226 JOURNAL OF CHEMICAL RESEARCH 2010
Table 2 Continued
Entry
27
Substrate
Time/h
5
Product
Yield/%a
93
OMe
OMe
OMe
OH
CO2Me
CO2Me
OMe
OMe
28
3
4
94
93
OH
OMe
CHO
CHO
OMe
OMe
29
OMe
O
OH
O
a Isolated yield.
b Molar ratio of substrate:AlCl3 = 1:4.
1
Experimental
5-Nitro-2-hydroxyacetophenone (Table 2, entry 9): H NMR: 2.76
(s, 3H), 6.90 (d, 1H, J = 8.4 Hz), 8.24 (dd, 1H, J = 8.4 Hz, J = 2.0 Hz),
8.60 (s, 1H), 12.77 (s, 1H). EI-MS: 181(M+), m.p. 94–96 °C (lit.16
101–102 °C).
Melting points were measured on a Kofler apparatus and were uncor-
1
rected. The H NMR and 13C NMR data were recorded in CDCl3
solution with Bruker AM-200 or AM-400 MHz spectrometers. The
chemical shifts are reported in ppm relative to TMS or CDCl . Mass
spectra were recorded on a ZAB-HS mass spectrometer (EI).3Micro-
analyses were performed on a MOD-1106 elemental analyser. Column
chromatography was generally performed on silica gel (200–300
mesh) eluting with petroleum ether:ethyl acetate mixtures.
1
4-Methyl-2-hydroxyacetophenone (Table 2, entry 10): H NMR:
2.35 (s, 3H), 2.60 (s, 3H), 6.71 (d, 1H, J = 8.0 Hz), 6.80 (s, 1H), 7.61
(d, 1H, J = 8.0 Hz), 12.30 (s, 1H). EI-MS: 150 (M+)
1,1’-(4,6-Dihydroxy-1,3-phenylene)diethanone (Table 2, entry 11):
1H NMR: 2.64 (s, 3H), 6.44 (s, 1H), 8.21 (s, 1H), 12.93 (s, 1H).
EI-MS: 194(M+), m.p. 204–206 °C (lit.17 178–180 °C).
4-Fluoro-2-nitrophenol (Table 2, entry 13): 1H NMR: 2.35 (s, 3H),
7.05 (d, 1H, J = 8.4 Hz), 7.40 (dd, 1H, J = 8.4 Hz, J = 2.0 Hz), 7.90
(d, 1H, J = 2.0 Hz), 10.43 (s, 1H). EI-MS: 157(M+), m.p. 70–72 °C
(lit.18 72.5 °C).
Demethylation by AlCl3; general procedure
To a solution of substrate (1.0 mmol) in CH2Cl (5mL) was added
AlCl3 (200 mg, 1.5 mmol, 1.5 equiv.) in one por2tion at –5 °C. After
being stirred at the same temperature for 5 minutes, the mixture was
warmed up to 25 °C and stirred for a further period (see Table 2). The
reaction mixture was then poured into cold water and extracted with
CH2Cl . The combined organic layer was washed successively with
saturat2ed NaHCO3 and brine, and then dried with Na2SO . The solvent
was evaporated under vacuum and the crude product 4was purified
by column chromatography on silica gel eluting with a mixture of
petroleum ether and ethyl acetate.
1-(3-Hydroxy-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octahydrophen-
anthren-2-yl)ethanone (Table 2, entry 1): 1H NMR: (CDCl3, 400 MHz)
ppm 0.94 (s, 3H), 0.96 (s, 3H), 1.18 (s, 3H), 1.20–2.25 (m, 9H), 2.58
(s, 3H), 2.82–2.92 (m, 2H), 6.67 (s, 1H), 7.40 (s, 1H), 11.93 (s, 1H).
13C NMR: (CDCl3, 100 MHz) ppm 19.0, 19.1, 21.7, 24.2, 26.4, 29.3,
33.2, 33.6, 38.5, 38.6, 41.5, 49.7, 113.5, 115.3, 117.7, 126.1, 130.6,
163.1, 203.8. PSI-MS: Found M+H = 287.2003, C19H26O2 requires
M+H = 287.2006. IR: 2926, 1642, 1566, 1485, 1265 cm−1.
1
2-Hydroxy-5-methylphenyldiphenylketone (Table 2, entry 15): H
NMR: 2.27 (s, 3H), 7.00 (d, 1H, J = 8.4 Hz), 7.32–7.37 (m, 2H),
7.51–7.54 (m, 2H), 7.58–7.70 (m, 3H), 11.86 (s, 1H). EI-MS: 212(M+),
m.p. 79–80 °C (lit.19 82–83 °C).
2-Hydroxy-4-methyl-5-methoxyacetophenone (Table 2, entry 19):
1H NMR: 2.35 (s, 3H), 2.38 (s, 3H), 3.86 (s, 3H), 6.88 (s, 1H), 7.21
(s, 3H). EI-MS: 180(M+), m.p:110–112 °C (lit.20 110–112 °C).
1
2-Hydroxy-5-methoxyacetophenone (Table 2, entry 20): H NMR:
2.62 (s, 3H), 3.80 (s, 3H), 6.92 (d, 1H, J = 8.4Hz), 7.12 (dd, 1H,
J = 8.4Hz, J = 2.0Hz), 7.16 (d, 1H, J = 2.0Hz), 11.86 (s, 1H), EI-MS:
166(M+), m.p. 49–50 °C (lit.21 51–52 °C).
1
Ethyl 2-hydroxy-3-methoxybenzoate(Table 2, entry 21): H NMR
(200 MHz): 1.34 (t, 3H, J = 7.2Hz), 3.86 (s, 3H), 4.32 (q, 2H,
J = 7.2Hz), 6.74 (t, 1H, J = 8.0Hz), 6.98 (d, 1H, J = 8.0Hz), 7.39 (d,
1H, J = 8.0Hz), 11.09 (s, 1H). 13C NMR: (CDCl3, 100MHz) ppm 13.7,
55.7, 61.2, 112.4, 116.1, 118.1, 120.7, 148.1, 151.8, 170.1. PSI-MS:
Found M+Na = 219.0624, C10H12O4 requires M+Na = 219.0628. IR:
3265, 2984, 1678, 1464, 1250 cm−1.
7-acetyl-6-hydroxy-1,1,4a-trimethyl-2,3,4,4a,10,10a-hexahydro-
phenanthren-9(1H)-one (Table 2, entry 2): 1H NMR: (CDCl3,
400MHz) ppm 0.90 (s, 3H), 0.95 (s, 3H), 1.18 (s, 3H), 1.23–2.26 (m,
7H), 2.63 (s, 3H), 2.55–2.66 (m, 2H), 6,89 (s, 1H), 8.43 (s, 1H), 12.55
(s, 1H). 13C NMR: (CDCl3, 100 MHz) ppm 18.7, 21.4, 22.9, 26.6,
32.5, 33.4, 35.9, 37.5, 38.7, 41.1, 48.6, 113.0, 118.0, 123.3, 131.7,
164.5, 166.4, 197.4, 204.6. PSI-MS: Found M+H = 301.1789,
C19H24O3 requires M+H = 301.1798. IR: 2957, 1684, 1649, 1564,
1475, 1361, 1290, 1219 cm−1.
1
2-Hydroxy-3-methoxybenzaldehyde (Table 2, entry 22): H NMR:
(CDCl3, 400MHz) ppm 3.92 (s, 3H), 6.95 (t, 1H, J = 8.0Hz), 7.11 (d,
1H, J = 8.0Hz), 7.17 (d, 1H, J = 8.0Hz), 9.92 (s, 1H), 11.13 (s, 1H).
13C NMR: (CDCl3, 100MHz) ppm 55.9, 117.6, 119.3, 120.4, 124.2,
147.8, 151.2, 196.3. PSI-MS: Found M+H = 153.0547, C8H8O3
requires M+H = 153.0546. IR: 3420, 2644, 1650, 1462, 1256 cm−1.
5-Bromo-2-hydroxyacetophenone (Table 2, entry 6): 1H NMR: 2.63
(s, 3H), 6.90 (d, 1H, J = 8.8 Hz), 7.54 (dd, 1H, J = 8.8 Hz, J = 2.4 Hz),
7.83 (d, 1H, J = 2.4 Hz), 12.18 (s, 1H). EI-MS: 214(M+).
1
2-Hydroxy-3-methoxyacetophenone(Table 2, entry 23): H NMR:
5-Fluoro-2-hydroxyacetophenone (Table 2, entry 7): 1H NMR: 2.63
(s, 3H), 6.96 (dd, 1H, J = 8.8Hz, J = 4.4Hz), 7.54 (ddd, 1H, J = 8.8Hz,
J = 4.4Hz, J = 2.8Hz), 7.40 (dd, 1H, J = 8.8Hz, J = 2.8Hz), 11.98
(s, 1H). EI-MS: 154(M+).
(CDCl3, 400MHz) ppm 2.63 (s, 3H), 3.89 (s, 3H), 6.82–6.86 (m, 1H),
7.04 (d, 1H, J = 7.6Hz), 7.32 (d, 1H, J = 8.2Hz), 12.58 (s, 1H). 13C
NMR: (CDCl3, 100MHz) ppm 27.0, 56.1, 116.9, 118.2, 119.6, 121.6,
148.8, 152.7, 204.9. PSI-MS: M+Na = 189.0519, C9H10O3 requires
M+Na = 189.0522. IR: 2907, 1698, 1457, 1365, 1261 cm−1.
5-Methyl-2-hydroxyacetophenone (Table 2, entry 8): 1H NMR: 2.32
(s, 3H), 2.63 (s, 3H), 6.90 (d, 1H, J = 8.4 Hz), 7.29 (dd, 1H, J = 8.4 Hz,
J = 2.0 Hz), 7.51 (s, 1H), 12.10 (s, 1H). EI-MS: 150 (M+).
Ethyl 2-hydroxy-3,4-dimethoxybenzoate (Table 2, entry 24): 1H
NMR: (CDCl3, 400MHz) ppm 1.37 (t, 3H, 7.2Hz), 3.88 (s, 3H), 3.96