Done some reading up and research into catalytic transfer hydrogenations using formate, formamide, formic acid as a hydrogen donor. After an initial false start with a magnesium mediated reaction, and a shitspeaking fuck submitting a crap paper for peer review (sorry...D-orbitals anybody? calling metals with D orbitals, have we got a MAGNESIUM in the crowd somewhere?...NO WE FUCKING DON'T!)
Its the same lot claiming the CTH reduction using zinc and ammonium formate in methanol works for reduction of arylalkyl aldoximes and arylalkyl ketoximes, though, so I'm suspicious. BUT, there is a member of the Swarm who has said 'works like a charm' in respect of a particular arylalkyl ketoxime to amine reduction. Although there is also some suggestion that it may in fact, be reducing partially, to the N-hydroxyamine.
Still if it does, that isn't a terrible thing, as a certain organic chemist in the same overall field, who is essentially one of the fathers of phenethylamine, tryptamine, and phenisopropylamine psychedelic chemistry did look into some similar concepts and found that, and it should apply to this theoretical N-OH-amine if the ketoxime does indeed go through a partial reduction to the N-hydroxyamine rather than all the way to the bare primary amine, the ones he synthesized resembled their primary amine counterparts so closely as to be almost identical, that one would be hard done by to tell one from the other in a double-blind bioassay.
And its close enough chemistry and pharmacology that it ought to act similarly on monoaminergic release and reuptake to the primary amine original target. So N-OH amine, in this case if it does result (and I will be wanting to find out if it does, so I can better comprehend the mechanistic minutiae of the reduction, of course
) then its no loss, almost certainly.
Should make it all the more interesting for a research project.
And indeed, could perhaps adapt it to other N-hydroxyamines via ketoximes. I wonder...I just wonder now. What that fine zinc dust has to offer in combination with ammonium formate, and possibly formic acid, or Zn/amm.formate/HCOOH. Still got to work up my ketone though, and check the density of the acid via a hydrometer so I can determine the concentration of the HCOOH via it's specific gravity.
And I have a plan to concentrate it too, from the OTC stuff, which could afaik be between 30% and twice that strength, so there wouldn't be so much water to need removing from the prepared salt. Pure formic acid, unfortunately cannot be treated with concentrated H2SO4 to remove the water and distilled, because it would decompose it to carbon monoxide. Which of course is unwelcome.
BUT, I had a neat idea, went to take a look up it's melting point, and i found that of pure HCOOH, it freezes at around 8-9 'C; so I had the idea to try selectively freezing the formic acid out of the H2O, lowering the temperature to below the freezing point of HCOOH but holding it above 0 'C, so that ideally, it will end up as chunks of ice floating about in a pool of liquid, the 'ice' however, being in fact, pure formic acid selectively frozen out of the water, which would then simply be dropped through a sieve into a bowl, and the solids transferred to a container for use in preparing the ammonium formate, after first subjecting the contents of the bowl to a couple more rounds of careful adjustment of the temperature until no more hunks of solidified formic acid 'ice' are deposited, or the PH is on the probably, slightly acidic side of neutral. That way, not having to neutralize the off the shelf acid product with ammonia, and then having to strip it of anything from 40 to 70% of the remainder, being just water. A pain in the arse, given the high boiling point of water due to the extensive intermolecular hydrogen bonding in H2O. Which also happens with HCOOH, formic acid hydrogen bonds extensively to form dimeric pairs of HCOOH molecules one bonded to another, like H2O does, which accounts for the high BP for such a small pair of molecular species. Which also makes the very first thing I thought to evaluate trying, distillation to separate the formic from the water, totally, completely fucking worthless, because H2O and HCOOH have a boiling point just 0.8 'C apart, with formic acid having the slightly higher BP of 100.08 'C and with such a miniscule difference in boiling point, distillation just isn't an option. Even though I haven't got one, they are quite possibly the most expensive kind of distillation column that I know of, something called a spinning band column, which uses a water current or gas jet to rapidly rotate a mobile collar that extends up inside a condenser, on the inner wall at high speed, they are used for the trickiest of distillations, where the differences in boiling points of one compound vs the other, or else there is an azeotrope somewhere, etc., not that it'll break the azeotrope, but I mean between two secondary compounds vs the distillate sought and whatever one is meant to be separating it from in a tertiary mixture or one of greater complexity.
Very expensive though. Expensive as hell, but very efficient for discriminating between the smallest practical boiling point differences that it is still practical to separate via distillation. I haven't got one though. Although I would most certainly like to own one in my laboratory kit items-set. I'll have to get saving up though. Because dear fucking baby jesus denying his own divinity to his own bloody father on a field trip to hell, the first one on ebay is listed for 4K, plus $132.30 shipping. Fucking hell.
Thats a fucking pisstake for shipping from the US too. I hate that, when they jack the shipping prices up for expensive items that don't weigh a huge amount, and that aren't actually any bigger physically than the likes of a condenser of conventional types that they often include the shipping for free! taking the fucking piss is what it is.
