METHYLAMINE HYDROCHLORIDE (part one, two)

By sbillinghurst
2HCHO + NH4Cl > CH3NH2.HCl + HCO2H
Submitted by C. S. Marvel
Checked by J.B. Conant
1. Procedure
In a 5-l. round-bottomed flask, fitted with a stopper holding a condenser set fo
r downward distillation and a thermometer which will extend well into the liquid
, are placed 4 kg. (3711 cc., 47-53 moles) of technical formaldehyde (35-40 per
cent; sp. gr. 1.078 at 20 degrees) (see Note 1 on p. 378) and 2 kg. (37 moles) o
f 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 so
lution reaches 104 degrees. The temperature is held at this point until no more
distillate comes over (four to six hours). the distillate, which consists of met
hylal, methyl formate, and water, may be treated as described in Note 1.
The contents of the reaction flask are cooled to room temperature (Note 2), and
the ammonium chloride which separates is filtered off and centrifuged (Note 3).
The mother liquor is concentrated on the steam bath under reduced pressure to 25
00 cc., and again cooled to room temperature, whereupon a second crop of ammoniu
m chloride is obtained. The total recovery of ammonium chloride up to this point
amounts to 780-815 g.
The mother liquor is again concentrated under reduced pressure until crystals be
gin to form on the surface of the solution (1400-1500 cc.). It is then cooled to
room temperature, and a first crop of methylamine hydrochloride, containing som
e ammonium chloride, is obtained by filtering the cold solution and centrifuging
the crystals (Note 3). At this point 625-660 g. of crude product is obtained. T
he mother liquor is now concentrated under reduced pressure to about 1000 cc. an
d cooled; a second crop of methylamine hydrochloride (170-190 g.) is then filter
ed off and centrifuged. This crop of crystals is washed with 250 cc. of cold chl
oroform, filtered, and centrifuged, in order to remove most of the dimethylamine
hydrochloride which is present;
[word count above: 306, current date, 6-20-09, time 6:53 a.m.]
after the washing with chloroform the product weighs 140-150 g. The original mot
her liquor is then evaporated under reduced pressure, as far as possible, by hea
ting on a steam bath, and the thick, sirupy solution (about 350 cc.) which remai
ns is poured into a beaker and allowed to cool, with occasional stirring, in ord
er to prevent the formation of a solid cake (Note 2). The thick paste so obtaine
d is centrifuged, and the crystals (170-190 g.) are washed with 250 cc. of cold
chloroform; the solution is filtered and the crystals are centrifuged, thus yiel
ding 55-65 g. of product. There is no advantage in further concentrating the mot
her liquor.
The total yield of crude centrifuged methylamine hydrochloride is 830-850 g. Thi
s product contains, as impurities, water, ammonium chloride, and some dimethylam
ine hydrochloride. In order to obtain a pure product, the crude methylamine hydr
ochloride is recrystallized from absolute alcohol (Note 4). The crude salt is pl
aced in a 5-l. round-bottomed flask fitted with a reflux condenser protected at
the top with a calcium chloride tube; 2 l. of absolute alcohol is added and the
mixture heated to boiling. After about one-half hour the the undissolved materia
l is allowed to settle and the clear solution is poured off. When the alcoholic
solution is cooled, methylamine hydrochloride crystallizes out. It is filtered o
ff and centrifuged, and the alcohol used for another extraction. The process is
repeated until the alcohol dissolves no more of the product (about five extracti
ons are necessary). In the flask 100-150 g. of ammonium chloride remains, making
the total recovery of ammonium chloride 850-950 g. The yield of recrystallized
of recrystallized methylamine hydrochloride is 600-750 g. (45-51 per cent of the
 theoretical amount, based on the ammonium chloride used up in the process) (Not
es 5 and 6).
2. Notes
[ At this point I'll put in my notes. Paraformaldehyde is the name given to a so
lid form of formaldehyde; it is usu used. Absolute alcohol is 100% ethyl alcohol
, "absolute" means definitely dry. Denatured alcohol can mean different things;
you have to read on the "SD-40" or whichever "SD" is the one ('specially denatur
ed") suitable. You're doing the cleanest work, but . . . lead and mercury are sa
d to make somebody take and water isn't, but water will prevent the reactions fr
om occurring sometimes. Notice they go through the utmost effort to recover the
maximum amount. This is understood by all, and performed by experiment, to decid
e which process to use, and what advance is real, to increase the yield over the
former process. This is the bullshit of the numbers people declare as to percen
t. This is the whole reason for the above-quoted publication. Chemists were not
supposed to be "estimated EPA mileage" guys. Would you pass up a gas station bec
ause you calculated that your car should go further? You can't knock 5% off thes
e numbers. If you can't do it like they said you are going to get lower numbers.
Lastly, you were not supposed to work in a lab to get this stuff. You just go o
ut and buy it. MeNH2.HCl comes in a 5-lb. brown bottle, MeNH2 gas comes in a cyl
inder, if you steal a cylinder it has to be the right one. You can't really poss
ess a cylinder. It is like a shopping cart. To have it legally it is about 50 ce
nts a day, with gas. The regulators are also specific to the gas. I am thinking
about hydrogen. I had one. The cart and the chains are an integral part. Gas cyl
inders are the one freight to know how to move. Actually, it is not very far up
in chemistry to order cops around. They turn into M.P.s and you are at war. Frit
z Haber got tired of the way he was treated as a Jew and gassed the English. Lou
is Feiser liked cats more than people and invented napalm, naphthalene on a palm
itate, sticky little flaming gel dropped on villages all over Vietnam. He invent
ed more things. Fritz Haber must have been his hero. Lastly, again, (I need some
duct tape over my mouth), what I am on is caffeine (my drug of choice), you get
-methylamine gas 40% in water. This is why it is no good; some tweak opened it u
p to smell it and the gas is gone. If you know ammonia, you could believe that a
little probably smells like a lot. Past lastly, the Bhopal incident (65,000 dea
ths) resulted from (probably) some onsite tweak engineers trying to obtain a buc
ket of methyl isocyanate, which hydrolyzes (changes immediately with water) to m
ethylamine, and it got away from them and the whole underground tank went. Notic
e the name methamphetamine. In order to say I wouldn't mind ethamphetamine, I mu
st use the name N-ethyl amphetamine. Ethylamine is a liquid.]