Method of synthesizing adamantyl-substituted phenols based on 1,3-dehydroadamantane

Article abstract of DOI:10.1134/S1070427209040284

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.

Full text of DOI:10.1134/S1070427209040284

ISSN 1070-4272, 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.
BRIEF
COMMUNICATIONS
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.
DOI: 10.1134/S1070427209040284
Sterically hindered phenols and their derivatives
are of practical interest as antioxidants possessing high
efficiency, 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 [3].
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 [9].
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
2
00°C) within a long time (up to 16 h) in the presence of
EXPERIMENTAL
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.
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.
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.
Scheme.
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.
I
II−V
VI−IX
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.
Here R1 = R2 = R3 = H (II), (VI); R1 = OH, R2 = R3 = H
1
3
2
1
(III), (VII); R = R = H, R = OH (IV), (VIII); R =
2
3
R = H, R = OH (V), (IX).
6
91

692
BUTOV et al.
4
-(Adamant-1-yl)phenol (VI). To 4.20 g (0.045
mol) of phenol in 10 ml of diethyl ether a solution of 4 g
0.0298 mol) of freshly distilled 1,3-dehydroadamantane
+
+
+
2
2
44 (M 83%), 187 ([М-С Н ] , 100%), 150 ([М-94] ,
4 9
4%).
(
in 20 ml of diethyl ether was added dropwise in the
presence of 0.03 g (0.0003 mol) of sulfuric acid in the
atmosphere of dry nitrogen at room temperature. The
mixture was exposed for 20 min at 30−35°С, the solvent
was evaporated, the precipitate was washed out with hot
water, and recrystallized from alcohol. Yield 6.45 g (94%)
of a solid product, mp 185−187°С (published 186−187°С
CONCLUSION
A convenient preparative method of synthesizing
adamantylated phenols was developed, which allows
these compounds to be obtained at low temperatures
(
30−35°С) within a short time.
[
(
1
8]). Found (%): C 83.94, Н 9.06. C H О. Calculated
16 20
REFERENCES
+
%): C 84.76, Н 8.83. Mass spectrum, I , %: 228 (M
rel
+
+
00%), 171 ([М-С Н ] , 94%), 134 (Ad , 30%).
4 9
1. Sorokina, I.V., Krysin, A.P., Khlebnikova, T.B., et al.,
4
-(Adamant-1-yl)pyrocatechol (VII). It was
synthesized analogously to compound VI from 4.95 g
0.045 mol) of 2-hydroxyphenol (pyrocatechol) and 4
Analit. obzor SO RAN; GPNTB, Ser. “Ekologiya”
(
Analit. Review. Siberian Branch of Russian Academy of
Sciences; State Public Scientific Technical Library. Series
Ecology”), Novosibirsk: Novosibirsk Institute of Organic
(
“
g (0.0298 mol) of 1,3-dehydroadamantane. Yield 5.9
g (81%) of a solid product, mp 143−144°C (published
43−144°С [5]). Found (%): C 78.51, Н 8.19. C H О .
Calculated (%): C 78.65, Н 8.25. Mass spectrum, I , %:
Chemistry, 1997.
. Khairullina, V.R., Kirlan, S.A., et al., Izv. Akad. Nauk, Ser.
Khim., 2006, no. 8, pp. 1274-1279.
. Sokolenko, V.A., Svirskaya, N.M., Velikov, A.A., and
Sizova, N.V., Kinet. Katal., 2002, vol. 43, no. 2, pp. 205−
2
3
1
16 20 2
rel
+
+
+
2
2
44 (M 83%), 187 ([М-С Н ] , 100%), 150 ([М-94] ,
4 9
6%).
-(Adamant-1-yl)resorcin (VIII). It was synthesized
2
08.
4
4
. Moiseev, I.K., Makarova, N.V., and Zemtsova, M.N., Usp.
analogously to compound VI from 4.95 g (0.045 mol)
Khim., 1999, vol. 68, no. 12, pp. 1102−1121.
of 3-hydroxyphenol (resorcin) and 4 g (0.0298 mol) of
5. Sokolenko, V.A., Kuznetsova, L.N., and Orlovskaya, N.F.,
1
,3-dehydroadamantane. Yield 6.40 g (88%) of a solid
Izv. Akad. Nauk, Ser. Khim., 1996, no. 2, p. 505.
. Sokolenko, V.A. and Semenov, S.Yu., Izv. Akad. Nauk
SSSR, Ser. Khim., 1989, p. 750.
7. Miryan, N.I., Yurchenko, A.G., and Kirienko, E.I., Ukr.
Khim. Zh., 1990, vol. 56, no. 2, pp. 183-186.
6
product, mp 234−235°С (published 235−236°С [10]).
Found (%): C 78.78, Н 8.14. C H О . Calculated (%):
C 78.65, Н 8.25. Mass spectrum, I , %: 244 (M 83%),
1
6
20
2
+
rel
+
+
1
87 ([М-С Н ] , 100%), 150 ([М-94] , 23,7%).
4 9
8
. USSR Inventor’s Certificate 1641801, IPC C 07 39/06,
7/16.
4
-(Adamant-1-yl)hydroquinone (IX). It was syn-
thesized analogously to compound (VI) from 2 4.95 g
0.045 mol) of 4-hydroxyphenol (hydroquinone) and
3
9
. Sokolenko, V.V. and Svirskaya, N.M., Prospects of
Evolution of Chemistry of Frame Compounds and their
Practical Application in Industries, Abstracts of Papers,
Kiev, 1986, p. 59.
(
4
6
2
g (0.0298 mol) of 1,3-dehydroadamantane. Yield
.14 g (84%) of a solid product, mp 212°С (published
10−212°С [7]). Found (%): C 78.59, Н 8.11. C H О .
10. Shwedov, V.I., Safonova, O.A., et al., Khim.-Farm. Zh.,
1980, no. 2, pp. 54−57.
1
6
20
2
Calculated (%): C 78.65, Н 8.25. Mass spectrum, I , %:
rel
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 82 No. 4 2009