Patented Feb.

24, 1931
1,784,057

UNITED STATES PATENT OFFICE

EDGAR. C. BRITTON AND WILLIAM. H. WILLIAMS, of MIDLAND, MICHIGAN, AssIGNORs
TO THE DOW CHEMICAL COMPANY, OF MIDLAND, MICH IGAN, A coRPORATION or
MICHIGAN
METHOD OF MAKING DIMETHYL ANILINE
NoDrawing. Application filed April 9, 1927. Serial No. 182,532.
The usual method of preparing dimethyl The methyl bromide can be introduced
aniline is to heat aniline, methyl alcohol and either as methyl bromide itself or in the form
a small amount of sulphuric acid at a tem of phenyltrimethyl ammonium bromide, for
perature of 220 to 230 degs. C. for from 7 to at the temperature of reaction the quaternary
510 hours. German Patent. No. 250,236 dis bromide produces methyl bromide by decom-55
closes a similar method in which elementary position according to Equation (II).
iodine is substituted for sulphuric acid, the viously any material capable of yielding
action of such iodine being described as that methyl bromide by decomposition under the
. . . . . of a catalyst, while in the more -recent
- - - United
10 States patent to Homer Rogers No. 1413,494, reaction
d
As a
conditions may similarly be used.
specific example of our improved 60
dated April 18, 1922, the use of phenyl process for making dimethyl aniline we add
trimethyl-ammonium iodide instead of such 1 to 2 parts of methyl bromide either as a
iodine is recommended as a catalyst. liquid or a gas, to 93 parts of aniline and 96
The sulphuric acid method referred to to 128 parts of methyl alcohol, the proportion
above has the objection that methyl ether is of methyl bromide being substantially less 65
produced as a troublesome by-product as well than amolecular equivalent while the propor
as phenyltrimethyl ammonium sulphate, tion of aniline to methyl alcohol is approxi
which is a very stable compound and has mately that of one molecule of the former to
later to be decomposed by caustic alkalies from 3 to 4 molecules of the latter.
20 under pressure. The modified processes in The foregoing mixture of ingredients is 70
volving the use of iodine and phenyltrimethyl then heated in an iron autoclave for from 12
ammonium iodide both produce a dimethyl to 20 hours at a temperature of from 230 to
aniline contaminated with the iodine deriva 240 degs. C. and under a corresponding pres
tive which can only be eliminated by special sure, e.g. about 700 pounds per square inch.
' and costly procedure. The presence of this The mixture should moreover be continu- 15
iodine compound causes the dimethyl aniline ously stirred while the reaction proceeds.
to darken very rapidly on exposure to air At the end of the reaction, which may readily
thus making the product unfit for sale or use. be determined by distillation and freezing
We have now discovered that methyl bro point of dimethyl aniline, the autoclave is
30 mide can well be employed in amounts equal cooled and the contents discharged into a 80
to from 1 to 2 per cent of the aniline to effect still. Here
a complete conversion of the latter to di alcohol whichthecomes entire mass is distilled, the
over first being set aside
methyl- aniline by reaction with methyl for use over again; water then follows mixed
alcohol. Not only does the use of such bro with dimethyl aniline; and finally the main
mide facilitate the reaction to a remarkable
degree but the dimethyl aniline product pro under reduced pressure. Most distilled
body of dimethyl aniline is over 85
duced is of very high purity and can be ex bromide in the form of the quaternary com of the methyl
posed to the air for a long time without any pound referred to above will be recovered
so detrimental effects. in the still residue although some will be lost
The invention then consists of the steps and in the distillate. . . . .30
detailed modifications thereof hereinafter The alcohol and such quaternary bromide
fully described and fully pointed out in the
claims, the following description setting compound are then used in making up a fresh
reaction mixture and the operation just de
forth but several of the various ways in which
the principle of the invention may be used. scribed The
is repeated.
products of the reaction as discharged 95
The action of the methyl bromide as em from the autoclave instead of being distilled
ployed in the present process may be in as a whole in the fashion just described may,
dicated by the following equations viz: on the other hand, be permitted to stand so
(1) CHs.NH+2CH3OH+CH, Br=C.H.N(CH3), Br-2H.O. as to effect a separation of the mass into
aqueous alcohol and dimethylaniline-alcohol 100
 1,794,057
layers. The latter may thereupon be washed aniline,2. In a method of making dimethyl
with water and distilled directly. The wash mixture the step which consists in heating a
of aniline and methyl alcohol (ap
water obtained from the Washing of this proximately one molecule of the former to
layer is thereupon added to the aqueous alco
hol layer which will then contain all the from 3 to 4 molecules of the latter) with sub 70
methyl bromide in the form of phenyltri stantially less than a molecular equivalent
methyl-ammonium bromide, so that upon of3.methyl bromide.
In a method of making dimethyl ani
concentrating this solution with consequent line, the step which consists in heating a mix
recovery of alcohol and dissolved dimethyl ture of aniline and methyl alcohol with addi 5
10 aniline, substantially all of the methyl bro tion of a relatively small amount of methyl
mide in the form of quaternary compound bromide at a temperature of from 200 to
may be recovered and so be available for re 260° C. and corresponding pressure until the
introduction into the system. reaction is complete. ... .
Whether such compound be obtained as 4. In a method of making dimethyl ani 80
15 the residue from the distillation method of
separating the products of the reaction, as tureline, the steps which consistin heating a mix
first described above, or as the residue re relatively of analine and methyl alcohol with a
maining from this last described method of recoveringsmall amount of methyl bromide,
phenyl-trimethyl-ammonium bro
recovery, the compound should be dissolved. ..
mide from the reaction products
20 in aniline, preparatory to its use over again. Such compound in a succeeding operation for
and usin 9 85
While the temperature of reaction is best
maintained at from 230° to 240° C., as above the5.methyl
In a bromideoftherein.
method making dimethyl ani
indicated, a somewhat lower temperature line, the steps which consistin heating a mix 90
may be employed although the use of a tem
25 perature as low as 200 degs. C. is not advis ture of aniline and methyl alcohol with a rel
able inasmuch as the decomposition of the atively small amount of methyl bromide at
quaternary bromide according to Equation acorresponding
temperature of from 2009 to 260° C. and a .
pressure until reaction is com
(II) will be so slow as to prolong the time plete, recovering
of the reaction. On the other hand, if the nium bromide fromphenyl-trimethyl-ammo
the reaction products 95
30 temperature be carried as high as 260 degs.
there is a tendency for such quaternary bro and using such compound in a succeeding
mide to decompose into toluidines and de operation 6. In a
for the methyl bromide therein.
method of making dimethyl ani
rivatives thereof.
As indicated above, any alcohol that goes ture of aniline and consist
line, the steps which
methyl
in heating a mix OU
alcohol with a
through the reaction unchanged is recovered relatively small amount of methyl
for use over again, and this will also apply permitting the reaction products bromide, to stand
to any of the aniline in case this is not en
tirely used up. Under certain conditions, With formation of one layer containing prin
moreover, more or less, monomethyl aniline cipally dinnethyl aniline and an aqueous
40 will be formed; for example by shortening layer containing phenyl-trimethyl-ammo
the time of reaction from that specified... or nium bromide dissolved therein, evaporating
by decreasing the relative amount of methyl said aqueous layer to recover said compound
alcohol employed. Indeed by proper con and using the latter in a succeeding opera
trol in these respects, the process can be run tion7. for
In
the methyl bromide therein.
a method of making a methyl ani ()
45 so as to produce substantially all mono line, the step
methyl, instead of di-methyl aniline. Where ture of anilinewhich consists in heating a mix
and methyl alcohol with addi
both are produced, they will be taken out tion of a relatively
together by either of the two methods of re trimethyl-ammoniumsmall amount of phenyl
covery, and if desired may be subsequently 8. In a method of making bromide.
dimethyl
-
ani 5
50 separated by appropriate treatment or may line, the step which consists in heating a mix
be utilized as a mixture.
Other modes of applying the principle of ture of aniline and methyl alcohol with addi
our invention may be employed instead of tion of a relatively small amount of phenyl
trimethyl-ammonium bromide, at a temper
the One explained, change being made as re ature of from 200° to 260° C. and corre
55 gards the process herein disclosed, provided
the step or steps stated by any of the follow siding pressure until the reaction is com
ing claims or the equivalent of such stated plete. -
Signed by us this 1st day of April, 1927.
steer steps be employed.
e therefore particularly point out and EDGAR C. BRITTON.
60 distinctly claim as our invention:- WILLIAM H. WILLIAMS.
: 1. In a method of making a methyl-ani
line, the step which consists in heating a mix
ture of aniline and methyl alcohol with ad
dition of a relatively small amount of methyl
65. bromide. .. . .