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 (3540 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 600750 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.

Methylamine Hydrochloride from HMTA and Paraformaldehyde

70 grams hexamethylenetetramine (0.5 mole) and 30 grams paraformaldehyde

(1 mole) was dissolved in 200 ml water and 200ml 37% HCl (2 moles) was
added. The mixture was slowly heated, and at approximately 80C, all
paraformaldehyde dissolved. The contents was slowly distilled, and the
temperature rose slowly over 1-2 hours to 109C. During this 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 white solids were placed in
150ml warm MeOH, and filtered. The insoluble portion was recrystallized from
water, to give 40 grams of ammonium chloride. The methanol solution was
evaporated and recrystallized from methanol and washed with acetone, to give
a deliquescent crystalline mass, which was dried in a desiccator over CaCl2, to
give 49 grams of methylamine hydrochloride (0.72 mole). Calculated on the
two moles of amine nitrogen put into the equation, 36% became methylamine,
and 37% (0.75 mole) became ammonium chloride. The net yield of
methylamine is therefore 58%.

Methylamine Hydrochloride from Ammonium Chloride and Paraformaldehyde

[1]

27 grams of ammonium chloride, 30 grams of paraformaldehyde (molar ratio

1:2), and 90 ml of water were gradually heated. At 80C a clear solution was
obtained, and the temperature was maintained at 104C for four hours. Slightly
more than one-third (9.06 grams) of the ammonium chloride was recovered,
whilst 18.96 grams of pure methylammonium chloride were obtained. This
equals 86% of the theoretical amount. The amount of dimethylammonium
chloride produced was not estimated. It is not suggested from the results of
this experiment that paraformaldehyde can economically be used on a large
scale with advantage, since, quite apart from the relatively high cost, neither
formic acid nor part of the unchanged aldehyde can be recovered as byproducts.

Methylamine Hydrochloride from Ammonium Chloride and Formaldehyde Under

Vacuum [2]

150 grams of ammonium chloride and 300g of 40% formaline solution were
slowly warmed together under vacuum, and soon a rapid evolution of carbon
dioxide began. The solution was refluxed at a 20 mm pressure for four hours,
until no more carbon dioxide was given off, as tested with barium hydroxide
solution. The reaction product was then distilled in a vacuum, 2 hours being
consumed in the distillation. As soon as the residue from the distillation was
cold, the ammonium chloride which had crystallized out was filtered off with
suction, and the filtrate further concentrated by evaporation and again cooled,
allowing further ammonium chloride to crystallize. As Werner has pointed out
[1], the separation of ammonium chloride and methylammonium chloride is
pretty sharp, and the crystals are so different that it is easy to see if one is
contaminated with the other. The collected ammonium chloride wighed 7.9
grams (0.17 mol). The mother liquor left was evaporated until crystals began to
form on the surface, and was set aside to cool, and the first crop of
methylammonium chloride was collected with suction. Further evaporation
gave additional crops. In all four crops that were obtained, which were freed
from dimethylamine hydrochloride by washing with chloroform, 27.2 grams of
dimethylamine hydrochloride (0.51 mol)was obtained. The distillate weighed
37.3 grams, the residue which didn't crystallize weighed 326 grams, and the
total yield of methylamine hydrochloride was 82.5 grams, or 37% of theory.