Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 4, pp. 691−692.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
G.M. Butov, V.M. Mokhov, K.R. Saad, E.A. Kamneva, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 4, pp. 694−695.
Method of Synthesizing Adamantyl-Substituted Phenols
Based on 1,3-Dehydroadamantane
G. M. Butov, V. M. Mokhov, K. R. Saad, and E. A. Kamneva
Polytechnic Institute of Volgograd State Engineering University,
Volgograd State Engineering University, Volgograd, Russia
Received November 28, 2007
Abstract—The possibility of obtaining adamantyl-substituted phenols by the reaction of 1,3-dehydroadamantane
with phenols in the presence of catalytic amounts of sulfuric acid was studied.
Sterically hindered phenols and their derivatives
are of practical interest as antioxidants possessing high
efﬁ ciency, thermal stability, and hypotoxicity [1, 2]. The
presence of an adamantyl fragment in the structure of such
compounds makes it possible to strengthen essentially or
to impart to them useful properties .
Existing methods of synthesizing such compounds
are based on the reactions of appropriate phenols with
hydroxy- [4−6] or haloadamantanes [7, 8]. These
reactions are carried out at elevated temperatures (up to
200°C) within a long time (up to 16 h) in the presence of
catalysts that complicates their application in preparative
or industrial syntheses. In this connection the development
of new effective methods for the synthesis of adamantyl-
substituted phenols is of interest.
The present work is devoted to the development of
a new method of synthesizing such compounds, which
is based on the reaction of 1,3-dehydroadamantane (1,3-
DHA) with phenols in the presence of catalytic amounts
of sulfuric acid.
It was found by chromato-mass-spectrometry methods
that 1,3-dehydroadamantane (I) in the presence of
catalytic amounts of sulfuric acid readily reacts with
phenol (II), pyrocatechol (III), resorcine (IV), and
hydroquinone (V) with an appreciable exothermic effect
according to the Scheme.
The reactions of 1,3-DHA (I) with compounds (II−V)
were carried out in an inert solvent at a 1,5-2-fold molar
excess of a corresponding phenol in the atmosphere of
dry nitrogen at 30−35°С within 20−30 min.
Products of reactions (VI)−(IX) were isolated
by a recrystallization from alcohol. The composition,
structure, and individuality of the compounds were
proved by the methods of chromato-mass-spectrometry,
thin-layer chromatography, and elemental analysis.
In the absence of a catalyst the main products of
the reaction are not adamantly-substituted phenols, but
phenyladamantyl ethers. Similar facts were observed in
the case of 1,3-DHA reactions with phenol .
Mass spectra were recorded on a Hewlett Рackard
GC 5890 Series, II/MSD 5972 Series chromato-mass-
spectrophotometer. The thin-layer chromatography
experiments were carried out on Silufol UV 254 plates
with benzene as an eluent.
= H (II), (VI); R
= OH, R
(III), (VII); R
= H, R
= OH (IV), (VIII); R
= H, R
= OH (V), (IX).
I II−V VI−I X