Beilstein J. Org. Chem. 2012, 8, 227–233.
MHz, C5D5N) δ 191.71, 164.37, 138.12, 130.79, 129.92, (d, J = 8.0 Hz, 1H), 3.69 (s, 2H), 2.17 (s, 3H), 2.10 (s, 2H),
129.80, 117.89, 40.87, 37.70, 29.82.
2.01–1.95 (m, 7H), 1.67 (s, 2H), 1.65–1.55 (m, 2H), 1.50 (br s,
4H); 13C NMR δ 170.46, 153.58, 134.47, 126.84, 126.75,
2-(1-Adamantyl)-4-hydroxybenzoic acid ethyl ester (3ga): 126.69, 116.14, 73.02, 41.38, 39.30 (overlapped with DMSO-
White powder; mp 250–252 °C; 1H NMR (500 MHz, C6D6N) δ d6), 38.20, 36.26, 35.95, 33.71, 28.19, 20.60; ESI–HRMS:
13.85 (s, 1H), 9.80 (d, J = 3.0 Hz, 1H), 9.53 (dd, J1 = 2.5 Hz, J2 [M − 1]+ calcd for C20H25O3, 313.1804; found, 313.1798.
= 10.5 Hz, 1H), 8.66 (d, J = 10.0 Hz, 1H), 5.88 (q, J = 9.0 Hz,
2H), 3.85 (d, J = 2.5, 6H), 3.54 (s, 3H), 3.25 (m, 6H), 2.78 (t, J 2-(3-Acetoxymethyl-1-adamantyl)-4-bromoanisole (3jc):
= 9.0 Hz, 3H); 13C NMR δ 167.59, 162.83, 137.37, 129.95, White powder; mp 110–112 °C; 1H NMR (400 MHz, CDCl3) δ
129.89, 122.07, 117.36, 61.00, 40.98, 37.71, 29.84, 15.08; 7.27 (d, J = 9.6 Hz, 1H), 7.26 (s, 1H), 6.73 (d, J = 9.2 Hz, 1H),
ESI–HRMS: [M − 1]+ calcd for C19H23O3, 299.1647; found, 3.80 (s, 3H), 3.74 (s, 2H), 2.16 (s, 2H), 2.06 (s, 3H), 2.00–1.95
299.1648.
(m, 4H), 1.83 (s, 2H), 1.75–1.65 (m, 2H), 1.55 (br s, 4H);
13C NMR δ 171.32, 157.82, 139.86, 129.68, 129.56, 113.40,
3-(1-Adamantyl)-4-hydroxyacetophenone (3ha): White 113.28, 73.92, 55.21, 41.78, 39.78, 38.61, 37.44, 36.31, 34.09,
powder; mp 183–185 °C; 1H NMR (400 MHz, CDCl3, 25 °C), 28.75, 20.91; ESI–HRMS: [M]+ calcd for C20H25BrO3,
δ 7.92 (d, J = 2.0 Hz, 1H), 7.74 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz, 392.0987; found, 392.0984.
1H), 7.01 (s, 1H), 6.80 (d, J = 8.4 Hz, 1H), 2.60 (s, 3H), 2.16,
2.10 (s + s overlapped, 9H), 1.80 (s, 6H); 13C NMR δ (100 2-(3-Carboxy-1-adamantyl)-4-bromophenol (3ab): White
MHz, C5D5N, 25 °C) δ 197.09, 163.02, 137.39, 129.90, 129.35, powder; mp 209–211 °C; 1H NMR (400 MHz, DMSO-d6) δ
128.59, 117.18, 41.01, 37.76, 29.89, 26.78; ESI–HRMS: 12.02 (br s, 1H), 9.68 (br s, 1H), 7.17 (d, J = 8.0 Hz, 1H), 7.11
[M − 1]+ calcd for C18H21O2, 269.1542; found, 269.1540. (s, 1H), 6.74 (d, J = 8.4 Hz, 1H), 2.11–2.01 (m, 4H), 1.95–1.92
(m, 4H), 1.80 (s, 4H), 1.66 (s, 2H); 13C NMR δ 178.36, 155.37,
2-(1-Adamantyl)-4-nitrophenol (3ia): White powder; mp 137.28, 129.25, 128.78, 118.37, 110.42, 40.56, 40.51 (over-
227–229 °C; 1H NMR (500 MHz, C6D6N) δ 8.29 (d, J = 3.5 lapped with DMSO-d6), 38.62, 37.90, 36.57, 35.41, 28.11;
Hz, 1H), 8.10 (dd, J1 = 3.5 Hz, J2 = 11.0 Hz, 1H), 7.06 (d, J = ESI–HRMS: [M − 1]+ calcd for C17H18BrO3, 349.0439; found,
11.5 Hz, 1H), 2.27 (s, 6H), 2.06 (s, 3H), 1.78 (m, 6H); 349.0440.
13C NMR δ 164.76, 141.08, 138.14, 124.20, 124.16 (over-
lapped with C6D6N), 117.31, 40.60, 37.81, 37.57, 29.74; Acknowledgements
ESI–HRMS: [M − 1]+ calcd for C16H18NO3, 272.1287; found, Financial support provided by the National Science Foundation
272.1291.
of China (20972049) is gratefully acknowledged.
References
2-(1-Adamantyl)-4-bromoanisole (3ja) [29]: mp 136–138 °C;
1H NMR (400 MHz, CDCl3, 25 °C) δ 7.31 (s, 1H), 7.28 (d, J =
8.4 Hz, 1H), 6.75 (d, J = 8.8 Hz, 1H), 3.83 (s, 3H), 2.08 (s, 9H),
1.79 (s, 6H); 13C NMR δ 157.95, 140.83, 129.79, 129.33,
113.36, 113.32, 55.23, 40.39, 37.22, 37.06, 29.07.
1. Shroot, B.; Eustache, J.; Bernardon, J.-M. Benzonaphthalene
derivatives and compositions. U.S. Patent 4,717,720, Jan 5, 1988.
2. Dawson, M. I.; Harris, D. L.; Liu, G.; Hobbs, P. D.; Lange, C. W.;
Jong, L.; Bruey-Sedano, N.; James, S. Y.; Zhang, X.-k.;
Peterson, V. J.; Leid, M.; Farhana, L.; Rishi, A. K.; Fontana, J. A.
3. Cincinelli, R.; Dallavalle, S.; Nannei, R.; Carella, S.; de Zani, D.;
Merlini, L.; Penco, S.; Garattini, E.; Giannini, G.; Pisano, C.; Vesci, L.;
Carminati, P.; Zuco, V.; Zanchi, C.; Zunino, F. J. Med. Chem. 2005, 48,
2-(3-Acetoxymethyl-1-adamantyl)-4-bromophenol (3ac):
White powder; mp 184–186 °C; 1H NMR (400 MHz, DMSO-
d6) δ 9.65 (s, 1H), 7.16 (dd, J1 = 8.4 Hz, J2 = 2.4 Hz, 1H), 7.11
(d, J = 2.4 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 3.69 (s, 2H), 2.10
(s, 2H), 2.01–1.94 (m, 7H), 1.80 (s, 2H), 1.60–1.50 (m, 2H),
1.49 (m, 4H); 13C NMR δ 170.38, 155.38, 137.47, 129.14,
128.80, 118.32, 110.38, 72.89, 40.99, 39.04 (overlapped with
DMSO-d6), 38.04, 36.62, 35.77, 33.69, 28.09, 20.57;
ESI–HRMS: [M − 1]+ calcd for C19H22BrO3, 377.0752; found,
377.0756.
4. Lorenzo, P.; Alvarez, R.; Ortiz, M. A.; Alvarez, S.; Piedrafita, F. J.;
de Lera, Á. R. J. Med. Chem. 2008, 51, 5431–5440.
5. Pérez-Rodríguez, S.; Ortiz, M. A.; Pereira, R.; Rodríguez-Barrios, F.;
de Lera, Á. R.; Piedrafita, F. J. Eur. J. Med. Chem. 2009, 44,
6. Dawson, M. I.; Xia, Z.; Jiang, T.; Ye, M.; Fontana, J. A.; Farhana, L.;
Patel, B.; Xue, L. P.; Bhuiyan, M.; Pellicciari, R.; Macchiarulo, A.;
Nuti, R.; Zhang, X.-K.; Han, Y.-H.; Tautz, L.; Hobbs, P. D.; Jong, L.;
Waleh, N.; Chao, W.; Feng, G.-S.; Pang, Y.; Su, Y. J. Med. Chem.
2-(3-Acetoxymethyl-1-adamantyl)-4-methylphenol (3cc):
White powder; mp 217–219 °C; 1H NMR (400 MHz, DMSO-
d6) δ 8.97 (s, 1H), 6.85 (s, 1H), 6.78 (d, J = 8.0 Hz, 1H), 6.63
232