S. V. Kalivendi, B. Sreedhar, et al.
MED
(s,9H), 3.57(s, 3H), 3.94 (s, 3H), 3.95 (s, 3H), 6.86 (s, 1H), 7.11(d, 2H,
J=8.3 Hz), 7.27 (d, 2H, J=11.3 Hz), 7.27 (d, 1H), 7.49 (d, 2H, J=
8.3 Hz), 7.73 ppm (d, 1H, J=13.6 Hz); 13C NMR (75 MHz, CDCl3): d=
56.2, 60.9, 61.1, 105.1, 105.6, 128.0, 128.2, 130.5, 134.3, 136.7, 137.9,
Anal. calcd for C19H19NO6: C 63.86, H 5.36, N 3.92, found: C 63.89, H
5.42, N 3.84.
(E)-Methyl 2’,3’,4’-trimethoxy-6’-(2-nitrovinyl)biphenyl-4-carbox-
ylate (14 f): Following general procedure B, purification by column
chromatography (hexane/EtOAc, 8:2) gave compound 14 f as a
yellow solid (0.317 g, 85%): mp: 98–1048C; 1H NMR (300 MHz,
CDCl3): d=3.57 (s, 3H), 3.95 (s, 3H), 3.96 (s, 3H), 6.89 (s, 1H), 7.29
(d, 2H, J=8.3 Hz), 7.33 (d, 1H, J=13.6 Hz), 7.64 (d, 1H, J=13.6 Hz),
8.12 ppm (d, 2H, J=8.3 Hz); 13C NMR (75 MHz, CDCl3): d=52.1,
56.1, 60.0, 60.1, 105.6, 123.8, 129.3, 129.5, 130.7, 131.5, 136.9, 137.2,
~
145.7, 151.7, 153.0 ppm; IR (neat): n=2930, 1625, 1589, 1481, 1323,
1145, 1094, 1059, 994 cmꢀ1; ESI-MS: m/z: 338 [M+Na]+; HRMS (ESI)
m/z: [M+H]+ calcd for C17H17NO5Na: 338.1107, found: 338.1009;
Anal. calcd for C17H17NO5: C 64.75, H 5.43, N 4.44, found: C 64.69, H
5.52, N 4.39.
(E)-2,3,4,4’-Tetramethoxy-6-(2-nitrovinyl)biphenyl (14b): Follow-
ing general procedure B, purification by column chromatography
~
139.2, 145.5, 151.4, 153.4, 166.6 ppm; IR (neat): n=2928, 1716,
1633, 1587, 1517, 1330, 1291, 1245, 1102, 946 cmꢀ1; ESI-MS: m/z:
374 [M+H]+; HRMS (ESI) m/z: [M+H]+ calcd for C19H19NO7Na:
396.1162, found: 396.1066; Anal. calcd for C19H19NO7: C 61.12, H
5.13, N 3.75, found: C 61.04, H 5.24, N 3.61.
(hexane/EtOAc, 9:1) gave compound 14b as
a yellow solid
1
(0.310 g, 90%): mp: 115–1188C; H NMR (300 MHz, CDCl3): d=3.54
(s, 3H), 3.87 (s, 3H), 3.93 (s, 3H), 3.95 (s, 3H), 6.85 (s, 1H), 6.94 (d,
2H, J=8.7 Hz), 7.11 (d, 2H, J=8.7 Hz), 7.30 (d, 1H, J=13.6 Hz),
7.75 ppm (d, 1H, J=13.6 Hz); 13C NMR (75 MHz, CDCl3): d=55.2,
56.2, 60.8, 61.1, 105.6, 113.4, 113.7, 131.7, 132.2, 136.6, 138.2, 145.7,
(E)-Methyl 2’,3’,4’-trimethoxy-6’-(2-nitrovinyl)biphenyl-3-carbox-
ylate (14g): Following general procedure B, purification by column
chromatography (hexane/EtOAc, 8:2) gave compound 14g as a
yellow solid (0.324 g, 87%): mp: 148–1518C; 1H NMR (300 MHz,
CDCl3): d=3.59 (s, 3H), 3.93 (s, 3H), 3.95 (s, 3H), 3.96 (s, 3H), 6.88
(s, 1H), 7.31 (d, 1H, J=13.6 Hz), 7.38 (d, 1H, J=7.5 Hz), 7.51–7.57
(m, 1H), 7.62 (d, 1H, J=13.6 Hz), 7.90 (s, 1H), 8.10 ppm (d, 1H, J=
7.5 Hz); 13C NMR (75 MHz, CDCl3): d=52.2, 56.2, 61.0, 61.1, 105.7,
124.1, 128.4, 129.2, 130.2, 131.6, 134.9, 135.0, 137.0, 137.4, 145.7,
~
147.6, 152.8, 159.3 ppm; IR (neat): n=2935, 1620, 1594, 1476, 1322,
1286, 1242, 1147, 1096, 997, 834 cmꢀ1; ESI-MS: m/z: 346 [M+H]+;
HRMS (ESI) m/z: [M+H]+ calcd for C18H20NO6: 346.1212, found:
346.1306; Anal. calcd for C18H19NO6: C 62.60, H 5.55, N 4.23, found:
C 62.54, H 5.71, N 4.18.
(E)-2’,3’,4’-Trimethoxy-6’-(2-nitrovinyl)biphenyl-4-ol (14c): Follow-
ing general procedure B, purification by column chromatography
(hexane/EtOAc, 8.5:1.5) gave compound 14c as a yellow solid
~
161.7, 163.5, 166.7 ppm; IR (neat): n=2934, 1720, 1633, 1587, 1497,
1331, 1243, 1102, 964 cmꢀ1; ESI-MS: m/z: 374 [M+H]+; 391 [M+
NH4]+; HRMS (ESI) m/z: [M+H]+ calcd for C19H20NO7: 374.1162,
found: 374.1236; Anal. calcd for C19H19NO7: C 61.12, H 5.13, N 3.75,
found: C 61.16, H 5.21, N 3.68.
1
(0.265 g, 80%): mp: 173–1778C; H NMR (300 MHz, CDCl3): d=3.56
(s, 3H), 3.93 (s, 3H), 3.95 (s, 3H), 6.85 (s, 1H), 6.88 (d, 2H, J=
8.7 Hz), 7.07 (d, 2H, J=8.7 Hz), 7.30 (d, 1H, J=13.6 Hz), 7.76 ppm
(d, 1H, J=13.6 Hz); 13C NMR (75 MHz, CDCl3): d=56.2, 60.9, 61.1,
105.6, 111.0, 115.3, 124.3, 126.4, 131.9, 136.6, 138.2, 145.7, 148.4,
(E)-2,3,3’,4,4’-Pentamethoxy-6-(2-nitrovinyl)biphenyl (14h): Fol-
lowing general procedure B, purification by column chromatogra-
phy (hexane/EtOAc, 8:2) gave compound 14h as a yellow solid
~
152.8, 155.6 ppm; IR (neat): n=3362, 3328, 2938, 1626, 1590, 1484,
1324, 1291, 1237, 1147, 1097, 972 cmꢀ1; ESI-MS: m/z: 332 [M+H]+;
HRMS (ESI) m/z: [M+H]+ calcd for C17H18NO6: 332.1056, found:
332.1069; Anal. calcd for C17H17NO6: C 61.63, H 5.17, N 4.06, found:
C 61.56, H 5.26, N 4.12.
1
(0.318 g, 85%): mp: 102–1058C; H NMR (300 MHz, CDCl3): d=3.56
(s, 3H), 3.87 (s, 3H), 3.92 (s, 3H), 3.95 (s, 3H), 3.96 (s, 3H), 6.69 (d,
1H, J=8.1 Hz), 6.74 (s, 1H), 6.87 (s, 1H), 6.91 (d, 1H, J=8.1 Hz),
7.34 (d, 1H, J=13.6 Hz), 7.78 ppm (d, 1H, J=13.6 Hz); 13C NMR
(75 MHz, CDCl3): d=55.8, 55.9, 60.9, 61.1, 105.5, 110.7, 113.7, 123.3,
124.3, 126.7, 132.7, 136.5, 138.2, 145.7, 148.5, 148.7, 151.8,
(E)-4’-tert-Butyl-2,3,4-trimethoxy-6-(2-nitrovinyl)biphenyl (14d):
Following general procedure B, purification by column chromatog-
raphy (hexane/EtOAc, 9:1) gave compound 14d as a yellow solid
(0.336 g, 90% yield): mp: 138–1418C; 1H NMR (300 MHz, CDCl3):
d=1.40 (s, 9H), 3.57(s, 3H), 3.94 (s, 3H), 3.95 (s, 3H), 6.86 (s, 1H),
7.11(d, 2H, J=8.3 Hz), 7.27 (d, 2H, J=11.3 Hz), 7.27 (d, 1H), 7.49 (d,
2H, J=8.3 Hz), 7.73 ppm (d, 1H, J=13.6 Hz); 13C NMR (75 MHz,
CDCl3): d=31.2, 34.6, 56.1, 60.9, 61.0, 105.6, 124.2, 125.1, 130.1,
~
152.8 ppm; IR (neat): n=2925, 1626, 1586, 1481, 1324, 1229, 1126,
1037 cmꢀ1; ESI-MS: m/z: 376 [M+H]+; HRMS (ESI) m/z: [M+H]+
calcd for C19H22NO7: 376.1318, found: 376.1409; Anal. calcd for
C19H21NO7: C 60.79, H 5.64, N 3.73, found: C 60.92, H 5.81, N 3.66.
(E)-3’,4’-Difluoro-2,3,4-trimethoxy-6-(2-nitrovinyl)biphenyl (14i):
Following general procedure B, purification by column chromatog-
raphy (hexane/EtOAc, 9:1) gave compound 14i as a yellow solid
(0.317 g, 90%): mp: 88–928C; 1H NMR (300 MHz, CDCl3): d=3.61
(s, 3H), 3.95 (s, 6H), 6.86 (s, 1H), 6.87–6.92 (m, 1H), 7.05–7.12 (m,
1H), 7.20–7.27 (m, 2H), 7.33 (d, 1H, J=13.6 Hz), 7.66 ppm (d, 1H,
J=13.6 Hz); 13C NMR (75 MHz, CDCl3): d=56.2, 60.9, 61.1, 105.6,
117.3 (d, J=17.1 Hz), 119.8 (d, J=17.1 Hz), 124.1, 126.9, 130.4,
131.2, 137.1, 137.2, 145.6, 148.3 (q, J=12.6 Hz), 151.6 ppm (q, J=
~
131.2, 133.0, 136.6, 138.2, 150.8, 151.8, 152.8 ppm; IR (neat): n=
2961, 1622, 1591, 1522, 1498, 1455, 1398, 1319, 1101, 967,
826 cmꢀ1; ESI-MS: m/z: 373 [M+H]+; 395 [M+Na]+; HRMS (ESI)
m/z: [M+H]+ calcd for C21H26NO5: 373.1162, found: 373.1154; Anal.
calcd for C21H25NO5: C 67.91, H 6.78, N 3.77, found: C 67.88, H 6.83,
N 3.71.
(E)-1-(2’,3’,4’-Trimethoxy-6’-(2-nitrovinyl)biphenyl-4-yl)ethanone
(14e): Following general procedure B, purification by column chro-
matography (hexane/EtOAc, 8:2) gave compound 14e as a yellow
solid (0.293 g, 82%): mp: 150–1528C; 1H NMR (300 MHz, CDCl3):
d=2.67 (s, 3H), 3.58 (s, 3H), 3.96 (s, 6H), 6.89 (s, 1H), 7.30–7.34 (m,
3H), 7.64 (d, 1H, J=13.4 Hz), 8.04 ppm (d, 2H, J=8.3 Hz); 13C NMR
(75 MHz, CDCl3): d=26.6, 56.2, 61.0, 105.6, 123.8, 128.1, 130.9,
131.5, 136.4, 137.0, 137.3, 139.5, 145.6, 151.5, 153.4, 197.6 ppm; IR
~
12.6 Hz), 153.5; IR (neat): n=2940, 1624, 1589, 1481, 1321, 1286,
1140, 1089 cmꢀ1; ESI-MS: m/z: 353 [M+H]+; HRMS (ESI) m/z: [M+
H]+ calcd for C17H15F2NO5: 351.0918, found: 351.1702; Anal. calcd
for C17H15F2NO5: C 58.12, H 4.30, N 3.99, found: C 58.03, H 4.45, N
4.12.
(E)-5-(2,3,4-Trimethoxy-6-(2-nitrovinyl)phenyl)benzo[d]-
[1,3]dioxole (14j): Following the general procedure B, purification
by column chromatography (hexane/EtOAc, 9:1) gave compound
14j as a yellow solid (0.324 g, 90%): mp: 140–1438C; 1H NMR
(300 MHz, CDCl3): d=3.60 (s, 3H), 3.93 (s, 3H), 3.94 (s, 3H), 6.06 (s,
~
(neat): n=2934, 1680, 1629, 1592, 1481, 1321, 1147, 1094, 961,
835 cmꢀ1; ESI-MS: m/z: 358 [M+H]+; 380 [M+Na]+; HRMS (ESI)
m/z: [M+H]+ calcd for C19H19NO6Na: 380.1212, found: 380.1201;
866
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ChemMedChem 2011, 6, 859 – 868