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ISSN 1070-4272, 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.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Waste-Free Technology for N-Methylmorpholine Synthesis
A. J. Markosyana, G. A. Baghdasaryanb, G. P. Hovhannisyana,
H. S. Attaryana, and G. V. Hasratyanb
a Institute of Organic Chemistry of Scientific-Technological Center of Organic
and Pharmaceutical Chemistry, Yerevan, Armenia
b “Ariac” Institute of Applied Chemistry,” Yerevan, Armenia
e-mail: baghdasaryangayane@rambler.ru
Received November 19, 2012
DOI: 10.1134/S1070427213060104
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 [1] 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].
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].
Besides of cellulose N-methylmorpholine-N-oxide
dissolves fibroin, natural polymer more than by 80%
consisting of simplest amino acids: glycine, alanine, and
serine [4]. Fibroin is the main component of natural fibers
such as a web and natural silk.
These reagents are usually quite expensive, and some
of them are very toxic and aggressive (dimethyl sulfate,
formic acid).
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 [9]:
Application of N-methylmorpholine-N-oxide is
enlarged both as solvent and reagent in fine organic
synthesis [5].
O
P, T
.
HCl
+ 2CH3NH2 HCl.
3CH2NH2 + ClCH2CH2OCH2CH2Cl
N
CH3
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 simplification 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
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