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Figure 5: A part of the liberated formic acid is oxidized to water and carbon
dioxide
Most of the formic acid which is formed above, is evolved during the reaction
as carbon dioxide during the heating of the solution.
This was misinterpreted by Eleusis, who thought the reaction proceeded like
HMTA + 4 HCl => 4 MeNH2*HCl + 2 CO2.
Here is an excerpt from a letter I got from him, when I told him that the
byproduct formed was ammonium chloride:
Not when I did it. NO Formaldehyde smell was ever noticed. In fact, the
mixing of Hexamine with HCl, if done *slowly* is fairly docile with no real
smell elicited. However when you heat the filtered mixture on the stove, it
*definitely* stinks to high heaven, but the smell at first is more like an
*isocyanate*. If one immediately dumps the reaction mixture onto the stove
(skipping the filtering) it takes *hours* (almost days!) to evaporate but 4
moles of methylamine are produced. If you wait for the precipitate to form,
then filter it, you get 240-270g of methylamine HCl from 140g of Hexamine.
Methylamine HCl weighs 67.5, and 4 times that is, not-so-coincidentally,
270g. I have only the slightest idea what the white precipitate that forms is,
but it smells like an isocyanate (very nasty, very poisonous).
I *do* have a text copy of the translation I did of the original french journal
article and it was by R. Cambier and A. Brochet [6]. In their article they state:
They also state, and I quote my own translation here (from 1800's french):
Unfortunately, Eleusis was wrong here. The reaction between Hexamine and
hydrochloric acid is the same as between ammonium chloride and
formaldehyde, and also the same as between ammonium chloride and
paraformaldehyde.
Synthesis
Methylamine Hydrochloride from Hexamethylenetetramine (HMTA)
140 grams HMTA (1 mole) was slowly dissolved in 400 ml water and 400ml
37% HCl (4 moles) was added. If the hydrochloric acid is added directly to the
HMTA, a lot of it is lost, as ammonium chloride starts to separate almost
immediately. The mixture was heated on a temperature controlled heating
plate, and the contents was slowly distilled while the temperature slowly rose
from 100C to 109C during 1-2 hours, during which time a lot of CO2 was
evolved, and approx 75ml of formaldehyde-smelling distillate was collected.
The solution was concentrated under vacuum until a lot of solids precipitated,
which were filtered off, and the solution was further concentrated, filtered etc
until everything was crystallized. The last crop of crystals was very hard to
crystallize, and care must be taken not to burn the contents of the flask, it
must not be allowed to rise over, say 75C. The white solids were placed in
150ml warm methanol (cheaper than denatured ethanol), and was filtered.
The insoluble portion was recrystallized from water, to give 40 grams of pure
ammonium chloride, which looked like very large snowflakes. The methanol
solution was evaporated, recrystallized from methanol and washed with
acetone, to give a deliquescent crystalline mass, which was dried in a
desiccator over CaCl2, to give XX grams of methylamine hydrochloride (XX
moles) as a fluffy soft powder. Calculated on the two moles of amine nitrogen
put into the equation, XX% became methylamine, and 37% (0.75 mole)
became ammonium chloride. The net yield of methylamine is therefore XX%
of the processed nitrogen.
which is enough, but gives less yield.] At any rate, filter off this white
precipitate which is obviously not an amine salt due to it being fluffy even in
Florida's humidity (almost all simple amine salts are hygroscopic) [With the
exception of ammonium chloride, and this is it]. Finally, remove the excess
water, hydrochloric acid and freako volatile products by, ideally, heating the
liquid at low to medium heat in a porcelain saucepan. Stove-proof glass would
be ideal, but stainless-steel, aluminum and copper are definitely not! [Rather
use a RB flask, with a water aspirator attached, smells considerably less]. The
concentration can generally be left unattended for a couple of hours, but try
to stick around and babysit it at least the first time so you will have a good
idea of how long it takes for your particular stove/pots/etc... [Or else it'll
BURN!] Also, the methylamine HCl will form a melt if heated too long at which
point it will sublimate off. It will then appear as if it's taking forever for the
stuff to concentrate when in fact you are merely boiling your product away.
After the concentrated slush has become sufficiently "thick", take it off the
heat every so often to see if it doesn't soldify, insuring that the water is
mostly gone and that not too much sublimation has occured (some is
inevitable and even desireable). The yield of Methylamine HCl should be
around 200g as white deliquescent crystals. Note, ACS-grade methylamine
HCl is colorless. We aren't using ACS-grade production techniques here, so
don't expect ACS-grade product. However, the methylamine produced by this
method is eminently suitable for the many purposes normally intended and if
allowed to sublimate some when heating, no adjustment for "purity" or
"water content" need be made in subsequent uses of it. [I can't understand
how he can get 200g of product. 140g hexamine gives 80 grams of NH4Cl,
and HOPEFULLY more than 100g of methylamine]. If the crystals are opaque
white and do not deliquesce quickly in air of average humidity (65% rh), they
may be contaminated with some Hexamine or some bizarre polymer. [Or
ammonium chloride. Recrystallize from methanol, then wash with CHCl3].
Washing 100g of the crude product with 100mL of Chloroform by stirring in a
beaker then filtering, repeated as many times as necessary, will remove
Hexamine. Methylamine HCl is insoluble in Chloroform whereas Hexamine is
at the rate of 1g to 10mL. As a final note, I have been informed that
hexamine is available in some areas in the form of "fuel tablets" for small
camping stoves. I have received mixed results from various individuals using
this so, as the saying goes, Caveat Emptor.