Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 1, pp. 107−110.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.A. Agaev, A.A. Bairamov, M.M. Muradov, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 1, pp. 107−110.
AND INDUSTRIAL ORGANIC CHEMISTRY
Catalytic Methylation of Phenol
A. A. Agaev, A. A. Bairamov, and M. M. Muradov
Sumgait State University, Sumgait, Azerbaijan
Received March 11, 2011
Abstract—Attempt was made to methylate phenol with methyl formate in the presence of a zeolite-supported
palladium and a ruthenium-titanium catalyst.
Analysis of published data on methylation of phenols
shows that these processes are for the most part studied
in order to obtain methyl derivatives of phenol and,
in particular, anisole, xylenols, and trimethylphenols.
Representatives of various classes of organic compounds
have been examined as methylating agents: methyl
halides, methanol, formaldehyde, dimethyl ether, methyl
formate, and sulfonic acid salts having methylol groups
in their structure [1–4].
As catalysts have been used chlorides, oxides of
various metals and their combinations, natural and
synthetic aluminosilicates, zeolites and their modiﬁ ed
forms, acids, superacids, and supported heteropolyacids
[2, 5–8]. It is known  that, in the presence of ZnCl
and ZnO, methyl formate methylates phenol to anisole
with good selectivity.
We made an attempt to methylate phenol with
methyl formate in the presence of a Pd-zeolite and
a ruthenium-titanium catalyst (RTC). An H-form of
high-silica zeolites (HSZ) (zeolite family of the ZSM-
5 type) was obtained in several stages from the Na-
form by ion exchange, with the zeolite treated with
a 0.1 N ammonium chloride solution at 75°C. Before
the ion exchange, the zeolites were calcined at 540°C
for 12 h. After the ion exchange was complete, the
zeolite was washed and thermostated at 120°C for
4 h. The resulting ammonium form of the zeolite
contained 0.04–0.08% sodium. H-forms of HSZs were
produced by calcination of the ammonium forms at
540°C for 6 h. A sample of the H-form was mixed with
a hydrogel of aluminum oxide in a 3 : 1 mass ratio,
thoroughly agitated, molded, granulated, dried at room
temperature, and calcined at 300 and 540°C for 3 h at
Palladium was deposited onto the H-forms of HSZs by
their impregnation with a palladium tetraaminochloride
The ruthenium–titanium catalyst was fabricated by
a special procedure used in the electrochemical industry.
The catalyst was composed of ruthenium and titanium
oxides in a 0.43 : 1 mass ratio.
Experiments were carried out in an 60-cm
electrically heated stainless steel autoclave with a reﬂ ux,
pressure gage, and sampling valve. The temperature in
the reaction zone was monitored with a thermocouple
connected to a potentiometer.
The reaction products were analyzed with a Khrom-5
chromatograph with a heat-conductivity detector and
a packed column (3.6 m × 4 mm) with dimenthylphthalate
as the liquid phase supported in an amount of 18 wt %
by Chromosorb W.
Dimenthylphthalate was synthesized by an accelerat-
ed procedure, developed by the authors, from special-
purity menthol and phthalic anhydride.
An effective analysis of difﬁ cultly separable
methylphenols and, in particular, meta- and para-