[bpyfiend]

Hello Folks,
I'm working on synthesizing 1,3,5-benzene triamine.  I found an old prep that takes "phloglucinol"  (a 1,3,5 triphenol) and converts it to the trioxime with hydroxylamine.  Interesting and straight forward chemistry.

The next step calls for the reduction of the trioxime to the triamine with Raney Nickel and H2. 

It says the trioxime was heated to 80C (in n-butyl acetate) for 3 hours, under H2.  Is that exactly what it means?  (Ie, the "balloon reduction"--with maybe a liter of hydrogen on top of the heated solvent?)

Also, my Raney Nickel is a slurry in water.  I had planned to remove water by washing it with THF, then washing it with n-butyl acetate, before the reaction.  THF should be stable with Raney Nickle, right?   thanks for any suggestions,
J.

[cpncoop]

I would be very cautious in heating anything up under a baloon, especially an H2 reduction.  That's why they make Parr reactors and the such.  However, if you can't find such a reactor, I would look up how to do transfer hydrogenation on this, which will obviate the need for a baloon.

If this is unsuccessful, I'd try the Raney Ni reaction in MeOH at r.t. before thinking about running it at elevated temps.  Good luck.

[cpncoop]

I forgot to add that reductions run fine in THF, just much slower than in a protic solvent (MeOH, AcOH, etc...)

[bromidewind]

I'm assuming you mean phloroglucinol when referencing your starting material. Phloroglucinol is prepared by adding a strong base like NaOH to triaminobenzene.. so logically, I would assume you could reverse this process by acidifying phloroglucinol with HNO₃ and H₂SO₄.

We just covered aromatic reactions a week or so ago in my OChem course, but I don't have those notes with me. So I'm probably wrong in my reasoning. But, it's my two cents.