Bugger. It looks like nickel boride reduction of nitroalkanes is a non-starter. At least using the P2 type boride (there are two, one formed in alcoholic media, the other in aqueous media, P1 being the form produced when a nickel (II) salt is reduced, ideally the acetate, using sodium borohydride, in alcoholic medium, and is the more active of the two, I've only tried P2 so far though, and not under pressurized hydrogen, but it appears that it won't do for reducing aliphatic nitroalkanes to aminoalkanes.
Thankfully though, I did get turned on to a rather nifty two-step onepot nitroalkene reduction (excess borohydride, a 4-6-fold molar excess with respect to the nitroalkene to be reduced to retard it's undergoing a parasitic Michael-type addition to the reduced nitroalkane intermediate which would give one polymerized tarry shite instead of a decent yield of various amphetamines and phenethylamines, although unfortunately no good for the non-fluorinated ring-halogenated ones, and then, once the nitroalkane has formed, cupric chloride is then added, which gets reduced to, unusually for copper, catalytically highly active species, giving good yields of at least straight amphetamine from P2NP)
Kind of neat, no pyrophoric chemistry (typically LiAlH4 is used to reduce the nitroalkenes to the aminoalkane in one step but it's pyrophoric, and can be dangerous to handle, borohydride needs the additional in-situ generation of copper nanoparticles, but it's so damn tame to handle, the excess can be quenched by directly adding acid in plenty of situations, or adding methanol, with which it reacts quickly, but not violently, giving off an effervescence of hydrogen gas)
Great shelf life, no spontaneous ignition, no need to dry THF or ether over sodium or potassium at reflux for two days to get it dry enough NOT to burst into flame, and for plenty of things to do with it, it doesn't even NEED an ether or THF etc. type solvent, which means less material that has any spontaneous nasty ass decomposition potential to keep around (THF and erther form explosive peroxides slowly in storage unless inhibited and ideally, regularly treated to destroy peroxide content. Some of them are more sensitive than others, but I don't want to encounter any of them, got a really nasty habit of forming under and in the screw threads on container caps, then detonating violently when opened. I've seen some rather nightmarish pictures, that rather drove that message home.....like a fridge, in a thousand tiny pieces, embedded in the ceiling of some lab somewhere that didn't watch out for peroxides.
Quite hilarious at the time...until you think of what''s lurking in the 'other things' fridge (contents vary, but generally a load of bottles of various less than stable things have to share with tubs of live maggots and casters, that my old man uses as fish bait. Gives me a mental picture that's even worse if that THF ever were to peroxidize and explode. Not only a fridge studded roof...but if those things hatched....jesus. I think I'm going to set to making sure I use up that 5l of THF I have in there, because it's been there, albeit inhibited and stored in as good a set of conditions, bar under liquid nitrogen or the likes, that one could hope to store THF or other ethers, and unopened. But that does on the other hand, leave me with five liters of the stuff, that'll have a shelf life of needing checking and possibly treating every 3 months or so to make a point of using and replacing with fresh stuff.
