Introduction and Reaction Mechanism

Figure 1: Hexamethylenetetramine (Hexamine) is hydrolyzed by HCl to

ammonium chloride and formaldehyde

When HCl is added to a solution of HMTA (Hexamine), it is hydrolyzed to

NH4Cl and CH2O. If formalin and ammonium chloride is used directly, instead
of HMTA, the solution also contains around 10% methanol as a stabilizer for
the formalin, and this reacts with the formaldehyde, creating the acetal
methylal, HC(OCH3)2, which has a low boiling point (42-43C), and will distill
off during the heating. As seen below, formic acid is also formed in the
reaction, which also reacts with methanol, forming methyl formate, also with
a low boiling point.

Figure 2: Ammonium chloride condenses with formaldehyde to form

methyleneimine

In the acid solution, the formaldehyde and ammonium chloride condenses to

the unsaturated compound methyleneimine instead of reverting back to
HMTA. The HCl is completely dissociated in the water solution.

Figure 3: Methyleneimine, water and formaldehyde reacts to form

methylamine and formic acid

The methyleneimine is reduced by the water(!) formed above to give

methylamine, while the formaldehyde is oxidized to formic acid, and is partly
carried away as its methyl ester.

Figure 4: Methylamine hydrochloride condenses with formaldehyde to form

dimethylamine

If formaldehyde is present in excess, at least some of the methylamine is

converted to dimethylamine. If too little formaldehyde is present, the

methyleneimine polymerizes to its trimer, (CH2=NH)3. Trimethylamine is

never formed, as long as the temperature of the solution never exceeds
110C. With an excess (4 moles) of formaldehyde, enough water and a reflux
temperature of 115C, dimethylamine is the main product, as the
temperature rises, more dimethylamine is formed. Dry heating of
paraformaldehyde and ammonium chloride produces trimethylamine through
reaction of dimethylamine with formaldehyde, giving rise to
tetramethylmethylenediamine and formic acid, and the base further reacts
with HCl, giving trimethylamine hydrochloride and methyleneimine
hydrochloride. A mixture of HMTA and HCl boils between 105 and 110C,
while NH4Cl/CH2O boils at 115C. No temperature control is really necessary
in the former case, as long as your heating plate isn't too hot. If the reaction
is carried out at a lower temperature, less dimethylamine is formed, and the
yield is higher. Vacuum reflux and distillation can yield at least 95% yield, in
contrast to the 45% gotten at 104C.

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).

And when asking for his references:

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:

C6H12N4 + 4 H2O 4 CH3NH2 + 2 CO2

They also state, and I quote my own translation here (from 1800's french):

"On the contrary, in the presence of excess formaldehyde, a considerable

pressure in the reaction flask is produced due to the formation of carbonic
anyhydride." (Carbonic anhydride is, I presume, what we know today as
carbon dioxide.)

They further refine the equation to include the effect of HCl:

C6H12N4 + 4 HCl + 4 H2O 4 CH3NH2*HCl + 2 CO2

Anyway, Cambier et Brochet agree that no "ammoniac" (i.e. - ammonium

chloride) is produced as long as enough water is present. This is why I say to
use "muriatic acid" INSTEAD of 36%. With a deficiency of water, all sorts of
products are formed, they say, including "ammoniacs and methylenic bases"
- whatever the hell they are.

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 Ammonium Chloride and Formalin [4]

In a 5 liter round-bottomed flask, fitted with a stopper holding a condenser

set for downward distillation and a thermomether which will extend well into
the liquid, are placed 4 kg (3711 ml, 47-53 moles) of technical formaldehyde
(35-40 percent; d 1.078 at 20C) and 2 kg (37 moles) of technical ammonium
chloride. The mixture is heated on the steam bath until no more distillate
comes over and then over a flame until the temperature of the solution
reaches 104C. The temperature is held at this point until no more distillate
comes over (four to six hours). The distillate, which consists of methylal (bp
42-43C), methylformate and water may be treated with NaOH solution to
recover methylal and sodium formate. The contents of the reaction flask are
cooled too room temp and the ammonium chloride which separates is filtered
off. The mother liquor is concentrated on the steam bath under reduced
pressure to 2500 ml, and again cooled to room temp, whereupon a second
crop of ammonium chloride separates. The total recovery of ammonium
chloride up to this point amounts to 780-815 grams. The mother liquor is
again concentrated under reduced pressure until crystals begin to form on
the surface of the solution (1400-1500 ml). It is then cooled to room
temperature, and a first crop of methylamine hydrochloride, containing some
ammonium chloride is obtained by filtering the cold solution. At this point
625-660 grams of crude product is obtained. The mother liquor is now
concentrated under reduced pressure to about 1000 ml, and cooled, and a
second crop of methylamine hydrochloride (170-190 grams) is then filtered
off. This crop of crystals is washed with 250 cc of cold chloroform, and filtered
to remove most of the dimethylamine hydrochloride which is present. After
the washing, the product weighs 140-150 grams. The original mother liquor is
then evaporated under reduced pressure, as far as possible, by heating on a
steam bath, and the thick syrupy solution (about 350 ml) which remains is
poured into a beaker and allowed to cool, with occasional stirring, in order to
prevent the formation of a solid cake, and the crystals obtained are washed
with 250 ml of cold chloroform, the solution is filtered yielding 55-65 grams of
product. There is no advantage in further concentrating the mother liquor,
which contains mostly tetramethylmethylenediamine hydrochloride, but no
trimethylamine hydrochloride. The total yield of methylamine hydrochloride is
830-850 grams. The product contains water, ammonium chloride and some
dimethylamine hydrochloride. In order to obtain a pure product, the impure
methylamine hydrochloride is recrystallized from absolute ethanol (solubility
0.6g/100ml at 15C), or preferably butyl alcohol (even less soluble). The

recovery of ammonium chloride amounts to 100-150 grams, making the total

recovery 850-950 grams. The yield of recrystallized methylamine
hydrochloride is 600-750 grams (45-51 percent of theory, based on the used
up ammonium chloride).

A standard run, from 250 grams ammonium chloride and 500g 37%
formaldehyde (containing 15% methanol), gives 100-134 grams methylamine
hydrochloride, 27 grams dimethylamine hydrochloride and 81 grams of
recovered ammonium chloride. The distillate contains methylal
(formaldehyde dimethyl acetal) and methyl formate, which after treatment
with NaOH can yield 25g of sodium formate and 30 grams of methylal, as the
compound cannot be separated by fractional distillation, neutralization is the
way to go. Ammonium chloride is very sparingly soluble in a concentrated
solution of methylammonium chloride, making the separation of the
compounds pretty sharp.

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.

Methylamine Hydrochloride from HMTA, Eleusis' version [with comments by

Rhodium]

140g of Hexamine is carefully dissolved in 400mL of Muriatic Acid (31.45%

HCl) to which at least 100mL of (preferably) absolute ethanol has been
added. Add the hexamine slowly while stirring vigorously and with good
ventilation as some nasty fumes are produced. Allow all to stir at room
temperature for at least 8 hours but preferably 16. The solution will become
turbid within several hours of the initial mixing. I *believe* this is the
formation of a formaldehyde trimer of some sort and I suspect that the
original equation for the conversion of hexamine into methylamine fragments
is therefore incorrect. [There is no trimer of any sort formed, if enough water
and formaldehyde is present. Eleusis uses 4 moles of amine to 6 methylenes,
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.