Hi!
This is a story of a girl named Lucky
Just kidding
This is a story of a young and clever hallucination whose name is SWIM
Once upon a time SWIM decided he needed some cyclohexylamine. I'll omit the reason why. He just thought it'd bee nice to synth some, of its own interest.
So he dreamt up some nice cyclohexanone oxime and set his imaginary PC to look for the best method of reducing it to the amine - of all the countless methods known to The Hive.
Much to his surprize, very soon he stumbled upon this document:
Post 435995
(gabd: "Patent FR971429", Chemistry Discourse). His surprize grew even more when he realized that it was completely overlooked! Not a single response on the subject has been submitted and the discussion in that thread quickly diverted to smth else.
He then thought: 'Fuck! Of all things, why bother making an oxime when it seems possible to convert a ketone directly to its corresponding amine in good yield?' So, although the oxime was sitting happily in the freezer, he decided to venture upon this route for the sake of satisfying his research cravings.
So here's what this fictional character has fictionally done
(i hope you forgive me this long preface :
In a 250 mls flask there was placed:
- 13g Ni(NH
4)
2(SO
4)
2*6H
2O (33mmole, Mr=395) (the reason SWIM used this particular salt was that the jar w/it was closer to his reach than the one with ordinary NiSO
4. Beesides, SWIM just loves its
really nice turqois color )
- 80mls of household ammonia (the mixture turns
divinely purplish-blue and the salt readily dissolves)
- 15mls cyclohexanone
- 20mls 95% EtOH
After that, the mixtr was subjected to a vigorous mech stirring and thence there was added 10g zinc dust (dark-grey in color). Naturally, the room beegan to stink of ammonia since SWIM's stirrer is of non-hermetic type
.
An ice bath was kept nearby, but the rxn appeared to bee not very exotermic, the highest the temp ever climbed was about 40° C.
After ~1,5hrs the temp fell to ambient and further 10g Zn was added. Another 10g was added after 1,5hrs more.
After 4,5hrs of total stirring the mixtr represented a rather thick dark-grey goo, all Zn was consumed at that point (no H2 evolution). Smell of the starting product was completely gone, as far as SWIM could judge, another smell - fragrant smell of cyclohexanol - was also apparent.
It was put overnight in the fridge (it was too late for the work-up) and the next day:
- diluted w/conc NaOH and some aqua to make it xtractable, total volume ~400mls (SWIM didn't manage to get it all to dissolve, but it isn't really needed)
- xtracted 3x~50mls toluene
- washed with a little dilute alkali, then - 20mls brine
- toluene back-xtracted with 30x20x10 dil. sulfuric acid
- aq. phase made basic w/conc NaOH (amine layer immediately forming at the top)
- xtracted w/3x40mls DCM
- NP phase washed with 2x30mls brine and dried w/Na
2SO
4- DCM removed on waterbath at 80-50 C, care being taken not to evaporate significant qtty of the rather volatile product
- Remaining liquid was chilled and the leftover DCM was removed as thoroughly as possible using a car vac cleaner with a tube attached to it
The result was a clear oil with a very slight yellow coloration, which amounted to 15mls
An 1,5mls aliquot was dissolved in dil. H2SO4 in a plastic syringe, and the product was found to contain about 25-30% non-polar liquid (the leftover toluene and some DCM).
Which gives us a total yield of
70%, exactly as stated in the patent
The oxime is still sitting in the freezer
SWIM wonders what to use it for now
Now - some discussion.
Obviously, this route is perfectly suitable for OTC production of simple amines - such as isopropyl- and isobutyl - both acetone and MEK are mentioned in the French patent as tested substrates. Those are usable for many a purpose - e.g., Henry condensation catalysts.
What is more important, i really see no obstacle to this reaction in case of the more interesting ketones
I would really appreciate if some adventurous bee with some P2P or MDP2P on his/her hands would give it a shot ASAP (as SWIM ain't gonna do that).
And of course, the BIG advantages of this reaction is the fact that it is very simple to perform and absolutely non-toxic: no mercury, no hydroxylamine.
Yours As Ever,
Antoncho
