, a violent reaction took place for about 30 seconds, where temps rose to 80*C, and most of the ethanol was boiled off.

Additional ethanol was added and the procedure continued.  Upon basification, the resulting supernatant was a dark reddish colour rather than the described yellow.  What went wrong?

lugh

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Re: Urushibara failure
« Reply #1 on: May 19, 2013, 02:14:10 PM »
You've admitted to changing one variable and have the nerve to post a thread asking why you got tar  :o  The author of that procedure was responsible for many procedures in wide use, obviously you' don't have the same skills and experience  ;)  You're going to have to study this route a lot more thoroughly, and expect a very bumpy road on the way to what you seek  :-X  There's some information about polymerization on that web page you linked to, perhaps you should read it again  ::) The end results do really come from the effort applied  8)
« Last Edit: May 20, 2013, 02:21:55 AM by lugh »
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antibody2

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Re: Urushibara failure
« Reply #2 on: May 21, 2013, 12:16:58 AM »
Urushibara is not active enough to reduce aliphatic nitro compounds. There are no mentions of such reductions in scientific literature.

Not true, Ritter reduced P2NP to amphetamine, and Antibody reduced TMP2NP to TMA2 in similar yields.
http://www.erowid.org/archive/rhodium/chemistry/tmp2np-red.html

However, that reaction is notoriously difficult to get reproducible yields from. You would be better off using the Al/Hg/GAA reduction, it is more consistent.

lugh

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Re: Urushibara failure
« Reply #3 on: May 21, 2013, 04:07:34 PM »
Urushibara is not active enough to reduce aliphatic nitro compounds. There are no mentions of such reductions in scientific literature.

Not true, Ritter reduced P2NP to amphetamine, and Antibody reduced TMP2NP to TMA2 in similar yields.
http://www.erowid.org/archive/rhodium/chemistry/tmp2np-red.html

However, that reaction is notoriously difficult to get reproducible yields from. You would be better off using the Al/Hg/GAA reduction, it is more consistent.
No references, no pictures, and no bioassays.

Pictures are a lot like training wheels on a toddler's bicycle, and thus unnecessary  :P They pose a security threat to the member :

http://127.0.0.1/talk/index.php/topic,2618.0.html

Published science has progressed for many centuries without such technology  ;)  The reduction of Phenyl-2-nitropropene to amphetamine isn't strictly aliphatic due to resonance involving the aromatic ring  :-X    There were many novel procedures posted and checked on the Hive, and with the demise of that web site where it was originally posted it's rather disingenuous to make those statements  ::)  This procedure hasn't been completely reduced to practice, and the fact that this thread was posted is yet more evidence that the database must bee returned to be publicly available for the same reasons the web site came into existence in the first place  :o  Antibody was and still is a contributor of very useful information to the swarm  ;D  As Jacked signature stated on the Hive, the end results from the effort applied  8)
« Last Edit: May 21, 2013, 06:22:26 PM by lugh »
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atara

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Re: Urushibara failure
« Reply #4 on: May 22, 2013, 09:53:41 PM »
If I had to guess, it depends on how you prepared the aluminum. If it was freshly torn, the passivating layer should be thin enough to allow a slow-ish reaction with HCl. But if it had been sitting out for a while, it would be covered in a lot of oxide, and it would require a certain concentration of acid to react, which means that once it did, you would see some sort of cascade. Aluminum's passivation can make it a pain to work with when there's nothing like Hg to break it for you.

It makes more sense to use Mg, added all at once, with HCl dripped in slowly. Then again, what do I know?

reckless: Aliphatic nitro compounds aren't very interesting to mainstream (i.e. real) scientists. They're mostly produced by meth cooks looking to get a fix. With that said, I haven't searched the literature (and don't plan to).

lugh

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Re: Urushibara failure
« Reply #5 on: May 23, 2013, 07:23:47 PM »
Quote from: lugh
  There were many novel procedures posted and checked on the Hive, and with the demise of that web site where it was originally posted it's rather disingenuous to make those statements  ::)
  I am aware of Millgram's experiment so trusting to authority is not an argument.
Quote from: atara
With that said, I haven't searched the literature (and don't plan to).
Very nice and professional. Keep going.
Quote from: J.March, Advanced organic chemistry (Sixth edition), p1268
The reaction of Al-NiCl2*6H2O-THF converted a,b-unsaturated nitro compounds to the corresponding aldehyde
Bezbaraua, M.S.;Bez, G; Barua N.C. Chem. Lett. 1999, 325
With p2np, that procedure would give p2p with lower yeilds.

Ritter and Antibody were both highly respected members of the Hive who helped provide many of the procedures still in wide use by the swarm  ;)  Checking a proposed procedure before publication is what is called peer review, which was practiced on the Hive and Rhodium's web site when possible since it's how published science is best done  :-X  The Hive was unique and the old saw that says "You would have to have been there to understand it" certainly applies  :P  The end really does result from the effort applied  8)
« Last Edit: May 23, 2013, 07:43:12 PM by lugh »
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carl_nnabis

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Re: Urushibara failure
« Reply #6 on: May 24, 2013, 02:52:02 PM »
substituting Al powder for foil
Never substitute some Aluminum with foil in a preparation, that is the worst source of Al in the home lab, it has no fresh surfaces means it must be one of the most Al2O3 containing aluminum preparations anyway, and it is also very impure Al containing only like 98 or 99% due to being greased.
Use very fresh milled powder instead for most thinnest oxide layer.
There are no mentions of such reductions in scientific literature.
US Patent 3458576 is attached ;)
« Last Edit: May 25, 2013, 11:07:39 PM by carl_nnabis »
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Impossible

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Re: Urushibara failure
« Reply #7 on: May 27, 2013, 06:06:37 PM »
substituting Al powder for foil
Never substitute some Aluminum with foil in a preparation, that is the worst source of Al in the home lab, it has no fresh surfaces means it must be one of the most Al2O3 containing aluminum preparations anyway, and it is also very impure Al containing only like 98 or 99% due to being greased.
Use very fresh milled powder instead for most thinnest oxide layer.
There are no mentions of such reductions in scientific literature.
US Patent 3458576 is attached ;)

I believe I mistyped in that post.  I used Al powder rather than the Al foil that Ritter used in the procedure.