NMF synthesis for secondary amine via leukart?

IndoleAmine · Dreamreader Deluxe

BTW: the rxn didn't produce anything but ammonium carbonate, further a 500ml "Schott" RBF and a vacuum takeoff adapter were broken, just to find out that making formamides via dehydration with dean-stark/toluene does not work.

Hope you're satisfied now. Evil or Very Mad

loki · guinea pig

i was just going to say the other day, but i'd trapped myself in console land on my computer, that i realised that my whole scheme was cracked. HCl/methanol *removes* formyl groups, in any case. I have learned more about it, and acetyl formic anhydride and other ways probably suit this thing more anyway.

sorry to hear about your broken glass, man, not nice to break glassware... unless you have got an on-tap supply of it of course. i feel bad now. I can't believe how stupid my idea was.

Bluechip · Tue Apr 19, 2005 5:32 pm

Hows about:
(Ive said this at another place)

Make some methylamine hcl from hexamine,etoh and hcl as per Organikums method described at the Hive.
This will leave you with MeAm.hcl in one pot and Ethyl formate in the other.
Hydrolysis of the ethylformate then distillation to leave formic acid.
Or convert the ethylformate to sodium formate and use dry distillation with sodium bisulfate to yield strong formic acid.
Add base to the MeAm.hcl to produce gas which is pumped into your now strong formic acid sollution with solvent.
Distill to leave MeAmformate which is heated to produce Methylformamide

Easy peesy. Rolling Eyes

loki · guinea pig

i'm not even sure that methylamine will behave properly in this situation, ammonia and methylamine are both very volatile. as you discovered, you got ammonia carbonate, i'd say that methylamine would do the same thing? although, maybe it would be different with a greater amount of formic acid used, maybe 4x or so. the heat decomposes the formic acid so getting the rxn to work well would require an excess (if it can be done at all) otherwise, well i for one am looking more deeply into formylation methods

bio · Working Bee

i

................I'm not even sure that methylamine will behave properly in this situation,

Dry MeNH2 bubbled into dry HCOOH does work quite nicely and of course proper cooling is necessary. Couldn't put my finger on the reference right now but a search should turn it up. I think even Uncle Fester has this with the reference also in his book.

Drying and making formic acid is simply a waste of time as it's cheap and very readily available. Hell, you might as well make your own water

loki · guinea pig

i wasn't concerned about the methylamine formate, but that it would not satisfactorily formylate with the same scheme described in this thread

IndoleAmine · Dreamreader Deluxe

But with straight heating methylamine and formic acid to 160°C until flow of distillate ceases, then vacuum distilling out the formed NMF, it works.

You just have to repeat distillation under strong vacuum several times to purify, and you need a big fat excess of formic acid...

(bio's right: better buy the 85% commercial HCOOH for a few bucks/gallon!)