Journal of Natural Products
Article
2.36 (t, 3H, J = 0.6 Hz, 5′-CH3), 3.71 (s, 3H, 2′-OCH3), 6.87 (d, 1H, J
= 8.1 Hz, H3′), 7.11 (dd, 1H, J = 2.1, 0.6 Hz, H6′), 7.21 (ddd, 1H, J =
8.1, 2.1, 0.6 Hz, H4′), 7.36 (ddd, 1H, J = 7.5, 1.5, 0.6 Hz, H6), 7.47
(ddd, 1H, J = 7.8, 7.5, 1.5 Hz, H4), 7.64 (td, 1H, J = 7.5, 1.5 Hz, H5),
7.99 (ddd, 1H, J = 7.8, 1.5, 0.6 Hz, H3), 9.80 (d, 1H, J = 0.6 Hz,
CHO); 13C NMR (75 MHz, CDCl3) δ 20.7 (5′-CH3), 55.7 (2′-
OCH3), 110.8 (C3′), 126.7 (C5′), 126.8 (C3), 127.9 (C5), 130.5
(C4′), 131.4 (C6′), 132.3 (C6), 133.9 (C4), 134.2 (C2), 142.2 (C1),
154.7 (C2′), 193.0 (CHO); HRMS (ESI TOF-MS) calcd for
127.7 (d, J = 8.0 Hz, C1′), 135.5 (C1), 148.8 (C5), 152.8 (d, J = 1.8
Hz, C2′), 153.5 (C4), 156.8 (d, J = 240.2 Hz, C5′), 191.0 (CHO);
+
HRMS (ESI TOF-MS) calcd for C16H15FNaO4 313.0847; found
313.0882.
3,4-Dimethoxy-6-(4-fluoro-2-methoxyphenyl)benzaldehyde
(5m). Colorless solid; mp 117.7−118.2 °C; IR (νmax) 3085, 3025,
2974, 2956, 2915, 2876, 1675, 1592, 1497, 1441, 1260, 1212, 1134,
1017, 946, 838, 728 cm−1; 1H NMR (300 MHz, CDCl3) δ 3.74 (3H, s,
OCH3), 3.95 (3H, s, OCH3), 3.97 (3H, s, OCH3), 6.71 (1H, dd, J =
10.0, 2.4 Hz, H3′), 6.76 (1H, s, H3), 6.77 (1H, td, J = 8.2, 2.4 Hz,
H5′), 7.21 (1H, dd, J = 8.2, 6.7 Hz, H6′), 7.50 (1H, s, H6), 9.61 (1H,
s, CHO); 13C NMR (75 MHz, CDCl3) δ 56.2 (OCH3), 56.3 (OCH3),
56.5 (OCH3), 99.1 (d, J = 26.0 Hz, C3′), 107.3 (d, J = 24.0 Hz, C5′),
108.2 (C6), 113.2 (C3), 122.4 (d, J = 2.5 Hz, C1′), 127.3 (C2), 132.3
(d, J = 9.8 Hz, C6′), 136.1 (C1), 148.7 (C5), 153.5 (C4), 158.0 (d, J =
9.9 Hz, C2′), 163.7 (d, J = 247.2 Hz, C4′), 191.1 (CHO); HRMS (ESI
+
C15H14NaO2 249.0886; found 249.0872.
2-(5-Chloro-2-methoxyphenyl)benzaldehyde (5f). White solid;
mp 95.1−96.3 °C; IR (νmax) 3065, 3008, 2941, 2842, 2750, 1697,
1
1597, 1495, 1255, 1025, 811, 771, 646 cm−1; H NMR (300 MHz,
CDCl3) δ 3.72 (s, 3H, 2′-OCH3), 6.90 (d, 1H, J = 9.0 Hz, H3′), 7.28
(d, 1H, J = 2.7 Hz, H6′), 7.33 (ddd, 1H, J = 7.8, 1.5, 0.6 Hz, H6), 7.37
(dd, 1H, J = 9.0, 2.7 Hz, H4′), 7.50 (ddd, 1H, J = 7.8, 7.5, 1.5 Hz, H5),
7.65 (td, 1H, J = 7.5, 1.5 Hz, H4), 7.99 (ddd, 1H, J = 7.5, 1.5, 0.6 Hz,
H3), 9.78 (d, 1H, J = 0.6 Hz, CHO); 13C NMR (75 MHz, CDCl3) δ
56.0 (2′-OCH3), 112.1 (C3′), 126.2 (C5′), 127.1 (C3), 128.4 (C5),
128.7 (C1′), 129.7 (C4′), 131.2 (C6′), 131.2 (C6), 134.0 (C4), 134.2
(C2), 140.4 (C1), 155.4 (C2′), 192.2 (CHO); HRMS (ESI TOF-MS)
+
TOF-MS) calcd for C16H15FNaO4 313.0847; found 313.0870.
3-(5-Fluoro-2-methoxyphenyl)isonicotinaldehyde (5n). White
solid; mp 105.8−106.9 °C; IR (νmax) 3036, 2996, 2953, 2913, 2846,
1700, 1581, 1493, 1400, 1212, 1191, 1177, 1022, 880, 749, 714 cm−1;
1H NMR (300 MHz, CDCl3) δ 3.69 (3H, s, 2′-OCH3), 6.92 (1H, dd, J
= 9.0, 4.3 Hz, H3′), 7.06 (1H, dd, J = 8.3, 3.1 Hz, H6′), 7.13 (1H, ddd,
J = 9.0, 7.9, 3.1 Hz, H4′), 7.72 (1H, dd, J = 5.0, 0.6 Hz, H5), 8.66 (3H,
s, H2), 8.77 (1H, d, J = 5.0 Hz, H6), 9.79 (1H, d, J = 0.6 Hz, CHO);
13C NMR (75 MHz, CDCl3) δ 56.1 (2′-OCH3), 112.1 (d, J = 8.2 Hz,
C3′), 117.0 (d, J = 23.0 Hz C4′), 118.1 (d, J = 24.0 Hz, C6′), 119.2
(C5), 124.5 (d, J = 7.5 Hz, C1′), 133.5 (C3), 139.5 (C4), 150.2 (C6),
152.2 (C2), 153.0 (C2′), 157.3 (d, J = 241.0 Hz, C5′), 191,3 (CHO);
+
calcd for C14H11ClNaO2 269.0340; found 269.0298.
2-(4-Fluoro-2-methoxyphenyl)benzaldehyde (5g). White solid;
mp 68.7−70.0 °C; IR (νmax) 3066, 3008, 2940, 2839, 2749, 1690,
1
1597, 1507, 1449, 1279, 1192, 1151, 830, 765 cm−1; H NMR (300
MHz, CDCl3) δ 3.73 (s, 3H, 2′-OCH3), 6.71 (dd, 1H, J = 10.8, 2.4 Hz,
H3′), 6.80 (td, 1H, J = 8.4, 2.4 Hz, H5′), 7.24 (dd, 1H, J = 8.4, 6.6 Hz,
H6′), 7.32 (ddd, 1H, J = 7.8, 1.5, 0.6 Hz, H6), 7.49 (ddd, 1H, J = 7.8,
7.5, 1.5 Hz, H5), 7.64 (td, 1H, J = 7.5, 1.5 Hz, H4), 7.99 (ddd, 1H, J =
7.5, 1.5, 0.6 Hz, H3), 9.77 (d, 1H, J = 0.6 Hz, CHO); 13C NMR (75
MHz, CDCl3) δ 55.9 (2′-OCH3), 99.3 (d, J = 26.3 Hz, C3′), 107.7 (d,
J = 21.2 Hz, C5′), 122.9 (d, J = 3.6 Hz, C1′), 127.1 (C3), 128.1 (C5),
131.5 (C6),132.3 (d, J = 10.4 Hz, C6′), 134.0 (C4), 134.3 (C2), 141.1
(C1), 157.9 (d, J = 9.7 Hz, C2′), 164.1 (d, J = 246 Hz, C4′), 192.6
+
HRMS (ESI TOF-MS) calcd for C13H10FNNaO2 254.0588; found
254.0561.
3-(5-Chloro-2-methoxyphenyl)isonicotinaldehyde (5o). Colorless
solid; mp 112.7−113.5 °C; IR (νmax) 3046, 2979, 2946, 2874, 2762,
1
1695, 1600, 1504, 1469, 1399, 1276, 1150, 1028, 840 cm−1; H NMR
(300 MHz, CDCl3) δ 3.73 (3H, s, 2′-OCH3), 6.93 (1H, d, J = 8.8 Hz,
H3′), 7.33 (1H, d, J = 2,6 Hz, H6′), 7.43 (1H, dd, J = 8.8, 2.6 Hz,
H4′), 7.75 (1H, dd, J = 5.0, 0.7 Hz, H5), 8.68 (1H, s, H2), 8.80 (1H,
d, J = 5.0 Hz, H6), 9.80 (d, J = 0.7 Hz, 1H, CHO); 13C NMR (75
MHz, CDCl3) δ 55.7 (2′-OCH3), 112.0 (C3′), 119.0 (C5), 124.6
(C1′), 126.3 (C5′), 130.4 (C4′), 130.7 (C6′), 133.0 (C3), 139.2 (C4),
149.9 (C6), 151.9 (C2), 155.2 (C2′), 190.9 (CHO); HRMS (ESI
+
(CHO); HRMS (ESI TOF-MS) calcd for C14H11FNaO2 253.0635;
found 253.0634.
2-(3-Bromo-5-methyl-2-methoxyphenyl)benzaldehyde (5j). Yel-
low oil; IR (νmax) 3060, 2996, 2927, 2849, 2750, 1693, 1595, 1469,
1
1419, 1266, 1237, 1196, 998, and 858 cm−1; H NMR (300 MHz,
CDCl3) δ 2.35 (3H, s, 5′-CH3), 3.32 (3H, s, 2′-OCH3), 7.07−7.05
(1H, m, H4′), 7.40 (1H, dd, J = 7.5, 0.6 Hz, H6), 7.47−7.45 (1H, m,
H6′), 7.56−7.49 (1H, m, H5), 7.65 (1H, td, J = 7.6, 7.6, 1.5 Hz, H4),
8.03 (1H, dd, J = 7.6, 7.6, 1.1 Hz, H3), 9.83 (1H, d, J = 0.6 Hz, CHO);
13C NMR (75 MHz, CDCl3) δ 20.4 (5′-CH3), 60.1 (2′-OCH3), 117.3
(C3′) 127.1 (C3), 128.2 (C5), 130.9 (C6), 131.3 (C4′), 132.7 (C5′),
133.5 (C4), 134.1 (C6′), 135.4 (C2), 140.6 (C1), 152.1 (C2′), 191.6
+
TOF-MS) calcd for C13H10ClNNaO2 270.0292; found 270.0312.
3-(3-Bromo-5-fluoro-2-methoxyphenyl)isonicotinaldehyde (5p).
White solid; mp 138.5−139.6 °C; IR (νmax) 3075, 2939, 2857, 2750,
1709, 1595, 1572, 1498, 1463, 1416, 1317, 1280, 1257, 1233, 1209,
1
1178, 1029, 1001, 871, 839, 798, 739 cm−1; H NMR (300 MHz,
CDCl3) δ 3.34 (s, 3H, 2′-OCH3), 7.10 (dd, 1H, J = 7.8, 3.0 Hz, H4′),
7.45 (dd, 1H, J = 7.5, 3.0 Hz, H6′), 7.82 (d, 1H, J = 5.0 Hz, H5), 8.75
(s, 1H, H2), 8.88 (d, 1H, J = 5.0 Hz, H6), 9.86 (d, 1H, J = 0.9 Hz,
CHO); 13C NMR (75 MHz, CDCl3) δ 60.7 (2′-OCH3), 117.4 (d, J =
23.5 Hz, C6′), 118.5 (d, J = 10.4 Hz, C3′), 119.9 (C5), 121.9 (d, J =
25.2 Hz, C4′), 130.8 (d, J = 8.0 Hz, C1′), 132.4 (C3), 139.1 (C4),
151.1 (C6), 151.3 (C2′), 151.8 (C2), 158.8 (d, J = 247.8 Hz, C5′),
190.3 (CHO); HRMS (ESI TOF-MS) calcd for C13H9BrFNNaO2
331.9693; found 331.9706.
+
(CHO); HRMS (ESI TOF-MS) calcd for C15H13BrNaO2 326.9991;
found 326.9888.
2,4-Dimethoxy-6-(5-bromo-2-methoxyphenyl)benzaldehyde
(5k). Yellow solid; mp 124.8−125.3 °C; IR (νmax) 3054, 3005, 2938,
2849, 2772, 1680, 1589, 1489, 1326, 1202, 1118, 1160, 1200, 803, 731
cm−1; 1H NMR (300 MHz, CDCl3) δ 3.70 (3H, s, OCH3), 3.87 (3H,
s, OCH3), 3.93 (3H, s, OCH3), 6.34 (1H, d, J = 2.3 Hz, H5), 6.50
(1H, d, J = 2.3 Hz, H3), 6.78 (1H, d, J = 8,8 Hz, H3′), 7.31 (1H, d, J =
2.5 Hz, H6′), 7.45 (1H, dd, J = 8.8, 2.5 Hz, H4′), 9.96 (1H, s, CHO);
13C NMR (75 MHz, CDCl3) δ 55.6 (OCH3), 55.7 (OCH3), 55.9
2-(5-Fluoro-2-methoxyphenyl)nicotinaldehyde (5q). White solid;
mp 130.1−131.0 °C; IR (νmax) 3070, 2998, 2968, 2908, 2840, 1694,
1
(OCH3), 98.1 (C3), 108.1 (C5), 112.0 (C3′), 112.7 (C1), 117.2
(C5′), 131.0 (C1′), 131.8 (C4′), 132.5 (C6′), 143.1 (C2), 155.5
(C2′), 162.6 (C6), 164.3 (C4), 189.5 (CHO); HRMS (ESI TOF-MS)
1580, 1566, 1495, 1435, 1251, 1191, 1169, 809, 749, 716 cm−1; H
NMR (300 MHz, CDCl3), δ 3.72 (s, 3H, 2′-OCH3), 6.93 (dd, 1H, J =
9.0, 4.2 Hz, H3′), 7.17 (ddd, 1H, J = 9.0, 7.8, 3.3 Hz, H4′), 7.33 (dd,
1H, J = 8.6, 3.3 Hz, H6′), 7.45 (ddd, 1H, J = 7.8, 4.8, 0.9 Hz, H5), 8.26
(dd, 1H, J = 7.8, 1.8 Hz, H4), 8.89 (dd, 1H, J = 4.8, 1.8 Hz, H6), 9.78
(d, 1H, J = 0.9 Hz, CHO); 13C NMR (75 MHz, CDCl3), δ 56.2 (2′-
OCH3), 112.2 (d, J = 8.1 Hz, C3′), 117.6 (d, J = 22.8 Hz, C4′), 118.4
(d, J = 24.0 Hz, C6′), 123.2 (C5), 127.7 (d, J = 7.4 Hz, C1′), 130.3
(C3), 134.9 (C4), 152.8 (C2), 154.0 (C6), 157.5 (d, J = 238.6 Hz,
C5′), 157.6 (C2′), 191.4 (CHO); HRMS (ESI TOF-MS) calcd for
+
calcd for C16H15BrNaO4 373.0046; found 373.0126.
3,4-Dimethoxy-6-(5-fluoro-2-methoxyphenyl)benzaldehyde (5l).
Colorless solid; mp 114.4−115.2 °C; IR (νmax) 3077, 3063, 3023,
3008, 2997, 2939, 2886, 2858, 1677, 1593, 1511, 1496, 1460, 1263,
1
1251, 1176, 1023, 731 cm−1; H NMR (300 MHz, CDCl3) δ 3.71
(3H, s, OCH3), 3.95 (3H, s, OCH3), 3.97 (3H, s, OCH3), 6.76 (1H, s,
H3), 6.90 (1H, dd, J = 8.7, 4.4, Hz, H3′), 7.20 (1H, dd, J = 8.5, 3.1 Hz,
H6′), 7.10 (1H, ddd, J = 8.7, 3.1 Hz, H4′), 7.50 (1H, s, H6), 9.62 (1H,
s, CHO); 13C NMR (75 MHz, CDCl3) δ 56.2 (OCH3), 56.3 (OCH3),
56.5 (OCH3), 108.1 (C6), 111.5 (d, J = 8.3 Hz, C3′), 112.8 (C3),
115.6 (d, J = 22.5 Hz, C4′), 118.2 (d, J = 23.5 Hz, C6′), 127.0 (C2),
+
C13H10FNNaO2 254.0588; found 254.0521.
2-(2-Methoxy-5-methylphenyl)nicotinaldehyde (5r). White solid;
mp 63.4−64.1 °C; IR (νmax) 2948, 2838, 1699, 1580, 1565, 1501,
1
1438, 1381, 1277, 1251, 1237, 1147, 1025, 835, 808 cm−1; H NMR
2239
dx.doi.org/10.1021/np4005882 | J. Nat. Prod. 2013, 76, 2234−2245