Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 9, pp. 1555−1559.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.B. Shishmakov, Yu.V. Mikushina, O.V. Koryakova, M.S. Valova, S.Yu. Men’shikov, L.A. Petrov, 2011, published in Zhurnal
Prikladnoi Khimii, 2011, Vol. 84, No. 9, pp. 1505−1509.
AND INDUSTRIAL ORGANIC CHEMISTRY
Oxidation of 2,3,6-Trimethylphenol on Titanium Dioxide
Xerogel by Hydrogen Peroxide in the Absence
of an Organic Solvent
A. B. Shishmakov, Yu. V. Mikushina, O. V. Koryakova, M. S. Valova,
S. Yu. Men’shikov, and L. A. Petrov
Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Yekaterinburg, Russia
Received October 11, 2010
Abstract—Fundamental aspects of the synthesis of 2,3,5-trimethylbenzoquinone by oxidation of
2,3,6-trimethylphenol adsorbed on the surface of a titanium dioxide xerogel and on TiO
modiﬁ ed with powdered
cellulose with hydrogen peroxide without any organic solvent involved in the process were studied.
The heterogeneous catalytic oxidation of 2,3,6-tri-
methylphenol (TMP) by hydrogen peroxide is of great
practical interest as one of the most ecologically safe
ways to obtain 2,3,5-trimehylbenzoquinone (TMBQ),
which is the main half-product for synthesis of vita-
min E. As catalysts serve aerogels TiO
, sol-gels of the TiO
system , titanosili-
cates SBA-15 , and commercial silica grafted with
Ti(IV) . The reaction of TMP oxidation into TMBQ
is conventionally performed with an aqueous solution
of hydrogen peroxide in an organic solvent, whose role
is played by alcohols, aldehydes, and carboxylic acids.
The oxidation of TMP is a heterogeneous process
mostly occurring at the catalyst surface , which
suggests that this process can be performed without an
organic solvent. This satisﬁ es the increasingly stringent
requirements to the ecological safety and efﬁ ciency
of chemical processes and markedly simpliﬁ es the
technology for synthesis of the target product.
We chose a titanium dioxide xerogel and TiO
modiﬁ ed with powdered cellulose (PCe) as catalysts
for peroxide oxidation. The choice of the TiO
composite was due to previously obtained experimental
data on formation and stabilization of highly dispersed
particles by hydrolysis of tetrabutoxititanium
(TBT) in the matrix of powdered cellulose [6, 7].
The goal of our study was to assess the possibility
of synthesizing TMBQ by oxidation of TMP adsorbed
on the surface of a TiO
xerogel and on TiO
hydrogen peroxide in the absence of an organic solvent.
The titanium dioxide xerogel was produced by
hydrolysis of a methanolic solution of TBT with
water (TBT : methanol = 1 : 1 v/v). The solution was
hydrolyzed with a triple volume of water at 20°C
under vigorous agitation. The resulting precipitate was
washed on a vacuum-ﬁ lter until no butanol was found
in washing water. The washed precipitate was dried at
100°C to constant weight. The speciﬁ c surface area S
of the xerogel was 60 m
Powdered cellulose was produced by hydrolysis
of sulfate cellulose from Baikal pulp-and-paper
combine [TU OP (Technical Speciﬁ cation for Nature
Preservation) 13-027 94 88-08–91] in 2.5 N hydrochloric
acid at 100°C. The hydrolysis was performed for 2 h.
The resulting product was washed with distilled water
on a vacuum-ﬁ lter to neutral pH and dried at 100°C.
To obtain a composite material of composition
: PCe = 0.4 : 0.6 (w/w), we dissolved 60 ml of
TBT in 60 ml of methanol and added 20 g of PCe to