A Synthesis of Z-Trisubstituted Olefins and 4-Aryl-2H-chromenes
NMR (75 MHz, CDCl3): δ = 158.9, 140.2, 138.2 (2 C), 133.2, 130.3, + H]+. C19H22O3 (298.38): calcd. C 76.48, H 7.43; found C 76.30,
127.9, 127.4 (2 C), 125.3, 124.5 (2 C), 113.7 (2 C), 70.1, 66.1, 55.3,
30.6, 15.3, 15.3 ppm. MS (APCI+): m/z = 329.0 [M + H]+.
C20H24O2S (328.47): calcd. C 73.13, H 7.36; found C 73.00, H 7.19.
H 7.26.
(Z)-1-[3-Ethoxy-1-(4-methoxyphenyl)prop-1-en-1-yl]-2-(methoxy-
methoxy)benzene (2p): Colorless oil (68%). Rf = 0.34 (EtOAc/c-
hexane, 1:9). IR: ν = 2930, 2149, 2010, 1606, 1510, 1487, 1450,
˜
(Z)-1-[4-Ethoxy-1-(4-methoxyphenyl)but-1-en-1-yl]-4-methoxy-2-
nitrobenzene (2l): Brown oil (65 %). Rf = 0.63 (EtOAc/c-hexane,
1373, 1246, 1198, 1180, 1152, 1076, 1036, 995, 906, 825, 755,
729 cm–1. The presence of Z/E isomers in a ratio of 9:1 complicates
4:6). IR: ν = 2972, 1606, 1509, 1434, 1375, 1289, 1245, 1180, 1107,
˜
1
1035, 828, 793, 742, 633 cm–1. 1H NMR (300 MHz, CDCl3): δ =
7.53 (d, J = 2.4 Hz, 1 H), 7.25 (d, J = 8.4 Hz, 1 H), 7.19 (dd, J =
8.4, 2.4 Hz, 1 H), 7.12 (d, J = 8.9 Hz, 2 H), 6.78 (d, J = 8.9 Hz, 2
H), 6.09 (t, J = 7.5 Hz, 1 H), 3.90 (s, 3 H), 3.77 (s, 3 H), 3.47–3.42
(m, 4 H), 2.22 (m, 2 H), 1.18 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 159.3, 159.1, 149.7, 138.6, 133.3, 133.7,
127.7 (2 C), 127.4, 125.0, 113.8 (2 C), 119.8, 109.3, 69.9, 66.3, 55.9,
55.4, 30.8, 15.3 ppm. MS (APCI+): m/z = 358.0 [M + H]+.
C20H23NO5 (357.41): calcd. C 67.21, H 6.49, N 3.92; found C
67.05, H 6.30, N 3.68.
the NMR spectroscopic data. Data for major Z isomer: H NMR
(300 MHz, CDCl3): δ = 7.43–7.04 (m, 6 H), 6.78 (d, J = 8.9 Hz, 2
H), 6.25 (t, J = 6.6 Hz, 1 H), 5.02 (s, 2 H), 3.95 (d, J = 6.6 Hz, 2
H), 3.77 (s, 3 H), 3.43 (q, J = 7.0 Hz, 2 H), 3.26 (s, 3 H), 1.17 (t,
J = 7.0 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 158.9,
154.7, 139.8, 133.9, 131.4, 129.3, 128.9, 127.7 (2 C), 124.7, 121.9,
115.2, 113.6 (2 C), 94.4, 68.7, 65.6, 55.9, 55.2, 15.3 ppm. Data for
minor E isomer (only the most significant signals are listed): 1H
NMR (300 MHz, CDCl3): δ = 6.83 (d, J = 8.9 Hz, 2 H), 5.95 (t, J
= 6.6 Hz, 1 H), 4.88 (s, 2 H), 4.18 (d, J = 6.6 Hz, 2 H), 3.79 (s, 3
H), 3.51 (q, J = 7.0 Hz, 2 H), 3.16 (s, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 131.2, 130.2, 129.1, 113.2, 94.5, 68.4,
55.8 ppm. MS (APCI+): m/z = 329.6 [M + H]+. C20H24O4 (328.41):
calcd. C 73.15, H 7.37; found C 72.97, H 7.08.
(Z)-4-Methoxy-2-(methoxymethoxy)-1-[1-(4-methoxyphenyl)oct-1-
en-1-yl]benzene (2m): Colorless oil (72%). Rf = 0.58 (EtOAc/c-hex-
ane, 3:7). IR: ν = 2978, 1514, 1434, 1375, 1183, 1107, 1035, 913,
˜
828, 793, 742, 650 cm–1. Only the major Z isomer is described in
(Z)-2-[3-Ethoxy-1-(4-methoxyphenyl)prop-1-en-1-yl]-1-(methoxy-
methoxy)-4-methylbenzene (2q): Yellow oil (50 %). Rf = 0.38
1
the NMR spectroscopic data. H NMR (300 MHz, CDCl3): δ =
7.16 (d, J = 8.6 Hz, 2 H), 6.99 (d, J = 8.3 Hz, 1 H), 6.80–6.73 (m,
3 H), 6.59 (dd, J = 8.3, 2.4 Hz, 1 H), 6.07 (t, J = 7.3 Hz, 1 H), 4.99
(s, 2 H), 3.83 (s, 3 H), 3.77 (s, 3 H), 3.25 (s, 3 H), 1.99 (q, J =
7.3 Hz, 2 H), 1.47–1.14 (m, 8 H), 0.85 (t, J = 6.8 Hz, 3 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 160.1, 155.8, 158.6, 136.9, 135.4,
132.1, 129.3, 127.4 (2 C), 122.8, 113.5 (2 C), 106.7, 102.3, 94.7,
55.9, 55.5, 55.4, 31.9, 30.1, 29.8, 29.2, 22.8, 14.2 ppm. MS
(APCI+): m/z = 385.0 [M + H]+. C24H32O43 (1008.49): calcd. C
74.97, H 8.39; found C 74.89, H 8.27.
(EtOAc/c-hexane, 2:8). IR: ν = 2918, 1606, 1511, 1494, 1464, 1292,
˜
1248, 1230, 1199, 1179, 1147, 1098, 1072, 1036, 1010, 985, 922,
823, 806, 732 cm–1. Only the major Z isomer is described in the
NMR spectroscopic data. 1H NMR (300 MHz, CDCl3): δ = 7.22
(d, J = 8.9 Hz, 2 H), 7.11 (dd, J = 8.4, 2.2 Hz, 1 H), 7.05 (d, J =
8.4 Hz, 1 H), 6.93 (d, J = 2.2 Hz, 1 H), 6.80 (d, J = 8.9 Hz, 2 H),
6.24 (t, J = 6.5 Hz, 1 H), 4.99 (s, 2 H), 3.96 (d, J = 6.5 Hz, 2 H),
3.78 (s, 3 H), 3.45 (q, J = 7.0 Hz, 2 H), 3.27 (s, 3 H), 2.30 (s, 3 H),
1.19 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
158.9, 152.5, 139.7, 133.9, 131.7, 131.2, 129.3, 129.0, 127.7 (2 C),
124.5, 115.3, 113.4 (2 C), 94.7, 68.7, 65.6, 55.8, 55.2, 20.5,
15.3 ppm. MS (ESI+): m/z = 365.2 [M + Na]+. C21H26O4 (342.43):
calcd. C 73.66, H 7.65; found C 73.37, H 7.31.
(Z)-4-Methoxy-1-[1-(4-methoxyphenyl)oct-1-en-1-yl]-2-nitrobenzene
(2n): Colorless oil (52%). R = 0.64 (EtOAc/c-hexane, 5:5). IR: ν =
˜
f
2972, 1701, 1606, 1509, 1434, 1289, 1180, 999, 802 cm–1. The pres-
ence of an inseparable impurity complicates the NMR spectro-
scopic data. 1H NMR (300 MHz, CDCl3): δ = 7.52 (d, J = 1.9 Hz,
1 H), 7.20 (d, J = 8.1 Hz, 1 H), 7.17 (dd, J = 8.1, 1.9 Hz, 1 H),
7.11 (d, J = 8.5 Hz, 2 H), 6.78 (d, J = 8.5 Hz, 2 H), 3.91 (s, 3 H),
3.77 (s, 3 H), 1.95–1.84 (q, J = 6.9 Hz, 2 H), 1.43–1.33 (m, 2 H),
1.29–1.11 (m, 4 H), 0.85 (t, J = 6.9 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 159.2, 158.9, 149.9, 136.7, 133.7, 133.6,
129.5, 127.8 (2 C), 127.7, 113.7 (2 C), 119.7, 109.1, 56.9, 55.4, 31.8,
30.0, 29.6, 29.1, 22.7, 14.2 ppm. MS (APCI+): m/z = 370.6 [M +
H]+.
(Z)-3-[3-Ethoxy-1-(4-methoxyphenyl)prop-1-en-1-yl]-4-(methoxy-
methoxy)benzonitrile (2r): Yellow oil (52%). Rf = 0.53 (EtOAc/c-
hexane, 3:7). IR: ν = 2926, 2227, 1600, 1511, 1491, 1244, 1148,
˜
1078, 1035, 923, 822, 785, 734, 669, 648 cm–1. Only the major Z
isomer is described in the NMR spectroscopic data. 1H NMR
(300 MHz, CDCl3): δ = 7.62 (dd, J = 8.6, 2.2 Hz, 1 H), 7.44 (d, J
= 2.2 Hz, 1 H), 7.22 (d, J = 8.6 Hz, 1 H), 7.13 (d, J = 8.9 Hz, 2
H), 6.80 (d, J = 8.9 Hz, 2 H), 6.28 (t, J = 6.6 Hz, 1 H), 5.09 (s, 2
H), 3.87 (d, J = 6.6 Hz, 2 H), 3.78 (s, 3 H), 3.42 (q, J = 7.0 Hz, 2
H), 3.22 (s, 3 H), 1.18 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 159.4, 158.1, 138.1, 135.2, 133.6, 132.8,
130.3, 127.6 (2 C), 125.9, 119.0, 115.0, 113.8 (2 C), 105.2, 94.1,
68.5, 65.9, 56.4, 55.4, 15.4 ppm. MS (ESI+): m/z = 376.1 [M +
Na]+. C21H23NO4 (353.42): calcd. C 71.37, H 6.56, N 3.96; found
C 71.09, H 6.37, N 3.78.
(Z)-1-[3-Ethoxy-1-(3-methoxyphenyl)prop-1-enyl]-2-methoxybenz-
ene (2o): Yellow oil (32%). Rf = 0.23 (EtOAc/c-hexane, 5:95). IR:
ν = 2924, 2834, 1597, 1578, 1482, 1469, 1434, 1373, 1335, 1294,
˜
1244, 1169, 1130, 1096, 1049, 1026, 907, 883, 785, 751, 661,
631 cm–1. The presence of Z/E isomers in a ratio of 96:4 compli-
1
cates the NMR spectroscopic data. Data for major Z isomer: H
NMR (300 MHz, CDCl3): δ = 7.33 (ddd, J = 8.2, 7.4, 1.9 Hz, 1
H), 7.16 (t, J = 8.2 Hz, 1 H), 7.09 (dd, J = 7.4, 1.9 Hz, 1 H), 6.99
(dd, J = 7.4, 1.1 Hz, 1 H), 6.94 (d, J = 8.2 Hz, 1 H), 6.88–6.81 (m,
(Z)-1-[3-Ethoxy-1-(4-methoxyphenyl)prop-1-en-1-yl]-4-methoxy-2-
(methoxymethoxy)benzene (2s): Brown oil (64%). Rf = 0.4 (EtOAc/
c-hexane, 3:7). IR: ν = 2835, 1605, 1575, 1510, 1464, 1442, 1395,
˜
2 H), 6.77 (ddd, J = 8.2, 2.5, 1.1 Hz, 1 H), 6.34 (t, J = 6.4 Hz, 1 1289, 1245, 1216, 1152, 1097, 1071, 1036, 1004, 992, 923, 825, 805,
H), 3.93 (d, J = 6.4 Hz, 2 H), 3.76 (s, 3 H), 3.70 (s, 3 H), 3.43 (q,
731 cm–1. The presence of Z/E isomers in a ratio of 93:7 compli-
1
J = 7.0 Hz, 2 H), 1.17 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR cates the NMR spectroscopic data. Data for major Z isomer: H
(75 MHz, CDCl3): δ = 159.6, 157.2, 142.8, 139.9, 131.3, 129.1 (2 NMR (300 MHz, CDCl3): δ = 7.20 (d, J = 8.9 Hz, 2 H), 7.01 (d,
C), 128.0, 127.0, 120.6, 119.4, 112.7, 112.4, 111.2, 68.8, 65.7, 55.7,
55.3, 15.4 ppm. Data for minor E isomer (only the most significant
J = 8.4 Hz, 1 H), 6.78 (d, J = 8.9 Hz, 2 H), 6.74 (d, J = 2.5 Hz, 1
H), 6.59 (dd, J = 8.4, 2.5 Hz, 1 H), 6.21 (t, J = 6.5 Hz, 1 H), 4.99
signals are listed): 1H NMR (300 MHz, CDCl3): 6.03 (t, J = 6.6 Hz, (s, 2 H), 3.95 (d, J = 6.5 Hz, 2 H), 3.83 (s, 3 H), 3.77 (s, 3 H), 3.43
1 H), 4.15 (d, J = 6.6 Hz, 2 H) ppm. MS (APCI+): m/z = 299.0 [M (q, J = 7.0 Hz, 2 H), 3.25 (s, 3 H), 1.17 (t, J = 7.0 Hz, 3 H) ppm.
Eur. J. Org. Chem. 2012, 1603–1615
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1611