Lu et al.
FULL PAPER
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CH3), 4.18— 4.25 (m, 2H, OCH2), 5.57 (s, 1H, 4-H),
6.36 (s, 2H, NH2), 7.14 (d, J= 8.4 Hz, 2H, ArH), 7.24—
7.28 (m, 3H, Naph-H), 7.38— 7.47 (m, 2H, ArH),
7.75— 7.80 (m, 2H, Naph-H), 7.94 (d, J= 8.4 Hz, 1H,
Naph-H); 13C NMR (CDCl3, 150 MHz) δ: 14.2, 37.6,
60.97, 78.6, 118.9, 123.1, 123.8, 124.1, 126.8, 128.9,
129.6, 130.5, 131.1, 132.3, 133.2, 135.7, 140.6, 153.-9,
1633 cm ; MS m/z: 374.92 [M ]. Anal. calcd for
C23H21NO4: C 73.58, H 5.64, N 3.73; found C 73.67, H
5.48, N 3.81.
2-Amino-3-ethoxycarbonyl-4-(2,3-dimethoxyphen-
1
yl)-4H-naphthopyran (4i) m.p. 196.8— 198 ℃; H
NMR (CDCl3, 600 MHz) δ: 1.28— 1.30 (t, J= 7.2 Hz, 3H,
CH3), 3.56 (s, 3H, OCH3), 3.73 (s, 3H, OCH3), 4.11—
4.22 (m, 2H, OCH2), 5.72 (s, 1H, 4-H), 6.38 (s, 2H,
NH2), 6.65— 6.67 (m, 1H, ArH), 6.90— 6.93 (m, 1H,
ArH), 7.12— 7.16 (m, 1H, ArH), 4.22 (d, J= 9 Hz, 1H,
Naph-H), 7.32— 7.34 (m, 1H, Naph-H), 7.44— 7.46 (m,
1H, Naph-H), 7.67— 7.74 (m, 2H, Naph-H), 8.28 (d, J=
8.4 Hz, 1H, Naph-H); 13C NMR (CDCl3, 150 MHz) δ:
14.2, 30.6, 57.4, 57.8, 60.0, 78.5, 113.8, 117.5, 119.1,
121.9, 123.3, 123.7, 124.1, 124.8, 127.5, 129.1, 129.6,
130.9, 134.9, 150.1, 151.3, 152.7, 160.8, 167.6; IR
1
161.8, 167.5; IR (NaCl) ν: 3413, 3308, 1735, 1677 cm ;
MS m/z: 378.9 [M+].
2-Amino-3-ethoxycarbonyl-4-(2,4-dichlorophenyl)-
4H-naphthopyran (4e) m.p. 196 ℃ (lit.3a 195— 197
1
℃); H NMR (CDCl3, 600 MHz) δ: 1.31 (t, J= 6.6, 7.2
Hz, 3H, CH3), 4.17— 4.24 (m, 2H, OCH2), 5.94 (s, 1H,
4-H), 6.42 (s, 2H, NH2), 7.01— 7.04 (m, 1H, Naph-H),
7.19— 7.28 (m, 4H, Naph-H and ArH), 7.42— 7.52 (t, J=
7.2 Hz, 1H, Naph-H), 7.74— 7.79 (m, 2H, Naph-H),
8.24 (d, J= 8.4 Hz, 1H, Naph-H); 13C NMR (CDCl3,
150 MHz) δ: 14.2, 33.6, 58.17, 79.1, 116.5, 122.6, 123.8,
124.7, 127.1, 128.2, 129.1, 129.6, 130.5, 131.7, 132.4,
134.3, 136.4, 134.8, 149.6, 153.8,-160.3, 168.1; IR
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(NaCl) ν: 3412, 3310, 1735, 1676 cm ; MS m/z: 405.3
[M+]. Anal. calcd for C24H23NO5: C 71.10, H 5.72, N
3.45; found C 71.02, H 5.79, N 3.56.
2-Amino-3-ethoxycarbonyl-4-(4-hydroxyphenyl)-
1
1
(NaCl) ν: 3409, 3304, 1735, 1676 cm ; MS m/z: 412.82
4H-naphthopyran (4j) m.p. 260— 262 ℃; H NMR
[M+].
(CDCl3, 600 MHz) δ: 1.34— 1.36 (t, J= 7.2 Hz, 3H,
CH3), 4.18— 4.25 (m, 2H, OCH2), 5.71 (s, 1H, CH, H-4),
6.40 (s, 2H, NH2), 7.29 (t, J= 9 Hz, 2H, Naph-H),
7.40— 7.48 (m, 5H, ArH, Naph-H), 7.77— 7.86 (m, 3H,
ArH, Naph-H), 8.16 (s, 1H, OH); 13C NMR (CD3COCD3,
150 MHz) δ: 14.2, 39.6, 60.87, 79.1, 116.3, 118.1, 123.1,
123.9, 124.6, 127.3, 129.2, 129.6, 130.2, 131.6, 133.7,
134.5, 152.9, 157.7, 160.3, 168.1; IR (NaCl) ν: 3624,
2-Amino-3-ethoxycarbonyl-4-(-bromophenyl)-4H-
1
naphthopyran (4f) m.p. 230.5— 231.8 ℃; H NMR
(CDCl3, 600 MHz) δ: 1.36 (t, J= 6.6, 7.2 Hz, 3H, CH3),
4.20— 4.23 (m, 2H, OCH2), 5.54 (s, 1H, 4-H), 6.39 (s,
2H, NH2), 7.19— 7.48 (m, 7H, ArH and Naph-H), 7.46—
7.79 (m, 2H, ArH), 7.93 (d, J= 8.4 Hz, 1H, ArH); 13C
NMR (CDCl3, 150 MHz) δ: 14.1, 39.6, 60.1, 78.8, 117.2,
121.6, 123.1, 123.8, 124.7, 127.5, 129.4, 129.7, 130.5
131.9, 133.4, 135.2, 141.5, 152.7,-160.3, 168.2; IR
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3402, 3308, 1738, 1677 cm ; MS m/z: 361.3 [M ].
Anal. calcd for C22H19NO4: C 73.12, H 5.30, N 3.88;
found C 73.25, H 5.19, N 3.95.
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(NaCl) ν: 3432, 3305, 1734, 1676 cm ; MS m/z: 422.85
[M+]. Anal. calcd for C22H18BrNO3: C 62.28, H 4.28, N
3.30; found C 62.43, H 4.19, N 3.38.
2-Amino-3-ethoxycarbonyl-4-(2-nitrophenyl)-4H-
naphthopyran (4k) m.p. 248— 250 ℃ (lit.3c 248 ℃);
1H NMR (CDCl3, 600 MHz) δ: 1.19 (t, J= 7.2 Hz, 3H,
CH3), 4.18— 4.24 (m, 2H, OCH2), 5.76 (s, 1H, 4-H),
6.40 (s, 2H, NH2), 7.15— 7.25 (m, 1H, Naph-H), 7.32—
7.46 (m, 2H, Naph-H), 7.49 (m, 2H, ArH), 7.52— 7.77
(m, 3H, ArH and Naph-H), 7.44 — 7.46 (m, 1H,
Naph-H), 8.25 (d, J= 8.4 Hz, 1H, ArH); 13C NMR
(CDCl3, 150 MHz) δ: 14.2, 34.3, 60.53, 78.2, 115.1,
122.9, 123.73, 124.8, 125.4, 126.2, 127.6, 129.2, 130.4,
130.7, 131.3, 134.6, 136.7, 139,6, 150.2, 153.9,-160.2,
2-Amino-3-ethoxycarbonyl-4-(4-cyanophenyl)-4H-
1
naphthopyran (4g) m.p. 239— 241.3 ℃; H NMR
(CDCl3, 600 MHz) δ: 1.35 (t, J= 7.2 Hz, 3H, CH3),
4.18— 4.25 (m, 2H, OCH2), 5.63 (s, 1H, 4-H), 6.39 (s,
2H, NH2), 7.28 (t, J= 9 Hz, 2H, Naph-H), 7.39— 7.48
(m, 5H, ArH and Naph-H), 7.78— 7.88 (m, 3H, ArH and
Naph-H); 13C NMR (CDCl3, 150 MHz) δ: 14.2, 39.6,
59.57, 79.8, 111.5, 116.6, 119.2, 123.2, 123.6, 125.7,
127.7, 129.3, 129.8, 130.2, 131.8, 133.9, 135.2, 146.7,
153.7, 159.8, 167.4; IR (NaCl) ν: 3421, 3308, 2226,
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168.75; IR (NaCl) ν: 3427, 3309, 1736, 1669 cm ; MS
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1735, 1678 cm ; MS m/z: 369.91 [M ]. Anal. calcd for
C23H18N2O3: C 74.58, H 4.90, N 7.56; found C 74.63, H
4.82, N 7.66.
m/z: 389.90 [M+].
References
2-Amino-3-ethoxycarbonyl-4-(4-methoxyphenyl)-
1
1
Hatakeyama, S.; Ochi, N.; Numata, H.; Takanao, S. J. Chem.
Soc., Chem. Commun. 1988, 1202.
(a) Lazzeri Andreani, L.; Lapi, E. Boll. Chim. Farm. 1960,
99, 583.
(b) Bonsignore, L.; Loy, G.; Secci, D.; Calignano, A. Eur. J.
Med. Chem. 1993, 28, 517.
(a) Jin, T. S.; Zhang, J. S.; Liu, L. B.; Wang, A. Q.; Li, T. S.
Synth. Commun. 2006, 36, 2009.
4H-naphthopyran (4h) m.p. 145.2— 146.8 ℃; H
NMR (CDCl3, 600 MHz) δ: 1.37 (t, J= 7.2 Hz, 3H,
CH3), 3.70 (s, 3H, OCH3), 4.18— 4.24 (m, 2H, OCH2),
5.54 (s, 1H, 4-H), 6.29 (s, 2H, NH2), 6.70 (d, J= 8.4 Hz,
2H, ArH), 7.22— 7.46 (m, 5H, Naph-H and ArH),
7.72— 7.78 (m, 2H, Naph-H), 8.0 (d, J= 8.4 Hz, 1H,
Naph-H); 13C NMR (CDCl3, 150 MHz) δ: 14.2, 37.6,
54.4, 59.9, 78.6, 115.9, 116.98, 123.1, 123.8, 124.3,
127.6, 129.3, 129.8, 130.2, 131.5, 133.7, 135.4, 152.7,
158.9, 160.5, 168.2; IR (NaCl) ν: 3415, 3307, 1735,
2
3
(b) Wen, X. M.; Wang, H. Y.; Li, S. L. J. Chem. Res. 2006,
12, 776.
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Chin. J. Chem. 2010, 28, 2469— 2473