METHYLAMINE HYDROCHLORIDE 347

alcoholwas the principal product. Severai methods proposed for the

dehydrationof diacetone alcohol were investigated. That of Hibbert2
(usinga very small quantity of iodine) is superior to the action of
eitherconcentratedsulfuric acid or aiuminum phosphate.

METHYLAMINE HYDROCHLORIDE
---+CHsNH2.HCI+ HCOrH
2HCHO + I\TH4CI
Submitted by C. S. Mrnvnl and R. L. JnNrrNs.
Checked by J. B. CoNaNr and F. C. WHroo,p.N.

1 . P ro c e d u re
Ix a 5-1. round-buttoned flask, fitted with a stopper holding a
condenser set for downward distillation and a thermometer which will
extend well into the liquid, are placed 4 kg. (3711 cc., 47-53 moles) of
technicalformaldehyde (35-40 per cent; sp. gr. 1.078 at 20") (see
Notel" on p. 378) and 2 kS. (37 moles) of technical ammoniurn chlo-
ride.The mixture is heated on the steam bath until no more disiillate
comesover and then over a flame until the temperature of the solu-
tionreaches104o. The temperature is held at this point until no more
distillatecomesover (four to six hours). The distillate, which con-
sistsof methylal, methyl formate, and water, may be treated as de-
scribedin Note 1.
The contents of the reaction flask are cooled to room temperature
(Note2), and the ammonium chloride rvhich separatesis filtered off
andcentrifuged(Notc 3). Tire mother liquor is concentratedon the
steambath under reduced pre,ssureto 2500 -cc., and again cooled to
roomtemperature,rvhereupon a second crop of ammonium chloride is
obtained.The total rccover)r of ammonium chloride up to this point
amountsto 780-815 g.
The mother liquor is again concentrated under reduced pressure
q!,td.c,rystals begin to form on the surface of the solution (1400-1500
cc.). It is then cooledto room temperature, and a first crop of meth-
ylaminehydrochloride, containing some ammonium chloride, is ob-
tainedby filtering the cold solution and centrifuging the crystals
(Note3). At this point 625-660 g. of crude product is obtained. The
motherliquor is now concentrated under reduced pressure to about
1000cc.and cooled;a seconderop of methylamine hydrochloride (170-
190g.) is then filtered off and centrifuged. This crop of crystals is
washedwith 250 cc. of cold chloroform, filtered, and centrifuged, in
orderto remove most of the dimethylamine hydrochloride which is
348 ORGANIC SYNTHESES METHYLI

present; after the washing with chloroform the product weighs 140- idly in order to bring the
150 g. The original mother iiquor is then evaporated under reduced easily purified.
pressure, as far as possible, by heating on a steam bath, and the 3. Centrifuging the pre
thick sirulry solution (about 350 cc.) which remains is poured into a drying, as all the produc
beaker and allowed to cool, with occasionalstirring, in order to pre- stand in the air.
vent the formation of a solid cake (Note 2). The thick paste so ob- 4. Since ammonium cli
tained is centrifuged, and the crystals (170*190 g.) are washed with cent ethyl alcohol (100 g
250 cc. of cold chloroform; the solution is filtered and tlie crystais hydrochloride purified in
are centrifuged, thus yielcling 55-65 g. of procluct. There is no ad- traces of it. A purer prod
vantage in further concentratingthe mother liquor. n-butyl alcohol, in rvhicht
The total yicld of crude eentrifuged methylamine hydroeliloride is the boiling temperatureis
830-850 g. This procluct contains, as impurities, water, ammonium ride is somewhat lesssolu
chloride, and some dimethylamine hydrochloride. In orcier to obtain as a rule three extraction
a pure product, the crude methylamine h.vdrochlorideis recrystallizecl fresh butyl alcohol for ea
f r om ab-.o i u tea l c o h o l (N o te 4 ). T h e erucl esal t i s pl aced i n a 5-1. plete separation. Sincetl
round-bottomed flask fitted rvith a reflux condenserprotected at the removed by exposureto a
top u'ith a calcium chloride tube; 2 l. of.absoh-rtealcohol is added and in a small quantity of wa
t he m ix t u rc h e a tc d to b o i l i n g . Afte r about one-hal f hour the undi s- and allowed to crystallize
solveclmaterial is allowed to settle and the clear solution is pourcd off. An entirely different n
\Vhen the alcohoiic solution is coolcd,rneth-vlaminehydrochloridc crys- drochloride free of amm
tallizes out. It is filtered off and centrifuged,and the alcohol used for based on the fact that wlr
anothcr extraction. The processis repcated until the alcohol dissolves reacts with an insufficien
no m or e o f th e p ro d u c t (a b o u t fi r' e c x tracti onsare necessary). In the mine is preferentially neu
flask 100-150 g. of ammonium chloriclelernains, making the total re- 5. The literature2 cla
covery of ammonium chloride 850-950 g. The -vield of recrystallized amounting to 79 per cent r
methylamine hyclrochloricieis 600-750 g. (-15-5i per cetrt of the theo- in the reaction. This figu
retical amount, based on the ammonium chlolide used up in tlie proc- methylamine hydrochlorid
6. Methylamine can
es s ) ( Note s 5 a n d 6 ).
which is distilled ancl tht
2 . N o te s acid.3 This method has I
of the editors.
1. Methylal ancl soclium formatc may be obtained from the first
distillate of thc main reaction mixture. The crude distillate is placed 3.M
in a flask fitted u'ith a rcflux condenser,and to it is acldeda solution of
Methylaminc can be P
200 g. of sodium hyclroxiclein 300 cc. of water. The methyl formate is
iodide,a methyl chloride
hydrolyzeclto socliumformatc. Thc rnethl'lal la1'eris -*eparated,dried
l Sharp and Solomon, J. C
over calcir"rmchloride, ancl distilled. In this rvay 240-260 g. of meth- 2 Werner. J. Chem. Soc. 1l
ylal, boiling at 37-42", is obtained. By evaporating the watery portion 3 Sommelet, Compt. rend.
to dryness, a residue of about 280 g. of crude sodium forrnate is ob- ^ a Hofmann, Ann. 79, 16 (1
- 5
t ained. Vincent and Chappuis, B
* 6
Ephrian and Gurewitsch,
2. T he m e th v l a m i n c h v c l ro c h l o ri clsol
e uti onssl i oul d be cool edrap-
Soc. 1t7, ZJ6 (1920).
 METHYLAMINE HYDROCHLORIDE 349

idlyin order to bring the salt down in small crystals which may be
easily purified.
3. Centrifugingthe precipitates is the only satisfactory method of
drying,as all the products tend to take up water when aliowed to
standin the air.
4. Sinceammonium chloride is not absolutely insoluble in 100 per
ceniethyl alcohol (100 g. dissolve 0.6 g. at 15o), the methylamine
hydrochloride purifiecl in the manner described contains apprcciable
traces of it. A purer product can be prepared by recrystallizing from
n-butylalcohol,in which the solubility of ammonium chloricleeven at
theboilingtemperatureis negligibly small. Methylamine hydrochlo-
rideis somewhatless soluble in this solvent than in ethyi alcohol, but
asa rule three extractions carried out at 90-100" r,r'ith 4-6 parts of
freshbuiyl alcohol for each extraction result in a substantially com-
pleteseparation.Since the last traces of the solvent are not rcadily
removed by exposureto air, a solution of the rccrystallizeclrnaterial
in a smallquantity of water should be distilled until free of alcoliol,
andallowedto crystallize.
An entirelydifferent method for preparing pure methylamine hy-
drochloride free of ammonium chloride has been described.l It is
based on the fact that when a mixture of methylamine and ammonia
reacts with an insufficientquantity of hvclrochloricacid the methyla-
mineis preferentially neutralized and the ammonia left free.
5. The literature2 claims a yield of methylamine hydrochloride
amounting to 79 per cent of the wcight of ammonium chloride used up
in thereaction. This figure is probably based on the weight of crucle
methylamine hydrochlorideand not of the recrystallized material.
6. I\{ethylaminecan be purified through its benzal derivative,
whiehis distilled and then hydrolyzed by concentratedhydrochloric
scid.3This method has been checked ancl found satisfactorv bv one
of ihe editors.

3. Methods of Preparation
Methylaminecan be prepared by the action of ammonia on methvl
methyl chloride,5dimethyl sulfate,6 methyl p-toluenesulfo-
iodide,a
lSharpand Solomon,J. Chem. Soc. 1477(1931).
2 W e r n eJr ., C h e m .S o c .1 1 1 ,8 5 0 ( 1 9 1 7 ) .
sSommelet, Compt. rend. 178, 2I7 (1924).
. aHofmann, Ann. 79, 16 (1851).
- sVincent and Chappuis,Bull. soc.chim. 45, 499 (1886).
- 6Ephrianand Curewitsch,Ber. 43, 139 (1910); Denham and Knapp, J. Chem.
Soc.117,236 (1920).
350 ORGANIC SYNTHESES ME

nate7 and methyl alcohol with a catalyst and at elevatedtemperatures;8

by the action of bromine and alkalie and of bleachingpowderl0 on ace- METI
tamide; by the action of sodamide on methyl iodide;tt by the reduc-
tion of chloropicrin,l2 hydrocyanic or ferrocyanic acid,ls hexamethyl-
enetetramine,lanitromethane,ls methyl nitrite,l6 or formalcloxime;1? cHscocHCozczHs
from acetyl chloride and sodium azide;18and by the action of for- I
(cH2)3cH3
malclehycieon ammonium chloricle.le
2CHTCOOHCOzNa* Hz
TRodionov,
Bull. soc.chim. (4) 45, 109 (1929).
8 D'vis and Elderfield,J. A.r. Ch.m. Soc. 50, 1286(1929);
I
E. I. du Pont de (CH')'CH'
N e m o u r sa n d C o . ,U . S . p a t . 2 , 0 1 7 . 0 5t C 1 . A.29,8001(tgBS)1.
e Hofmann, Ber. 15, 765 (1882); Frangois,Compt.
rend. 147, 430, 680, gg3 Subm
(1908).
loBader and Nightingale,u*. S. prt. 1,489,480 Check
iC. A. 18, 1g36(IgZ4)1.
l l C h a b l a y , C o m p t . r e n d . 1 5 6 , 3 2 8( 1 9 1 3 ) .
1 2 G e i s s eA,n n . 1 0 9 , 2 S 2( 1 8 5 9 ) ;\ \ r a l l a c ha n d B o c h r i n g e r ,
A n n . 1 8 4 ,5 l ( l g Z T ) ;
Frankland, Challenger,ancl Nicholls, J. Chcm. Soc. 115, l5g (1919). Ix a 12-1.round-bot
l s M e n d i u s ,A n n . l 2 l , 1 3 9 ( 1 8 6 2 ) ; D e b u s ,A n n . 1 2 8 , 2 0 1 ( 1 9 6 8 ) ;
D e n h a m .Z . stirrer, is pl:iceii 5 l. of a
p h y s i k .C h e m . 7 2 , 6 7 4 ( 1 9 1 0 ) ;R i e d e l ,G e r . p a t . Z 6 q , S 2t8F r d l . 1 1 , 1 1 0 ( 1 9 1 2 - t a ) l ;
moles). To this is add
Dreyfus,U. S. pat. 2,072.217 fC. A. 31, 2619(1937)1.
laMeister, Lucius,and Briining, Ger. pat.78,812 925 g. ) obt ained ( p. 2a8)
tFrdl.3, lb (lgg0-4)l; Trillat
and Fayollat, Bull. soc.chint. (3) 11, 23 (1894);Iiuntlsen,Ger. pat. 74B,lgZiFrcll. fure is stirred at room t
7,24 (l9VLa)l; Mcisfsl, Lucius, and Briining, Ger. pat. 148,054tFrdl. 7,26 the monosubstituted ac
(190U)J; Isono,J. Pharm. Soc.Japan No. 397,209 (1915)tC. A. g,22BZ (1915)1. passesinto solution. T,
15Pierron, Bull. soc. chirn. (3) zt, ZSB (lg9g) Mailhe
; and Murat, ibid. (4) unsaponifiedrnaterialse
7,954 (1910); Zerewitinovand Ostromisslensky, Ber. 44,2402 (1911).
1 6 G a u d i o nB, u l l . s o c .c h i m . ( 4 ) 7 , 8 2 4 ( 1 9 1 0 )a n d A n n . ous layer is separateclI
c h i m .p h y s . ( g ) 2 5 , 1 3 6
(1912). with a stopper fitted wir
17Takaki and Ueda, J. Pharm. Soc. Japan tube leading to a conde
SB, 226 (1998) tC. A. 32, EgZ6
( 1 e 3 8l). Through the separa
18Naegeli, Griintuch and Lendorff, Helv. chim.
Acta lz, 222 (rg2g). cent ( sp. gr . 1. 40) sulf u
l s B r o c h e t a n d C a m b i e r ,B r . r l l s. o c .c h i m . ( 3 ) 1 3 , 5 8 4 ( 1 8 9 5 ) ;
F r a n g o i sC
, ompt.
r e n d .1 4 7 , 4 2 9( 1 9 0 8 ) ;W e r n e r ,J . C h e m .S o c .1 1 1 , 8 4 8( l g l 7 ) ; J o n e sa n d \ V h e a t l e y , than the amount requir
J . A m . c h e m . s o c . 4 0 , 1 4 1 1( 1 9 1 8 ) ;\ \ z i e t z e al n d r ( o h l e r ,G c r . p a t . 4 6 8 , g g st c . A . in the saponificationof
23,846(1929)1. oxicle ceasesto be vigor
boiling, and from one-
tilled. The clistillate is
(N ote 2) and r edist ille
In the distillate the l
the latter is distilled un
layer in this distillate ri
tilled. This procedureir
of ketone is obtainedin
fraction is washed four
trated solution of calciu
* Commercially availabl