Selective O-adamantylation of dihydric phenols by 1,3-dehydroadamantane

Article abstract of DOI:10.1134/S1070427211040318

Possibility of synthesis of 1-adamantyl phenyl ethers by one stage without use of a catalyst was researched.

Full text of DOI:10.1134/S1070427211040318

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 4, pp. 730−731. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © G.M. Butov, E.A. Kamneva, K.R. Saad, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 4, pp. 695−696.
BRIEF
COMMUNICATIONS
Selective O-Adamantylation of Dihydric Phenols
by 1,3-Dehydroadamantane
G. M. Butov, E. A. Kamneva, and K. R. Saad
Volzhskii Polytechnic Institute of Volgograd State Technical University, Volzhskii, Volgogradckaya oblast, Russia
Received April 14, 2010
Abstract—Possibility of synthesis of 1-adamantyl phenyl ethers by one stage without use of a catalyst was
researched.
DOI: 10.1134/S1070427211040318
It was shown previously [1] that mono- and dihydric
phenols in the presence of catalytic amounts of sulfuric
acid are subjected to selective C-adamantylation by
1,3-dehydroadamantane (DHA).
As initial reagents in reaction with DHA (I) we
used dihydric phenols: catechol (IIa), resorcinol (IIb)
and hydroquinone (IIc). Reaction of DHA and IIa–IIc
occurred in diethyl ether at 1.5–2-fold mole excess
of appropriate phenol in a dry argon at 30–35°С for
20–30 min. After the reaction completion the ether was
distilled and an obtained residue was washed with hot
In our study we performed regioselective reactions
of O-adamantylation of dihydric phenols by DHA to
synthesize 1-adamantyl phenyl ethers:
water to remove unreacted phenol. Then it was analyzed
by gas chromatography mass spectrometry
Cleaning of the reaction products was conducted
by recrystallization from benzene. All produced
compounds were solids. Individuality of the obtained
1-adamantyl phenyl ethers was confirmed by TLC, and
their composition and structure, by elemental analysis
and mass-spectra.
The analysis showed that in the case of lacking of
an acidic catalyst a main direction of the DHA reaction
was O-adamantylation of dihydric phenols with formation
of 1-adamantyl phenyl ethers of 80–88% yield. As side
products were also C-adamantylated dihydric phenols
(8–10% yield). Formation of fundamentally different
products of DHAreaction with dihydric phenols without
an acidic catalyst is associated with a change in the
reaction mechanism. It was known [2, 3] that in the
presence of DHAproton an adamantyl-cation is relatively
easily formed and this fact explains formation of products
of C-adamantylation of phenols.
1 - A d a m a n t y l 2 - p h e n y l e t h e r (IIIa). To
4.95 g (0.045 mol) of catechol in diethyl ether in a dry
argon at a room temperature 4 g (0.0298 mol) of fresh
distilled 1,3-dehydroadamantane in 20 ml of absolute
diethyl ether was added. The mixture was kept 30 min
at 30–35°С. After completion of the reaction the ether
was distilled and the residue was washed with hot water.
The products was purified after recrystallization from
730

SELECTIVE O-ADAMANTYLATION OF DIHYDRIC PHENOLS
731
benzene. Yield was 6.3 g (88%), mp 102–103°С. Found
(%): С 78.51, Н 8.35. С17Н22O. Calculated (%): С 78.65,
Н 8.25. Mass spectrum , m/z (intensity, %): 244 (М+, 9),
135 (Ad+, 100), 109 ([М–Ad]+, 7).
spectrophotometer “Hewlett Рackard” GC 5890 Series
II/MSD. Thin layer chromatography was carried out on
plates Silufol UV 254, eluent benzene.
CONCLUSIONS
1-Adamantyl 3-phenyl ether (IIIb). Similarly to
IIIa were synthesized 4.95 g (0.045 mol) of resorcinol
and 4 g (0.0298 mol) of fresh distilled 1,3-dehydroada-
mantane . Yield was 6.4 g (92%); mp 41–42°С. Found
(%): С 78.69, Н 8.24. С17Н22O. Calculated (%): С 78.65,
Н 8.25. Mass spectrum , m/z (intensity, %): 244 (М+, 11),
135 (Ad+, 100), 109 ([М–Ad]+, 9).
One stage method of 1-adamantyl phenyl ethers
production was developed, that enabled synthesis of
target products with high yield for small time without
use of a catalyst.
REFERENCES
1-Adamantyl 4-phenyl ether (IIIc). Similarly to IIIa
were synthesized 4.95 g (0.045 mol) of hydroquinone and
4 g (0.0298 mol) of fresh distilled 1,3-dehydroadamantane.
Yield was 5.7 g (80%); mp 130–131°С. Found (%):
С 78.74, Н 8.20. С17Н22O. Calculated (%): С 78.65,
Н 8.25. Mass spectrum , m/z (intensity, %): 244 (М+, 15),
135 (Ad+, 100), 109 ([М–Ad]+, 8).
1. Butov, G.M., Mokhov, V.M., Saad, K.R., and Kamneva, E.A.,
Zh. Prikl. Khim., 2009, vol. 82, no. 4, pp. 694–695.
2. Shchapin, I.Yu., Belopushkin, S.I., Tyurin, D.A. et al., Dokl.
Akad. Nauk, 2000, vol. 372, no. 1, pp. 60–65.
3. Fokin, A.A., Schreiner, P.R., von R. Schleyer, P., and
Gunchenko, P.A., J. Org. Chem., 1998, vol. 63, no. 19,
pp. 6494–6502.
Mass spectra were recorded by chromatography–mass
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 4 2011