Synthesis of 6,12-di(adamantane-2′-spiro)-6H,12H-dibenzo[b,f][1,5] dioxocine

Full text of DOI:10.1134/S1070428009020272

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 2, pp. 302−303. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.A. Osyanin, Yu.V. Popova, Yu.N. Klimochkin, 2009, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 2,
pp. 304−305.
SHORT
COMMUNICATIONS
Synthesis
of 6,12-Di(adamantane-2'-spiro)-6H,12H-dibenzo[b,f][1,5]dioxocine
V.A. Osyanin, Yu.V. Popova, andYu.N. Klimochkin
Samara State Technical University, Samara, 443100 Russia
e-mail: orgchem@samgtu.ru
Received June 17, 2009
DOI: 10.1134/S1070428009020272
In the absence of nucleophilic agents O-
hydroxybenzyl alcohols through the formation of O-
methylenequinones suffer di- and trimerization by [4+2]-
cycloaddition [1, 2].At the same time the cases of formal
[4+4]-cycloaddition of O-methylenequinones are
extremely seldom [3, 4]. We showed that the sterically
hindered 2-(2-hydroxyphenyl)-2-adamantanol (I) [5] at
a temperature higher than the melting point (>160°C)
DMF did not result in the formation of the spiro dimer II.
In the 1H NMR spectrum of compound II the group
of signals from aromatic protons was observed in the
region 6.74–7.05 ppm, and the signals from the
adamantane fragment, in the region 1.36–3.43 ppm. In
the 13C NMR spectrum the most deshielded in the
adamantane fragment is atom C2 (89.28 ppm), and in the
aromatic fragment, carbon atoms attached to oxygen
(156.86 ppm). In the mass spectra the most abundant
peak belongs to the product of the dimer decomposition,
O-methylenequinone A.
underwent
a
dimerization into 6H,12H-
dibenzo[b,f][1,5]dioxocine (II).
The heating for long hours in the boiling O-xylene or
2,4,8,10), 6.96 t (2Harom–3,9, J 7.34 Hz), 7.05 d (2Harom
,
–1,7
The reverse transformation of dioxocine II into alcohol
I easily occurs at its dissolution in CF3COOH and pouring
the reaction mixture in water.
J 8.08 Hz). 13C NMR spectrum (50 MHz, CDCl3), δ,
ppm: 27.13, 27.46, 33.12, 34.22, 35.00, 35.68, 36.05, 36.85,
38.45 (18CAd–1,3-10), 89.28 (2CAd–2), 122.78 and 124.85
(4Carom–2,4,8,10), 128.25 and 129.28 (4Carom–1,3,7,9), 135.72
(2C, Carom, CAd–2), 156.86 (2C arom–O). Mass spectrum,
m/z (Irel , %): 452 (1) [M]+, 226 (82) [C16H18O], 225 (100),
219 (10), 183 (27), 169 (18), 145 (19), 131 (20), 107 (21),
71 (48), 69 (43), 57 (66), 55 (49), 43 (48). Found, %: C
84.78; H 7.98. C32H36O2. Calculated, %: C 84.84; H 7.95.
6,12-Di(adamantane-22-spiro)-6H,12H-dibenzo-
[b,f][1,5]dioxocine (II). Yield 87%, mp 240–242°C
(DMF). IR spectrum, ν, cm–1: 3059 (CHarom), 2939, 2901,
2851 (CHAd), 1597, 1481, 1447, 1234 (C–O–C), 1099,
1038 (C–O–C), 968, 918, 768, 741. 1H NMR spectrum
(400 ΜHz, CDCl3), δ, ppm: 1.36 δ (2HAd, J 12.47 Hz),
1.67–1.80 m (12HAd), 1.99 s (4HAd), 2.30 d (4HAd, J
12.48 Hz), 2.59 s (2HAd), 2.69 d (2HAd, J 12.47 Hz),
The IR spectrum was recorded on a spectrophotometer
Shimadzu FTIR-8400S from KBr pellet. 1H and 13C NMR
–
2.90–2.97 m (2HAd), 3.43 s (2HAd), 6.74–6.77 m (4Harom
302

SYNTHESIS OF 6,12-DI(ADAMANTANE-2'-SPIRO)-6H,12H-DIBENZO[b,f][1,5]DIOXOCINE
303
vol. 58, p. 5367.
2. Cavitt, S.B., Sarrafizadeh, H., and Gardner, P.D., J. Org. Chem.,
1962, vol. 27, p. 1211.
3. Pisova, M. and Soucek, M., Coll. Czech. Chem. Commun.,
1982, vol. 47, p. 838.
spectra were taken on a spectrometer BrukerAM400 (400
ΜHz), internal reference TMS. Mass spectrum was
obtained on an instrument Finnigan Trace DSQ, ionizing
electrons energy 70 eV. The elemental analysis was carried
out on an automatic CHNS-analyzer Euro-Vector EA-3000.
4. Patel, A., Mazzini, F., Netscher, T., and Rosenau, T., Res.
Lett. Org. Chem., 2008, p. 1.
5. Talley, J.J. and Evans, I.A., J. Org. Chem., 1984, vol. 49,
p. 5267.
REFERENCES
1. Van De Water, R.W., and Pettus, T.R.R., Tetrahedron, 2002,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 2 2010