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          Reduction of 2,4,5-Trimethoxyphenyl-2-nitropropene to TMA-2
                                  by Antibody2
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Have been been investigating a few different nitropropene reductions recently.
There isn't alot available in terms of proceedures, so I will post these.

Reduction of TMP2NP using NaBH4 in THF/IPA
followed by Al/Hg in aqueous MeOH

An ovendriied 250ml rb flask sitting in an ice/salt bath is charged with 50ml
IPA (driied w/ MgSO4), 1g 8-20 mesh indicating silica gel and 80mmol NaBH4 (3g)
with mag stirring. When temp of solution was 0C a solution of 20mmol of
desicated TMP2NP (5g) in 100ml dry THF, is added dropwise from a pressure
equalized addition funnel over 1.5 hours. Rxn is allowed to stir for an
additional 0.5 hours, until all traces of orange had disappeared. Ice bath is
removed and rxn mixture was vacuum filtered and the solvent stripped off using
low vac on a water bath. 150ml MeOH is added to the residue followed by the slow
addition of 320mmol GAA (19g) from a pressure equalized addition funnel vented
by a hose out of doors. The funnel is removed and 15ml dH2O is added with 50mg
HgCl2. With vigourous mag stirring 0.5 moles Al (13.4g) (regular reynolds wrap)
is slowly added over a 2 hour period and allowed to stir an additional hour
while remaining Al goes into suspension. Rxn is transferred to a 500ml
eyrlenmeyer flask and slowly basified with 50% NaOH. When rxn with remaining Al
has subsided, it is a viscous gel. Flask is stopped and shaken until the gel
breaks down into a fluid again. It is then extracted 2X with 100ml toulene.
Extracts pooled and washed 1X w/ Saturated NaCl soltion, 1x w/ dH2O, dryed over
MgSO4. Then pregassed aliquots of toulene are added with filtration between
aliquots until no more crystals precipitate.

Yeild 11mmol TMA2.HCl (2.75g) 55% molar yield


Reduction of TMP2NP using Uruishibara Catalyst

Catalyst prep

To a solution of 1ml 31% HCl, 40g NiCl2.6(H20) in 350ml EtOH in a 500ml beaker
at 50C is added 35g of shredded Al (regular reynolds wrap) slowly over a 3.5
hour period, when evolution of hydrogen had ceased the the rxn was a viscous
gel. This was placed in a 4l beaker and rinsed several times with tap water,
each time allowing suspension to settle before decanting. This precipitated
nickel was air driied overnight on a filterpaper. (note larger peices of foil
were removed)

Activation

10g of the above catalyst was placed in a beaker containing 385mls 40%aqueous
AcOH and 89g NaCl at 70C for 7 minutes, then the solution is decanted and the
Nickel rinsed with 60C dH2O, then rinsed with EtOH then placed in a 500ml
erylenmeyer flask containing 250ml EtOH and charged with 20mmol TMP2NP (5g).
With moderate overhead stirring, 10g of Al is added 1g at a time followed by a
3ml aliquot of 31% HCl with each addition. Addition takes 2 hours, it is then
allowed to stir an additional hour while evolution of Hydrogen subsides. Rxn
become one viscous gel to which and 100ml EtOH is added with stirring. Rxn is
then slowly basified with 50% NaOH. After AlO hassettled the alcoholic overhead
is decanted and the sludge extracted with 100ml toulene. The EtOH is stripped
off using low vac on a water bath, the residue being taken up with the toulene
extract. Extract was washed 1x w/ Saturated aqueous NaCl and 1x with dH2O. This
is driied over MgSO4. Pregassed toulene is added in small aliquots with
pecipitated crystals being vac filtered between aliquots.

Yield 10mmol TMA2.HCl (2.5g) 50% Molar yield

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