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Me), 2.97 (dd, JZ15.8, 3.2 Hz, 1H, CH), 3.03 (dd, JZ15.3,
5.6 Hz, 1H, CH), 3.74 (s, 3H, OMe), 4.32 (dd, JZ5.6, 3.2 Hz,
1H, CH), 6.79 (d, JZ8.6 Hz, 2H, ArH), 6.83 (br s, 2H, ArH),
6.95 (d, JZ8.6 Hz, 2H, ArH). 13C NMR (CDCl3, 75.5 MHz) d
18.53, 20.99, 37.13, 37.89, 55.15, 114.38, 115.32, 120.43,
127.21, 127.94, 132.28, 136.48, 138.58, 151.97, 158.74, 167.54.
3.12 (dd, JZ2.7, 10.6 Hz, 1H, CH), 3.19 (dd, JZ4.0,
10.6 Hz, 1H, CH), 3.76 (s, 3H, OMe), 4.89 (dd, JZ2.7,
4.0 Hz, 1H, CH), 5.52 (s, 1H, OH), 6.60–6.62 (m, 2H, ArH),
6.77–6.80 (m, 1H, ArH), 7.32–7.51 (m, 3H, ArH), 7.79–
7.82 (m, 3H, ArH). 13C NMR (CDCl3, 75.5 MHz) d 37.20,
37.58, 55.69, 109.17, 114.79, 117.31, 117.82, 119.68,
122.96, 125.14, 127.32, 128.59, 129.74, 130.88, 130.96,
132.37, 144.94, 146.96, 149.51, 167.31.
4.2.8.
4-(4-Methoxyphenyl)-7-methyl-3,4-dihydro-
coumarin (3ah).12 Mp 85–87 8C (CH2Cl2/hexane). 1H
NMR (CDCl3, 300 MHz) d 2.34 (s, 3H, Me), 2.93 (dd,
JZ15.2, 8.1 Hz, 1H, CH), 3.01 (dd, JZ15.6, 6.6 Hz, 1H,
CH), 3.77 (s, 3H, OMe), 4.23 (app. t, JZ6.9 Hz, 1H, CH),
6.84–6.92 (m, 5H, ArH), 6.95 (app. d, JZ9.0 Hz, 2H, ArH).
13C NMR (CDCl3, 75.5 MHz) d 20.97, 37.30, 39.51, 55.21,
114.38, 117.38, 123.01, 125.33, 127.93, 128.49, 132.47,
138.94, 151.44, 158.86, 168.08.
4.2.14. 1,2-Dihydro-1-(4-methylphenyl)-3H-naphtho-
[2,1-b]pyran-3-one (3da). Mp 108.5–109.5 8C (CH2Cl2/
hexane). H NMR (CDCl3, 300 MHz) d 2.26 (s, 3H, Me),
1
3.13 (dd, JZ15.9, 2.7 Hz, 1H, CH), 3.20 (dd, JZ15.9,
6.6 Hz, 1H, CH), 4.92 (app. d, JZ3.9 Hz, 1H, CH), 6.99–
7.08 (m, 4H, ArH), 7.34 (d, JZ9.0 Hz, 1H, ArH), 7.40–7.49
(m, 2H, ArH), 7.79 (d, JZ7.8 Hz, 1H, ArH), 7.85 (d, JZ
9.0 Hz, 2H, ArH). 13C NMR (CDCl3, 75.5 MHz) d 20.87,
37.19, 37.44, 117.45, 117.80, 123.01, 125.12, 126.71,
127.34, 128.64, 129.71, 129.80, 130.95, 131.01, 137.12,
137.49, 149.67, 167.12. Anal. Calcd for C20H16O2: C,
83.31; H, 5.59. Found: C, 83.41; H, 5.58.
4.2.9.
4-(4-Methoxyphenyl)-6-methyl-3,4-dihydro-
coumarin (3ai).12 Mp 120.2–120.6 8C (CH2Cl2/hexane). H
NMR (CDCl3, 300 MHz) d 2.24 (s, 3H, Me), 2.93 (dd, JZ15.2,
7.5 Hz, 1H, CH), 3.00 (dd, JZ15.6, 7.5 Hz, 1H, CH), 3.77
(s, 3H, OMe), 4.22 (t, JZ6.8 Hz, 1H, CH), 6.77 (s, 1H, ArH),
6.86 (app. d, JZ8.7 Hz, 2H, ArH), 6.99 (d, JZ8.4 Hz, 1H,
ArH), 7.03–7.07 (m, 3H, ArH). 13CNMR(CDCl3, 75.5 MHz)d
20.71, 37.28, 39.92, 55.24, 114.34, 116.77, 125.74, 128.54,
128.56, 129.15, 132.43, 134.22, 149.57, 158.92, 167.91.
1
4.2.15. 4-(3,4-Dimethoxyphenyl)-6,7-dimethyl-3,4-di-
hydrocoumarin (3bf). Mp 141.7–142.8 8C (CH2Cl2/
1
hexane). H NMR (CDCl3, 300 MHz) d 2.15 (s, 3H, Me),
2.24 (s, 3H, Me), 2.94 (dd, JZ15.8, 7.4 Hz, 1H, CH), 3.01
(dd, JZ15.8, 5.9 Hz, 1H, CH), 3.82 (s, 3H, OMe), 3.85
(s, 3H, OMe), 4.21 (t, JZ6.6 Hz, 1H, CH), 6.66–6.68 (m,
2H, ArH), 6.74 (s, 1H, ArH), 6.81 (app. d, JZ8.7 Hz, 1H,
ArH), 6.89 (s, 1H, ArH). 13C NMR (CDCl3, 75.5 MHz) d
18.87, 19.37, 37.33, 39.91, 55.75 (2OMe), 110.45, 111.43,
117.63, 119.34, 122.70, 128.78, 132.76, 133.17, 137.19,
148.22, 149.20, 149.42, 168.05. Anal. Calcd for C19H20O4:
C, 73.06; H, 6.45. Found: C, 73.00; H, 6.46.
4.2.10. 7-Bromo-4-(4-methoxyphenyl)-3,4-dihydro-
coumarin (3aj). Mp 149.5–150.5 8C (CH2Cl2/hexane). H
1
NMR (CDCl3, 300 MHz) d 2.96 (dd, JZ16.1, 8.3 Hz, 1H,
CH), 3.04 (dd, JZ15.8, 6.2 Hz, 1H, CH), 3.81 (s, 3H, OMe),
4.26 (app. t, JZ7.2 Hz, 1H, CH), 6.89 (app. d, JZ8.7 Hz,
2H, ArH), 7.00 (d, JZ8.4 Hz, 1H, ArH), 7.05–7.09 (m, 3H,
ArH), 7.40 (dd, JZ8.7, 2.4 Hz, 1H, ArH). 13C NMR
(CDCl3, 75.5 MHz) d 36.78, 39.82, 55.32, 114.69, 117.29,
118.84, 128.44, 128.57, 131.02, 131.26, 131.72, 150.72,
159.22, 166.94. Anal. Calcd for C16H13BrO3: C, 57.68; H,
3.93. Found: C, 57.77; H, 3.94.
4.2.16. 4-(4-Hydroxy-3-methoxyphenyl)-6,7-dimethyl-3,
4-dihydrocoumarin (3cf). Mp 141.7–142.8 8C (CH2Cl2/
1
hexane). H NMR (CDCl3, 300 MHz) d 2.15 (s, 3H, Me),
2.24 (s, 3H, Me), 2.92(dd, JZ16.1, 7.4 Hz, 1H, CH), 3.00 (dd,
JZ15.9, 6.0 Hz, 1H, CH), 3.82 (s, 3H, OMe), 4.19 (t, JZ
6.8 Hz, 1H, CH), 6.62–6.63 (m, 2H, ArH), 6.74 (s, 1H, ArH),
6.85 (d, JZ8.7 Hz, 1H, ArH), 6.89 (s, 1H, ArH). 13C NMR
(CDCl3, 75.5 MHz) d 18.91, 19.41, 37.45, 40.00, 55.82,
139.77, 114.71, 117.66, 120.26, 122.82, 128.85, 132.55,
132.83, 137.23, 144.88, 146.86, 149.44, 168.24. Anal. Calcd
for C18H18O4: C, 72.47; H, 6.08. Found: C, 72.56; H, 6.12.
4.2.11. 4-(4-Methoxyphenyl)-3,4-dihydrocoumarin
(2ak).12 Mp 136.9–138.1 8C (CH2Cl2/hexane). 1H NMR
(CDCl3, 300 MHz) d 2.98 (dd, JZ16.2, 7.8 Hz, 1H, CH),
3.53 (dd, JZ17.4, 6.0 Hz, 1H, CH), 3.79 (s, 3H, OMe), 4.30
(t, JZ6.8 Hz, 1H), 6.87 (app. d, JZ8.7 Hz, 2H, ArH), 6.98
(d, JZ7.5 Hz, 1H, ArH), 7.06–7.13 (m, 4H, ArH), 7.29 (td,
JZ7.8, 1.8 Hz, 1H, ArH). 13C NMR (CDCl3, 75.5 MHz) d
37.19, 39.90, 55.28, 114.48, 117.08, 124.60, 126.20, 128.26,
128.60, 128.68, 132.20, 151.66, 159.00, 167.73.
4.2.17. 4-(3,4-Dimethoxyphenyl)-5,7-dimethyl-3,4-di-
hydrocoumarin (3bg).15 Mp 137.9–138.9 8C (CH2Cl2/
hexane). H NMR (CDCl3, 300 MHz) d 2.16 (s, 3H, Me),
1
4.2.12.
1,2-Dihydro-1-(3,4-dimethoxyphenyl)-3H-
naphtho[2,1-b]pyran-3-one (3ba).13 Mp 156–159 8C
(CH2Cl2/hexane). H NMR (CDCl3, 300 MHz) d 3.14 (dd,
2.34 (d, 3H, Me), 2.94–3.08 (m, 2H, CH2), 3.80 (s, 3H,
OMe), 3.82 (s, 3H, OMe), 4.29–4.32 (m, 1H, CH), 6.52 (d,
JZ8.1 Hz, 1H, ArH), 6.59 (s, 1H, ArH), 6.73 (d, JZ8.1 Hz,
1H, ArH), 6.83 (br s, 2H, ArH). 13C NMR (CDCl3,
75.5 MHz) d 18.54, 20.98, 37.55, 37.87, 55.79 (2OMe),
110.16, 111.51, 115.28, 118.96, 120.25, 127.23, 132.83,
136.51, 138.64, 148.25, 149.30, 151.93, 167.59.
1
JZ3.0, 15.3 Hz, 1H, CH), 3.20 (dd, JZ5.7, 15.3 Hz, 1H, CH),
3.78 (s, 3H, OMe), 4.90 (dd, JZ3.0, 5.7 Hz, 1H, CH), 6.57–
6.60 (m, 1H, ArH), 6.69–6.72 (m, 2H, ArH), 7.33–7.51 (m, 3H,
ArH), 7.80–7.88 (m, 3H, ArH). 13C NMR (CDCl3, 75.5 MHz)
d 37.14, 37.49, 55.70, 55.74, 110.05, 11.56, 117.34, 117.76,
118.94, 122.94, 125.13, 127.32, 128.61, 129.75, 130.88,
130.95, 132.97, 148.34, 149.39, 149.55, 167.15.
4.2.18. 4-(4-Hydroxy-3-methoxyphenyl)-5,7-dimethyl-3,
4-dihydrocoumarin (3cg). Mp 176.8–177.6 8C (CH2Cl2/
1
hexane). H NMR (CDCl3, 300 MHz) d 2.16 (s, 3H, Me),
4.2.13. 1,2-Dihydro-1-(4-hydroxy-3-methoxyphenyl)-
3H-naphtho[2,1-b]pyran-3-one (3ca).14 Mp 150.4–
151.4 8C (CH2Cl2/hexane). H NMR (CDCl3, 300 MHz) d
2.34 (s, 3H, Me), 2.97 (dd, JZ3.0, 15.6 Hz, 1H, CH), 3.03
(dd, JZ5.7, 15.6 Hz, 1H, CH), 3.79 (s, 3H, OMe), 4.30 (dd,
1