61.0 (2OCH3), 56.2 (4OCH3), 56.1 (2OCH3); MS (APCI posi-
tive, m/z): 347 [M + H]+; HRMS found (ESI) (M + Na)+
369.1328 C19H22O6Na requires 369.1314.
(C), 146.1 (CH), 138.1 (C), 137.7 (C), 134.8 (C), 134.0 (C),
121.4 (C), 117.8 (CH), 115.2 (CH), 111.0 (CH), 108.7 (2CH),
60.5 (OCH3), 60.4 (OCH3), 56.4 (2OCH3), 55.8 (OCH3); Minor
E isomer (only the most significant resonances are listed): (E)-2-
methoxy-5-(2-methoxy-1-(3,4,5-trimethoxyphenyl)vinyl)benz-
enamine: 1H NMR (300 MHz, CDCl3, δ, ppm) 6.50 (s, 2H),
6.46 (s, 1H), 4.26 (s, 2H); MS (APCI positive, m/z): 346
[M + H]+; HRMS found (ESI) (M + H)+ 346.1655 C19H24NO5
requires 346.1654.
4c (Z/E)-1-Methoxy-4-(2-methoxy-1-(3,4,5-trimethoxy-
phenyl)vinyl)-2-nitrobenzene was obtained as a mixture of two
diastereoisomers (Z/E = 30/70); yield 61%; white oil; Rf = 0.23
(cyclohexane/EtOAc: 7/3); IR (thin film, neat) νmax/cm−1: 3428,
3405, 3385, 3334, 3191, 2938, 2842, 2315, 2252, 2232, 2167,
2082, 2037, 2004, 1983, 1961, 1940, 1725, 1636, 1616, 1581,
1529, 1504, 1465, 1453, 1413, 1354, 1341, 1282, 1236, 1185,
1154, 1127, 1008, 910, 835, 763, 728, 680, 662, 624; Major
Z-4e (Z)-2-Methoxy-5-(2-methoxy-1-(3,4,5-trimethoxy-
phenyl)vinyl)benzenamine was obtained from the Z/E mixture
of 4e, separation was performed using an HPLC Sunfire C18
column (19 × 150 mm, 5 μm) in isocratic mode, by using a
mobile phase containing H2O/MeOH 45/55; IR (thin film, neat)
νmax/cm−1: 3484, 3461, 3412, 3368, 3351, 3334, 3250, 3231,
2932, 2867, 2589, 2364, 2250, 2230, 2164, 2023, 1985, 1954,
1680, 1597, 1579, 1450, 1412, 1248, 1208, 1177, 1149, 1127,
1
E isomer: H NMR (300 MHz, CDCl3) δ (ppm): 8.01 (d, J =
2.1 Hz, 1H), 7.54 (dd, J = 8.2, 2.1 Hz, 1H), 7.01 (d, J = 8.2 Hz,
1H), 6.43 (s, 1H), 6.39 (s, 2H), 3.96 (s, 3H), 3.87 (s, 3H), 3.81
(s, 6H), 3.80 (s, 3H); 13C NMR (75 MHz, CDCl3) δ (ppm):
153.4 (2C), 151.3 (C), 147.1 (CH), 139.6 (C), 137.5 (C), 135.3
(CH), 135.1 (C), 130.4 (C), 126.8 (CH), 118.1 (C), 113.0 (CH),
106.1 (2CH), 61.1 (OCH3), 61.0 (OCH3), 56.7 (OCH3), 56.3
(2OCH3); Minor Z isomer (only the most significant resonances
are listed): (Z)-1-methoxy-4-(2-methoxy-1-(3,4,5-trimethoxy-
phenyl)vinyl)-2-nitrobenzene: 1H NMR (300 MHz, CDCl3)
δ (ppm): 7.74 (d, J = 2.2 Hz, 1H), 7.35 (dd, J = 8.2, 2.2 Hz,
1H), 6.56 (s, 2H), 6.43 (s, 1H); 13C NMR (75 MHz, CDCl3)
δ (ppm): 153.1 (2C), 146.7 (vCH), 134.0 (CH), 126.8 (CH),
118.4 (C), 113.6 (CH), 107.3 (2CH). MS (APCI positive, m/z):
376 [M + H]+; HRMS found (ESI) (M + H)+ 376.1385
C19H22NO7 requires 376.1396.
1
1068, 1027, 1003, 973, 806, 772, 757, 701, 633, 618; H NMR
(300 MHz, CD3COCD3) δ (ppm): 6.74 (d, J = 8.2 Hz, 1H), 6.65
(s, 2H), 6.56 (d, J = 2.2 Hz, 1H), 6.47 (dd, J = 8.2, 2.1 Hz, 1H),
6.40 (s, 1H), 4.31 (s, 2H), 3.81 (s, 3H), 3.73 (s, 3H), 3.72 (s,
9H); 13C NMR (75 MHz, CD3COCD3) δ (ppm): 153.7 (2C),
146.9 (C), 146.2 (CH), 138.1 (C), 138.0 (C), 134.8 (C), 134.0
(C), 121.3 (C), 117.8 (CH), 115.2 (CH), 111.0 (CH), 108.7
(2CH), 60.5 (OCH3), 56.4 (3 OCH3), 55.8 (OCH3); MS (APCI
positive, m/z): 346 [M + H].+
E-4e (E)-2-Methoxy-5-(2-methoxy-1-(3,4,5-trimethoxy-
phenyl)vinyl)aniline was obtained from the Z/E mixture of 4e,
separation was performed using an HPLC Sunfire C18 column
(19 × 150 mm, 5 μm) in isocratic mode, by using a mobile phase
4d (Z/E)-5-(1-(3-Fluoro-4-methoxyphenyl)-2-methoxy-
vinyl)-1,2,3-trimethoxybenzene was obtained as a mixture of
two diastereoisomers (Z/E = 56/44); yield 58%; yellow oil; R =
0.46 (cyclohexane/EtOAc: 7/3); IR (thin film, neat) νmax/cm−1
:
containing H2O/MeOH 45:/55; IR (thin film, neat) νmax/cm−1
:
3383, 3283, 3268, 3179, 2940, 2358, 2199, 2166, 2143, 2033,
2017, 1637, 1580, 1516, 1507, 1466, 1452, 1412, 1340, 1270,
1244, 1234, 1127, 1101, 1030, 1007, 924, 761, 731, 680, 663,
635; Spectroscopic NMR data for the mixture of isomers:
1H NMR (300 MHz, CDCl3) δ (ppm): 7.25 (dd, J = 13.0,
2.0 Hz, 1H), 7.09 (m, 1H), 6.91 (m, 1H), 6.41 (s, 2H), 6.39 (s,
1H), 3.89–3.70 (m, 15H); 13C NMR (75 MHz, CDCl3) δ (ppm):
153.2 (2C), 151.2 (C), 146.2 (CH), 146.0 (C), 137.2 (C), 135.9
(C), 130.8 (C), 125.6 (CH), 119.4 (C), 117.5 (CH), 112.9 (CH),
106.1 (2CH), 61.0 (OCH3), 60.8 (OCH3), 56.4 (OCH3), 56.3
(2OCH3); Minor E isomer (only the most significant resonances
are listed): (E)-5-(1-(3-fluoro-4-methoxyphenyl)-2-methoxy-
vinyl)-1,2,3-trimethoxybenzene: 1H NMR (300 MHz, CDCl3)
δ (ppm): 6.59 (s, 2H), 6.38 (s, 1H). MS (APCI positive, m/z):
349 [M + H]+; HRMS found (ESI) (M + H)+ 349.1450
C19H22O5F requires 349.1451.
4e (Z/E)-2-Methoxy-5-(2-methoxy-1-(3,4,5-trimethoxy-
phenyl)vinyl)benzenamine was obtained as a mixture of two
diastereoisomers (Z/E = 60/40); yield 74%; yellow oil; Rf = 0.19
(cyclohexane/EtOAc: 7/3); IR (thin film, neat) νmax/cm−1: 3488,
3449, 3425, 2235, 2163, 2071, 2014, 1995, 1906, 1700, 1578,
1504, 1464, 1449, 1410, 1376, 1246, 1206, 1175, 1149, 1124,
1103, 1050, 1026, 1004, 924, 680, 638, 616; Major Z isomer:
(Z)-2-methoxy-5-(2-methoxy-1-(3,4,5-trimethoxyphenyl)vinyl)-
benzenamine: 1H NMR (300 MHz, CD3COCD3) δ (ppm):
6.79–6.71 (m, 1H), 6.66 (s, 2H), 6.58 (d, J = 2.2 Hz, 1H), 6.48
(m, 1H), 6.41 (s, 1H), 4.32 (s, 2H), 3.85–3.67 (m, 15H);
13C NMR (100 MHz, CD3COCD3) δ (ppm): 153.7 (2C), 146.9
3396, 3372, 3333, 2186, 2164, 2010, 1635, 1579, 1514, 1503,
1465, 1451, 1410, 1368, 1340, 1286, 1247, 1218, 1150, 1125,
1103, 1028, 1004, 833, 760, 736, 652; 1H NMR (300 MHz,
CD3COCD3) δ (ppm): 6.74 (s, 2H), 6.64 (dd, J = 8.5, 1.6 Hz,
1H), 6.49 (s, 2H), 6.46 (s, 1H), 3.70–3.82 (m, 15H); 13C NMR
(75 MHz, CD3COCD3) δ (ppm): 154.0 (C), 146.4 (CH), 137.7
(C), 137.3 (C), 131.5 (C), 121.4 (C), 120.1 (CH), 117.1 (CH),
110.6 (CH), 106.9 (2CH), 60.6 (OCH3), 60.5 (OCH3),
56.4 (2OCH3), 55.8 (OCH3); MS (APCI positive, m/z): 346
[M + H].+
4f (Z/E)-5-(2-Ethoxy-1-(3,4,5-trimethoxyphenyl)vinyl)-
2-methoxyphenol was obtained as a mixture of two diastereo-
isomers (Z/E = 50/50); yield 65%; yellow oil; Rf = 0.26 (cyclo-
hexane/EtOAc: 5/5); IR (thin film, neat) νmax/cm−1: 2838, 2359,
2154, 2022, 1633, 1580, 1507, 1465, 1412, 1339, 1271, 1249,
1197, 1170, 1126, 1101, 1054, 1029, 1005, 928, 810, 762,
723, 615; (E)-5-(2-ethoxy-1-(3,4,5-trimethoxyphenyl)vinyl)-2-
methoxyphenol: 1H NMR (400 MHz, CD3COCD3) δ (ppm):
6.98 (d, J = 1.8 Hz, 1H), 6.87 (d, J = 8.4 Hz, 1H), 6.82 (dd, J =
8.4, 1.8 Hz, 1H), 6.55 (s, 1H), 6.50 (s, 2H), 3.98 (m, 2H),
3.83–3.72 (m, 12H), 1.31 (m, 3H). Spectroscopic 13C NMR data
for the mixture of isomers: 13C NMR (100 MHz, CD3COCD3)
δ (ppm): 154.1 (2C), 153.7 (2C), 147.2 (C), 147.2 (C), 146.8
(C), 146.7 (C), 145.4 (CH), 145.3 (CH), 138.0 (C), 137.6 (C),
137.5 (C), 134.7 (C), 134.6 (C), 132.0 (C), 122.1 (CH), 120.6
(C), 120.5 (C), 120.3 (CH), 117.7 (CH), 116.1 (CH), 112.3
(CH), 111.8 (CH), 108.6 (2CH), 107.1 (2CH), 69.2 (2 CH2),
60.6 (OCH3), 60.5 (OCH3), 56.4 (2OCH3), 56.4 (2OCH3), 56.3
Org. Biomol. Chem.
This journal is © The Royal Society of Chemistry 2012