ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 7, pp. 895−898. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © A.S. Frolov, E.A. Kurganova, G.N. Koshel’, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 7, pp. 902−906.
ORGANIC SYNTHESIS AND INDUSTRIAL
Liquid-Phase Oxidation of Isopropyl-meta-Xylene
to Tertiary Hydroperoxide
A. S. Frolov, E. A. Kurganova, and G. N. Koshel’
Yaroslavl State Technical University, Moskovskii pr. 86, Yaroslavl, 150023 Russia
Received July 22, 2014
Abstract—Fundamental aspects and the mechanism of the reaction of liquid-phase oxidation of isopropyl-meta-
xylene to a tertiary hydroperoxide by atmospheric oxygen, initiated by isopropylbenzene hydroperoxide or catalyzed
by N-hydroxyphthalimide were studied. It was found that using N-hydroxyphthalimide in the course of oxidation
of isopropyl-meta-xylene makes it possible to raise, compared with the initiator (isopropylbenzene hydroperoxide),
the oxidation rate and the conversion of the hydrocarbon by a factor of 2–2.5 at a 90–95% formation selectivity
of a tertiary hydroperoxide of isopropyl-meta-xylene up to a conversion of 20–25%.
The liquid-phase oxidation of alkyl aromatic hydro-
carbons underlies promising methods for production of
various oxygen-containing compounds (alkyl)phenols
and aliphatic ketones widely used in syntheses of poly-
meric materials possessing a set of valuable properties .
The “cumene” method for obtaining phenol and ac-
etone and the joint synthesis of styrene and propylene
oxide (“chalcone-process”) have been studied in detail
and are widely used in the industry. The key stage in these
methods is the liquid-phase initiated oxidation of isopro-
pylbenzene (IPB) and ethylbenzene to the corresponding
This important way to obtain valuable organic syn-
thesis products can be enhanced by using other alkyl
aromatic hydrocarbons and their HPs.
The present study is concerned with the reaction of
liquid-phase selective oxidation of isopropyl-meta-xylene
(IP-m-X) to a tertiary HP, which underlies the synthesis
of 1,3,5-xylenol, a large-tonnage product of petrochemi-
cal synthesis, widely used in manufacture of plasticizers,
paint-and-varnish materials, and disinfectants. The oxida-
tion process is shown in Scheme 1.
The choice of meta-xylene to obtain an isopropyl
derivative of benzene is not accidental. The point is that,
among the three isomers of xylenes, only para- and
ortho-xylenes are the most widely used in large-tonnage
manufacture of therephthalic acid and phthalic anhydride.
At the same time, meta-xylene does not ﬁ nd efﬁ cient use
and expanding its application ﬁ eld is a topical task.
The oxidation of IP-m-X is, in fact, rather close to
the process of UPB oxidation to an HP. However, the