Synthesis of N-Alkylacrylamides from Commercial Fractions
of Higher Olefins by the Ritter Reaction
O. A. Kazantsev, A. P. Sivokhin, K. V. Shirshin, O. P. Gur’yanov, and S. I. Samodurova
Alekseev Nizhni Novgorod State Technical University, Nizhni Novgorod, Russia
Dzerzhinsk Polytechnic Institute, Dzerzhinsk, Nizhni Novgorod oblast, Russia
Received November 3, 2009
Abstract—The influence of temperature, reactant ratio, and catalyst (sulfuric acid) concentration on the
product composition in synthesis of higher N-acrylamides from acrylonitrile and commercial fractions of α-
, and of propylene trimers and tetramers by the Ritter reaction was examined.
AND POLYMERIC MATERIALS
ISSN 1070-4272, Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 6, pp. 1062–1068. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © O.A. Kazantsev, A.P. Sivokhin, K.V. Shirshin, O.P. Gur’yanov, S.I. Samodurova, 2010, published in Zhurnal Prikladnoi Khimii,
2010, Vol. 83, No. 6, pp. 1009–1014.
Higher N-alkylacrylamides are promising monomers
for preparing a wide range of commercial substances
used in production of additives to oils and petroleum
products, of cosmetics, and also in photographic
industry and in other fields [1–3]. Recently the interest
in these compounds increased owing to their use for
preparing hydrophobically modified water-soluble
polymers exhibiting a set of interesting properties .
One of the most convenient routes to N-substituted
acrylamides is the Ritter reaction, i.e., the reaction of
acrylonitrile (AN) with olefins or alcohols in the
presence of acid catalysts . The influence of
conditions on the course of this reaction with alkylat-
ing agents of different structures is specific .
Preparation of higher N-alkylmethacrylamides from
methacrylonitrile and fractions of olefins C
, and C
, and also 1-dodecene  has been
reported. The corresponding acrylic monomers were
synthesized from AN and 1-dodecene, 1-octadecene,
[9, 10], propylene trimers and
tetramers , and isobutylene dimer . The isomer
composition of the products, kinetic features, and
influence of the reaction conditions on the competition
of the main and side reactions was not studied in detail
From the practical viewpoint, it is appropriate to
use for the synthesis of higher N-alkylacrylamides
commercially available α-olefin fractions and pro-
pylene trimers and tetramers.
The goal of this study was to determine the
composition of products, examine the transformation
kinetics, and optimize the conditions of the synthesis
of N-alkylacrylamides by the Ritter reaction using as
raw materials the above-mentioned olefin fractions.
Experiments were performed with fractions of α-
[TU (Technical Specification) 2411-
(TU 2411-067-05766801–97), and
fractions of propylene trimers (TU 2211-031-
05766801–95) and tetramers (TU 2211-044-057-
66801–95) from the Nizhnekamskneftekhim Joint-
Stock Company. The olefin fractions were used
without additional purification. Acrylonitrile was
distilled before use.
Synthesis of the monomer was performed in a glass
reactor equipped with a stirrer and a reflux condenser.
To a vigorously stirred mixture of olefins and
acrylonitrile, we added through a reflux condenser
sulfuric acid of concentration from 80 to 93.4% at such
a rate that the temperature in the reactor did not exceed
10°C. Then the mixture was quickly heated to the
required temperature and kept for 4 h. After the
synthesis completion, the target amides were extracted
from the reaction mixture with toluene. The toluene
extract was washed two times with water, treated with
ammonia solution, and again washed with water to