JOURNAL OF CHEMICAL RESEARCH 2010 329
CDCl3) 1.83–1.65 (2H, m), 2.15–2.30 (2H, m), 2.72–2.84 (2H, m),
3J = 8.4 Hz), 7.12 (2H, d, 3J = 8.8 Hz); δC (100.5 MHz, CDCl3) 14.1
(CH3), 22.7 (CH2), 23.0 (CH2), 25.4 (CH2), 26.1 (CH2), 29.4 (CH2),
29.6 (CH2), 29.7 (15C, CH2), 31.9 (CH2), 55.7 (OCH3), 67.9 (OCH2),
108.2 (CH), 113.9 (2C, CH), 125.8 (CH), 126.1 (CH), 127.5 (Cquat),
127.6 (CH), 128.9 (Cquat), 129.5 (Cquat), 131.2 (2C, CH), 135.5 (Cquat),
156.4 (Cquat), 158.0 (Cquat); MS 561.5 (MH+).
3-(3-Hydroxy-2,2-dimethyl-propyloxy)-benzo[b]thiophene (12a):
Colourless solid; m.p. 93 °C. (Found: M+, 236.0869. C13H16O2S
requires M+, 236.0871). (KBr/cm−1) νmax 3850 (bs, OH), 2960, 2870,
1572, 1530, 1466, 1439, 1378, 1352, 1181, 1161, 1138, 1120, 1046,
1013, 866, 760, 732; δH 1.10 (6H, s, 2 CH3), 3.61 (2H, bs), 3.94 (2H,
s), 6.31 (1H, s), 7.34–7.39 (2H, m), 7.73–7.79 (2H, m); δC 21.7 (2C,
CH3), 36.6 (Cquat), 69.7 (–), 96.2 (CH), 120.8 (CH), 122.9 (CH), 123.7
(CH), 125.2 (CH), 133.2 (Cquat), 137.7 (Cquat), 150.9 (Cquat); MS (EI,
70 eV) m/z (%) 236 (17) [M+], 150 (100), 121 (20).
1,3-(2,2,-Dimethyl)propyl bis(benzo[b]thien-3-yl) ether (12b):
Colourless solid; m.p. 83 °C. (Found: M+, 368.0904. C21H20O2S2
requires M+, 368.0905). (KBr/cm−1) νmax 3116, 2912, 1572, 1530,
1460, 1433, 1351, 1179, 1161, 1138, 1118, 867, 798, 758, 717; δH
(270 MHz, CDCl3) 1.29 (6H. s, 2 CH3), 4.07 (4H, s), 6.31 (2H, s),
7.30–7.37 (4H, m), 7.71–7.82 (4H, m); δC 22.1 (2C, CH3), 36.3 (|Cquat),
75.2 (2C, -), 96.1 (2C, CH), 120.9 (2C, CH), 122.8 (2C, CH), 123.6
(2C, CH), 125.2 (2C, CH), 132.2 (2C, Cquat), 137.6 (2C, Cquat), 151.0
(2C, Cquat); MS (EI, 70 eV) 368 (65) [M+], 219 (31), 150 (100),
121 (76).
3
4
3
5.75 (1H, dt, J = 11.9 Hz, J = 3.9 Hz), 6.33 (1H, dt, J = 11.9 Hz,
4J = 1.9 Hz), 7.09–7.11 (4, m); MS (EI, 70 eV) m/z (%) = 144 (M+)
(36), 129 (100).
3,4-Dihydrobenzo[a]anthracene (7k):14 (Found: M+, 230.1098.
C18H14 requires M+, 230.1096). νmax (KBr/cm−1) 1656, 1540, 875, 740,
706, 679; δH (270 MHz, CDCl3) 2.42–2.44 (2H, m), 2.97 (2H, t,
3
3
3J = 8.7 Hz), 6.31 (1H, dt, J = 10.0 Hz, J = 4.9 Hz), 7.28 (1H, d,
3J = 8.6 Hz), 7.41–7.45 (3H, m), 7.83 (1H, d, 3J = 8.6 Hz), 7.94–7.99
(2H, m), 8.36 (1H, s), 8.63 (1H, s); δC (67.8 MHz, CDCl3) 22.9 (CH2),
28.5 (CH2), 120.8 (CH), 123.3 (CH), 125.1 (CH), 125.3 (CH), 126.7
(CH), 127.0 (CH), 127.1 (CH), 127.9 (CH), 128.3 (Cquat), 128.4 (Cquat),
128.5 (CH), 129.0 (CH), 130.9 (Cquat), 131.4 (Cquat), 131.8 (Cquat),
132.3 (Cquat), MS (EI, 70 eV) m/z (%) = 230 (100) [M+], 215 (22).
9,10-Dihydrobenzo[a]pyrene (7l):15 Colourless solid, m.p. 146 °C.
(Found: M+, 254.1098. C20H14 requires M+, 254.1096). (KBr/cm−1)
ν
max 3028, 2926, 2874, 2824, 1598, 1438, 1418, 1297, 1180, 882, 840,
823, 705, 682; δH 2.53–2.61 (2H, m), 3.49 (2H, dd, 3J = 8.2 Hz, 3J =
3
3
3
8.1 Hz), 6.25 (1H, dt, J = 9.7 Hz, J = 3.9 Hz), 6.84 (1H, d, J =
9.7 Hz), 7.84 (1H, s), 7.90–8.12 (6H, m), 8.25 (1H, d, J = 9.4 Hz);
3
δC 23.3 (2C), 123.0, 123.2, 124.6, 124.8, 125.0, 125.6, 126.7, 127.5,
128.0 (2C), 128.3, 128.7, 129.3, 129.6, 129.7, 130.7, 131.3, 131.9;
MS (EI, 70 eV) m/z (%) = 254 (100) [M+], 239 (23).
7,8-Dihydrobenzo[a]pyrene (7m):9 Colourless solid, mp. 127 °C.
(Found: M+, 254.1100. C20H14 requires M+, 254.1096). (KBr/cm−1)
νmax 1176, 883, 839, 827, 775, 756, 730, 704, 677; δH 2.47–2.54
3
3
3
Ms. Y. Tanaka is thanked for MS and HRMS measurements of
many of the compounds.
(2H, m), 3.23 (2H, dd, J = 8.1 Hz, J = 7.8 Hz), 6.41 (1H, dt, J =
10.0 Hz, 3J = 4.9 Hz), 7.55 (1H, d, 3J = 10.0 Hz), 7.91–8.14 (7H, m),
8.35 (1H, d, J = 9.4 Hz); δC 23.1 (–), 29.1 (–), 122.3 (CH), 123.8
3
(CH), 124.5 (CH), 124.7 (CH), 125.0 (CH), 125.1 (Cquat), 125.5 (CH),
126.0 (Cquat), 126.9 (CH), 127.2 (CH), 127.4 (CH), 128.0 (Cquat), 129.3
(Cquat), 130.1 (Cquat), 130.5 (CH), 130.7 (Cquat), 131.2 (Cquat), 134.1
(Cquat); MS (EI, 70 eV) m/z (%) = 254 (100) [M+].
Received 11 April 2010; accepted 15 May 2010
Paper 1000065 doi: 10.3184/030823410X12753214605445
Published online: 2 July 2010
3,17-Di-(O-methyl)-7-estra-1,3,5(10),6-tetraen-3,17β-diol (7n):
Colourless solid; m.p. 121 °C; (Found: M+, 312.2089. C21H28O2
requires M+, 312.2089). (KBr/cm−1) νmax 2924, 2848, 1605, 1500,
1459, 1266, 1202, 1105, 1039, 871; δH (270 MHz, CDCl3) 0.78 (3H,
s, CH3), 1.30–2.45 (11H, m), 1.96 (3H, s, CH3), 3.25 (1H, m), 3.38
(3H, s, CH3), 3.78 (3H, s, CH3), 6.20 (1H, s), 6.56 (1H, d, 4J = 2.7 Hz),
6.68 (1H, dd, J 8.4 Hz, J = 2.7 Hz), 7.16 (1H, d, J = 8.4 Hz); δC
(67.8 MHz, CDCl3) 11.5, 24.5 (2C), 26.9, 27.5, 36.7, 41.8, 42.1, 44.8,
47.3, 55.3, 57.9, 89.7, 110.4, 111.0, 124.34, 125.3, 131.4, 135.9,
143.7, 158.2; MS (EI, 70 eV) m/z (%) 312 (M+, 23).
References
1
2
3
4
5
6
7
8
9
T.W. Greene and P.G.M. Wuts, Protective groups in organic synthesis, 2nd
edn, John Wiley & Sons, N.Y. 1991, pp. 185.
E. Piers, J. Banville, C.K. Lau and I. Nagakura, Can. J. Chem., 1982, 60,
2965
M.A. Avery, C. Jennings-White and W.K.M. Chong, Tetrahedron Lett.,
1987, 28, 4269.
G. Ribeiro Morais, M.C. das Neves Oliveira and T. Thiemann, Lett. Org.
Chem., 2006, 3, 214.
3
4
3
T. Thiemann, K. Umeno, E. Inohae, M. Imai, Y. Shima, and S. Mataka,
J. Chem. Res. (S), 2002, 1; (M), 2002, 101.
5-Bromo-6-methoxy-1,2-dihydronaphthalene (7o): Οff-white solid;
3
M.C. Melo e Silva, L. Patricio, L. Gano, M.L. Sa e Melo, E. Inohae,
S. Mataka and T. Thiemann, Appl. Rad. Isotop., 2001, 54, 227.
C. Oliveira, G. Ribeiro Morais, M. Imai, E. Inohae, C. Yamamoto,
S. Mataka, T. Thiemann, J. Chem. Res., 2010, 158.
V. Vuligonda,Y. Lin and R.A.S. Chandraratna, Tetrahedron Lett., 1996, 37,
1941.
δH (200 MHz, CDCl3) 2.27–2.79 (2H, m), 2.89 (2H, dd, J = 8.6,
3J = 8.2 Hz), 3.86 (3H, s, OCH3), 5.86–5.93 (1H, m), 6.33 (1H, d,
3
3
3J = 9.8 Hz), 6.67 (1H, d, J = 8.2 Hz), 6.90 (1H, d, J = 8.2 Hz);
δC (50.3 MHz, CDCl3) 22.5 (CH2), 27.3 (CH2), 55.8 (OCH3), 108.6
(CH), 111.2 (Cquat), 124.9 (CH), 125.9 (CH), 126.2 (CH), 128.3 (Cquat),
136.2 (Cquat), 154.6 (Cquat); MS: 241.0 (81BrMH+), 239.0 ([79Br]MH+)
5-(4-Docosanyloxyphenyl)-6-methoxy-1,2-dihydronaphthalene
(7p): Colourless solid; m.p. 88 °C. (KBr/cm−1) 3033, 2920, 2849,
1607, 1571, 1512, 1472, 1239, 1175, 1065, 826, 718, 589; δH
(400 MHz, CDCl3) 0.88 (3H, t, 3J = 6.8 Hz, CH3), 1.24–1.27 (36H, m),
1.46 (2H, m), 1.78–1.82 (2H, m), 2.12–2.18 (2H, m), 2.52 (2H, t,
3J = 8.0 Hz), 3.71 (3H, s, OCH3), 3.99 (2H, t, 3J = 6.8 Hz, OCH2), 5.90
(dt, 1H, 3J = 9.6 Hz, 3J = 4.4 Hz), 6.47 (dt, 1H, 3J = 9.6 Hz, 4J = 1.8
Hz), 6.76 (1H, d, 3J = 8.4 Hz), 6.94 (2H, d, 3J = 8.8 Hz), 7.00 (1H, d,
F. Oesch, G. Stillger, H. Frank and K.L. Platt, J. Org. Chem., 1982, 47,
568.
10 R.A.W. Johnstone and M.E. Rose, Tetrahedron, 1979, 35, 2169.
11 I. Pravst, M. Zupana and S. Stavber, Tetrahedron Lett., 2006, 47, 4707.
12 cf., K. Fuchibe and T. Akiyama, J. Am. Chem. Soc., 2006, 128, 1434.
13 R.W. Thies and R.H. Chiarello, J. Org. Chem., 1979, 44, 1342.
14 R.A. Lehr, M. Schaefer-Ridder and D.M. Jerina, J. Org. Chem., 1977, 42,
736.
15 S.A. Klassen, G.H. Daub and D.L. VanderJagt, J. Org. Chem., 1983, 48,
4361.