Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 7, pp. 1238−1242.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
A.R. Tuktarov, A.R. Akhmetov, G.N. Kirichenko, V.I. Glazunova, L.M. Khalilov, U.M. Dzhemilev, 2010, published in Zhurnal Prikladnoi
Khimii, 2010, Vol. 83, No. 7, pp. 1132−1136.
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Functionally Substituted Methanofullerenes
and Study of Their Tribological Properties
A. R. Tuktarov, A. R. Akhmetov, G. N. Kirichenko, V. I. Glazunova,
L. M. Khalilov, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Received October 26, 2009
Abstract—Possibility of synthesizing functionally substituted methanofullerenes by cycloaddition of diazo
derivatives of methionine and threonine to C
fullerene in the presence of a three-component catalytic system
Al was examined. Tribological characteristics of the resulting compound as an additive to
an industrial oil were studied.
A report appeared in 2003  that fulleroids are
promising as nanomodiﬁ ers for lubricating and antifric-
tion materials. Because most of additives presently used
in the industry are sulfur-containing compounds, it was
assumed that sulfur-containing fullerene derivatives can
be used as new materials for improvement of lubricating
and antifriction properties of additives and as materials
substantially improving the antiscoring and antiwear
properties of oils.
Recently, cycloaddition to C
fullerene has been
performed in the presence of a three-component
catalytic system Pd
Al for diazo acetic ester
 and α-substituted diazo acetates . In continuation
of these studies and with the aim of developing sulfur-
containing fullerene derivatives with various structures,
the reaction of C
fullerene with a diazo acetate
containing simultaneously an ester and a sulﬁ de groups
was examined and the tribological properties of the
cycloadducts obtained were analyzed.
As objects of study were chosen diazo derivatives of
ethyl esters of d,l-methionine and threonine. It was found
that the reaction of a diazo derivative of methionine
fullerene (5 : 1 molar ratio) in the presence
of 20 mol % three-component catalyst Pd(acac)
Al (1 : 2 : 4) at a temperature of 80°C in the course
of 1 h in ortho-dichlorobenzene gives a mixture of
stereoisomeric [5,6]-closed, (I) and (II), and [6,6]-closed
(III) adducts with a total yield of about 45%. Making the
reaction longer (1.5 h and more) fails to noticeably raise
the yield of the target products. Changing the relative
amounts of the components of the catalytic system
Al from 1 : 2 : 4 to 1 : 4 : 4 results
in selective formation of a methanofullerene in a ~40%
yield by Scheme 1.
According to the data furnished by
D NMR spectroscopy, the adducts synthesized, (I)–
(III), are represented by three set of signals with an
intensity ratio of 8 : 1 : 4 (found from the integral curves
H NMR spectra).
According to the characteristic signals of the
methylene (δH = 4.24 ppm) and methyl (δH = 1.37 ppm)
groups, the highest-intensity set belongs to a [5,6]-
open isomer (I) in the syn-conﬁ guration (with the
ester group situated over the six-membered ring of the
fullerene molecule). Protons of the α-methylene group
of the sulﬁ de moiety at δH = 4.06 pp exhibit geminal
interactions with the bridge (δC = 58.33 ppm) and
vicinal interactions with nodal sp
atoms (δC = 134.37 ppm) of the fullerene skeleton.
Isomer (II) is represented in the proton magnetic
resonance spectrum by the weakest ﬁ eld quartet
) = 4.61 ppm], characteristic of the