The Journal of Organic Chemistry
ARTICLE
(10 mL) at ꢀ78 °C under an inert atmosphere was added a solution of
phthalide (1 mmol) in THF (5 mL). The resulting yellow solution was
stirred at ꢀ78 °C for 25 min, after which a solution of a Michael acceptor
(1.2 mmol) in THF (5 mL) was added to it. The cooling bath was
removed after about 1 h at ꢀ78 °C, and the reaction mixture was
brought to room temperature over a period of 1 h and further stirred for
5ꢀ6 h. The reaction was then quenched with 10% NH4Cl (15 mL) or
10% aq HCl (15 mL), and the resulting solution was concentrated under
reduced pressure. The residue was diluted with ethyl acetate (3 ꢁ
50 mL), and the layers were separated. The combined extracts were
washed with brine (3 ꢁ 1/3 vol), dried (Na2SO4), and concentrated to
provide the crude product. The crude solid product was purified by
column chromatography on silica gel to obtain a pure product.
2-Methylnaphthalen-1-ol (3). Red solid. Mp: 58ꢀ61 °C (lit.2
60ꢀ63 °C). 1H NMR (400 MHz, CDCl3): δ 8.13 (d, 1H, J = 8 Hz), 7.78
(d, 1H, J = 8 Hz), 7.49ꢀ7.41 (m, 2H), 7.38 (d, 1H, J = 8.4 Hz), 7.25 (d,
1H, J = 8.8 Hz). 13C NMR (50 MHz, CDCl3): δ 148.6, 133.4, 129.0,
127.6, 125.4, 125.3, 124.2, 120.9, 120.1, 116.3, 15.7.
8-Methoxy-2-methylnaphthalen-1-ol (6). Colorless oil. νmax
(KBr, cmꢀ1): 3398, 2927, 1587, 1398, 1251, 1074. 1H NMR (400 MHz,
CDCl3): δ 9.54 (s, 1H), 7.37 (d, 1H, J = 8.0), 7.27ꢀ7.21 (m, 3H), 6.77
(d, 1H, J = 7.6), 4.06 (s, 3H), 2.36 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 155.8, 151.2, 135.3, 130.5, 124.5, 121.8, 119.1, 118.2, 114.8,
103.9, 56.1 (OCH3), 15.9 (CH3). A satisfactory mass spectrum could
not be obtained due to its susceptibility to aerial oxidation.
7,8-Dimethoxy-2-methylnaphthalen-1-ol (9a). Colorless oil.
νmax (KBr, cmꢀ1): 2356, 1344, 1220, 1027, 771. 1H NMR (400 MHz,
CDCl3): δ 9.81 (s, 1H), 7.52 (d, 1H, J = 8.8), 7.21ꢀ7.12 (m, 3H), 4.07
(s, 3H), 3.98 (s, 3H), 2.36 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
150.0, 147.2, 142.4, 130.2, 128.5 (CH), 125.1 (CH), 118.9, 118.3 (CH),
117.7, 114.2 (CH), 62.0 (OCH3), 56.9 (OCH3), 15.7 (CH3). LRMS:
m/e calcd for C13H15O3 (MH)þ 219.1023, found 219.0887.
7.46ꢀ7.36 (m, 3H), 7.22 (d, 1H, J = 8.4 Hz), 5.79 (br s, 1H), 5.43ꢀ5.39
(m, 1H), 3.52 (d, 1H, J = 7.2 Hz), 1.87 (s, 3H), 1.81 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ 149.6, 135.7, 133.5, 128.2, 127.4, 125.5, 125.2,
124.8, 121.7, 121.3, 120.0, 119.5, 30.5, 25.8, 18.0.
4-Allyl-2-methylnaphthalen-1-ol (21)33. Yellow oil. 1H NMR
(400 MHz, CDCl3): δ 8.19ꢀ8.14 (m, 1H), 7.96ꢀ7.91 (m, 1H),
7.50ꢀ7.44 (m, 2H), 7.10 (s, 1H), 6.14ꢀ6.04 (m, 1H), 5.09 (s, 1H),
5.06 (dd, 1H, J = 1.2 Hz, 8.8 Hz), 3.74 (d, 2H, J = 6 Hz), 2.40 (s, 3H). 13C
NMR (100 MHz, CDCl3): δ 137.5 (CH), 131.6, 129.4 (CH), 128.1,
125.3 (CH), 125.0 (CH), 124.7, 124.1 (CH), 121.6 (CH), 115.8 (CH2),
36.8 (CH2), 15.7 (CH3).
2-Methyl-4-p-tolylnaphthalen-1-ol (23). White solid. Mp:
70ꢀ72 °C. νmax (KBr, cmꢀ1): 3435, 2925, 1778, 1691, 1579, 1512,
1456, 1306, 1221, 1169, 1099, 821, 762. 1H NMR (400 MHz, CDCl3): δ
8.22 (d, 1H, J = 8 Hz), 7.88 (d, 1H, J = 8.4 Hz), 7.49 (t, 1H, J = 7.4 Hz),
7.42ꢀ7.36 (m, 3H), 7.29 (d, 2H, J = 7.6 Hz), 7.21 (s, 1H), 5.20 (br s,
1H), 2.46 (s, 3H), 2.45 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 147.9,
137.7, 136.5, 132.7, 131.3, 130.0 (CH), 129.9 (CH), 128.9 (CH), 125.9
(CH), 125.4 (CH), 125.1 (CH), 124.4, 121.1 (CH), 115.7, 21.2 (CH3),
15.6 (CH3). HRMS: m/e calcd for C18H17O (MH)þ 249.1209, found
249.1201.
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2-Phenylnaphthalen-1-ol (25) . Colorless oil. H NMR (200
MHz, CDCl3): δ 8.34ꢀ8.29 (m, 1H), 7.87ꢀ7.82 (m, 1H), 7.58ꢀ7.45
(m, 8H), 7.38 (d, 1H, J = 8.4 Hz), 5.89 (br s, 1H). 13C NMR (50 MHz,
CDCl3): δ 147.9, 137.5, 134.3, 129.6, 129.5, 127.9, 127.7, 127.6, 126.6,
125.6, 124.5, 122.6, 121.4, 120.3.
Dibenzo[c,h]chromen-6-one (27). White solid. Mp: 178ꢀ180 °C
(lit.38 182ꢀ183 °C). 1H NMR (200 MHz, CDCl3): δ 8.61 (d, 1H, J =
9.4 Hz), 8.49 (d, 1H, J = 8 Hz), 8.22 (d, 1H, J = 8 Hz), 8.09 (d, 1H,
J = 8.8 Hz), 7.89 (d, 1H, J = 7.2 Hz), 7.87 (d, 1H, J = 6.6 Hz), 7.79 (d, 1H,
J = 8.8 Hz), 7.69ꢀ7.58 (m, 3H). 13C NMR (100 MHz, CDCl3): δ 161.2,
147.2, 135.4, 134.9, 134.2, 130.6, 128.6, 127.9, 127.6, 127.1, 124.5, 123.9,
122.3, 122.0, 121.2, 119.1, 113.0.
Methyl 6-Oxo-6H-dibenzo[c,h]chromene-12-carboxylate
(28). White solid. Mp: 172 °C. νmax (KBr, cmꢀ1): 2358, 1732, 1259,
1020, 755. 1H NMR (400 MHz, CDCl3): δ 8.83 (d, 1H, J = 8.4 Hz), 8.56
(s, 1H), 8.45 (d, 1H, J = 8 Hz), 8.32 (d, 1H, J = 7.6 Hz), 8.02 (d, 1H, J = 8
Hz), 7.78 (t, 1H, J = 7.4 Hz), 7.61ꢀ7.52 (m, 3H), 3.99 (s, 3H). 13C
NMR (50 MHz, CDCl3): δ 166.9, 160.4, 149.8, 135.1 (CH), 134.4,
132.0, 130.6 (CH), 129.3 (CH), 129.0 (CH), 127.2 (CH), 125.9 (CH),
124.6 (CH), 124.0, 123.2, 122.5 (CH), 122.0 (CH), 120.9, 111.6, 52.4
(CH3). HRMS: m/e calcd for C19H12O4 (MH)þ 305.0814, found
305.0810.
4-Hydroxy-2,3-dimethyl-3,4-dihydro-2H-naphthalen-1-
one (37). Yellow oil. 1H NMR (400 MHz, CDCl3): δ 8.02 (d, 1H, J =
7.6 Hz), 7.59 (t, 1H, J = 7.4 Hz), 7.49 (d, 1H, J = 7.6 Hz), 7.43 (t, 1H, J =
7.4 Hz), 4.72 (d, 1H, J = 4.4 Hz), 3.39ꢀ3.21 (m, 1H), 2.49ꢀ2.38 (m,
1H), 1.22 (d, 3H, J = 3.6 Hz), 0.95 (d, 3H, J = 3.6 Hz). 13C NMR (100
MHz, CDCl3): δ 200.3, 142.0, 134.0, 131.1, 129.1, 128.7, 126.9, 72.7,
42.0, 41.9, 13.0, 11.7.
1,2,8-Trimethoxy-7-methylnaphthalene (9b). Colorless oil.
νmax (KBr, cmꢀ1): 2931, 1452, 1334, 1265, 1070, 1002. 1H NMR
(400 MHz, CDCl3): δ 7.56 (d, 1H, J = 8.8), 7.45 (d, 1H, J = 8.4), 7.23 (d,
1H, J = 8.8), 7.16 (d, 1H, J = 8.4), 3.99 (s, 3H), 3.91 (s, 3H), 3.85 (s, 3H),
2.45 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 152.2, 150.1, 142.2,
130.9, 128.2, 127.4, 124.8 (CH), 124.0 (CH), 123.7, 113.5 (CH), 61.9
(OCH3), 61.4 (OCH3), 56.6 (OCH3), 15.9 (CH3).
5,7-Dimethoxy-2-methylnaphthalen-1-ol (10). Yellow solid.
Mp: 158ꢀ160 °C (lit.25 162ꢀ165 °C). 1H NMR (400 MHz, CDCl3): δ7.66
(d, 1H,J= 8.4 Hz), 7.08 (d, 1H, J= 8.4 Hz), 6.99 (s, 1H), 6.46 (s, 1H), 3.95 (s,
3H), 3.94 (s, 3H), 2.39 (s, 3H). 13C NMR (50 MHz, CDCl3): δ 158.2, 156.8,
147.8, 125.8, 121.8, 117.8, 114.4, 100.1, 97.4, 91.6, 55.7, 55.6, 16.0.
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2,3-Dimethylnaphthalen-1-ol (12) . Colorless oil. H NMR
(400 MHz, CDCl3): δ 8.06ꢀ8.01 (m, 1H), 7.72ꢀ7.67 (m, 1H), 7.27 (s,
1H), 5.15 (br s, 1H), 2.44 (s, 3H), 2.33 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 148.3, 135.9, 132.6, 127.0 (CH), 125.5 (CH), 124.5 (CH),
122.9, 120.7 (CH), 120.3 (CH), 116.7, 21.0 (CH3), 11.8 (CH3).
Methyl 4-Hydroxy-3-methylnaphthalene-2-carboxylate (14)27.
White solid. νmax (KBr, cmꢀ1): 3483, 1707, 1448, 1385, 1298, 1228,
1039, 791. 1H NMR (200 MHz, CDCl3): δ 8.16 (d, 1H, J = 8 Hz), 8.06
(s, 1H), 7.85 (d, 1H, J = 7.6 Hz), 7.62ꢀ7.46 (m, 2H), 3.96 (s, 3H), 2.61
(s, 3H). 13C NMR (50 MHz, CDCl3): δ 168.7, 149.5, 131.6, 129.1,
128.7 (CH), 127.5 (CH), 126.3, 125.9, 123.9 (CH), 121.3 (CH), 116.0,
52.2 (CH3), 12.7 (CH3).
1,2-Dimethoxy-8,10,12-trioxacyclopenta[b]chrysen-13-
one (38). White solid. Mp: 295ꢀ297 °C (lit.41 299ꢀ300 °C). 1H NMR
(400 MHz, CDCl3): δ 7.89 (d, 1H, J = 9.2 Hz), 7.85 (s, 1H), 7.83 (d, 1H,
J = 9.6 Hz), 7.54 (d, 1H, J = 8.8 Hz), 7.45 (d, 1H, J = 8.8 Hz), 7.14 (s,
1H), 6.10 (s, 2H), 4.03 (s, 3H), 3.99 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 157.7, 153.0, 151.9, 148.8, 148.5, 146.0, 131.1, 129.7, 123.1,
120.2, 119.6, 117.8, 117.7, 115.4, 112.0, 103.9, 101.5, 99.1, 61.5, 56.5.
HRMS: m/e calcd for C20H14O6 (M)þ 350.0790, found 350.0796.
2-Allylnaphthalen-1-ol (18)29. Yellow semisolid. 1H NMR (400
MHz, CDCl3): δ 8.18 (d, 1H, J = 7.2 Hz), 7.81ꢀ7.77 (m, 1H),
7.51ꢀ7.39 (m, 3H), 7.24ꢀ7.16 (m, 1H), 6.13ꢀ6.05 (m, 1H), 5.57 (s,
1H), 5.29ꢀ5.24 (m, 2H), 3.59 (d, 2H, J = 6 Hz). 13C NMR (50 MHz,
CDCl3): δ 149.6, 136.1, 133.8, 128.4, 128.3, 127.5, 125.8, 125.3, 121.3,
120.4, 117.8, 117.0, 35.8.
7H-Furo[30,40:4,5]benzo[1,2-d][1,3]dioxol-5-one (39)43a
.
This compound was prepared as a white solid by heating piperonylic
acid (166 mg, 1 mmol), Pd(OAc)2 (22 mg, 0.1 mmol), and K2HPO4
(520 mg, 3 mmol) in dibromomethane (4 mL) in a pressure tube at
140 °C for 36 h. Yield: 78%. Rf: 0.5 (1:5 ethyl acetate/petroleum ether).
1H NMR (200 MHz, CDCl3): δ 7.23 (s, 1H), 6.85 (s, 1H,), 6.13 (s, 2H),
2-Prenylnaphthalen-1-ol (19)30. Yellow semisolid. 1H NMR
(400 MHz, CDCl3): δ 8.15 (d, 1H, J = 7.6 Hz), 7.76ꢀ7.75 (m, 1H),
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dx.doi.org/10.1021/jo2003677 |J. Org. Chem. 2011, 76, 3392–3398