Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 6, pp. 845−847.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.J. Markosyan, G.A. Baghdasaryan, G.P. Hovhannisyan, H.S. Attaryan, G.V. Hasratyan, 2013, published in Zhurnal Prikladnoi
Khimii, 2013, Vol. 86, No. 6, pp. 902−905.
AND INDUSTRIAL ORGANIC CHEMISTRY
Waste-Free Technology for N-Methylmorpholine Synthesis
A. J. Markosyan
, G. A. Baghdasaryan
, G. P. Hovhannisyan
H. S. Attaryan
, and G. V. Hasratyan
Institute of Organic Chemistry of Scientiﬁ c-Technological Center of Organic
and Pharmaceutical Chemistry, Yerevan, Armenia
“Ariac” Institute of Applied Chemistry,” Yerevan, Armenia
Received November 19, 2012
Morpholine and its derivatives, (N-formylmorpholine,
N-acetylmorpholine, N-methylmorpholine-N-oxide, etc.)
due to their high solvency are widely used for extracting
aromatic hydrocarbons  and also as solvents of natural
polymers. Thus, in manufacturing cellulosic fibers
N-oxides of tertiary amines, often N-methylmorpholine-
N-oxide, are widely used as solvents for cellulose [2, 3].
Besides of cellulose N-methylmorpholine-N-oxide
dissolves ﬁ broin, natural polymer more than by 80%
consisting of simplest amino acids: glycine, alanine, and
serine . Fibroin is the main component of natural ﬁ bers
such as a web and natural silk.
Application of N-methylmorpholine-N-oxide is
enlarged both as solvent and reagent in ﬁ ne organic
In the study the sunthesis of N-methylmorpholine, the
basic starting material for the synthesis of N-methylmor-
pholine-N-oxide was descibed.
In preparative practice N-methylmorpholine is gener-
ally prepared by N-methylation of morpholine by clas-
sical methylating agents, methyl halide (usually methyl
iodide), dimethyl sulfate, a mixture of formic acid with
formalin, etc. [6–8].
These reagents are usually quite expensive, and some
of them are very toxic and aggressive (dimethyl sulfate,
The way of the direct synthesis of N-methylmorpho-
line (IV) from methylamine (I) and 2,2'-dichlorodiethyl
ether (II) was suggested according the scheme :
By this way the reaction is carried out at 100–200°C
for 5 hours. Hardware design of the process requires
an autoclave that increases the technology cost and
makes it unsafe. Furthermore, recovery of methylamine
from the resulting hydrochloride should be carried out
that implies the use of additional reaction equipment.
We have modified the process of preparation of
N-methylmorpholine (IV) from methylamine (I) and
2,2'-dichlorodiethyl ether (II). For simpliﬁ cation the
synthesis was carried out in a dilute aqueous solution
of methylamine at 90–95°C in the presence of sodium
hydroxide solution with simultaneous removal of the