JOURNAL OF CHEMICAL RESEARCH 2014 421
Table 2 Oxidative ether formation of 1,3-diarylpropenesa
R3
O
NHPI/O2
R3OH
+
CuBr/NiCl2
R1
R2
R1
R2
3
1
2
Entry
1, R1, R2
2, R3
Product (3)
Yield/%b
1
2
3
4
5
6
7
8
9
1a, R1=H, R2=H
1a, R1=H, R2=H
1a, R1=H, R2=H
1a, R1=H, R2=H
1a, R1=H, R2=H
1a, R1=H, R2=H
1a, R1=H, R2=H
1a, R1=F, R2=H
1b, R1=H, R2=Br
2a, R3=Me
3a
3b
3c
3d
3e
3f
3g
3h
3i
59
62
55
42
29
65
40
40
55
22
69
63
2b, R3=Et
2c, R3=i–Pr
2d, R3=t–Bu
2e, R3=C6H11
2f, R3=allyl
2g, R3=PhCH2
2b, R3=Et
2b, R3=Et
10
11
12
1c, R1=Cl, R2=Br
1d, R1=OMe, R2=H
1e, R1=H, R2=OMe
2b, R3=Et
3j
3k
3I
2b, R3=Et
2b, R3=Et
a0.5 mmol 1,3-diaryllpropene, 5 mmol alcohol, 40 mol% NHPI, 10 mol% CuBr, 10 mol% NiCl2, 2 mL
ClCH2CH2Cl, O2, 60 °C, 24 h.
bIsolated yields.
1,2‑dichloroethane was removed under reduced pressure. The residue
obtained was purified through silica gel using petroleum ether/ethyl
acetate (20:1–10:1) as an eluent.
(E)-3-Methoxy-1,3-diphenylprop-1-ene (3a):17 Oil. 1H NMR
(500 MHz, CDCl3): δ 7.43–7.38 (m, 6H), 7.34–7.31 (m, 3H), 7.28–7.24
(m, 1H), 6.66 (d, J=15.9 Hz, 1H), 6.32 (dd, J=7.1, 15.9 Hz, 1H), 4.83 (d,
J=7.0 Hz, 1H), 3.41 (s, 3H) ppm.
131.3, 130.52, 130.50, 130.4, 129.8, 128.51, 128.49, 128.45, 128.39,
128.1, 128.0, 127.7, 127.6, 126.8, 126.6, 115.4, 115.3, 115.27, 115.2,
82.4, 81.8, 64.0, 15.3 ppm, IR (KBr): 2969, 2926, 2859, 1706, 1588,
1487, 1449, 1289, 1072, 824, 752, 699 cm–1. EI‑MS (m/z): 256, 255, 227,
225, 183, 149, 136, 133, 123, 118, 105, 95, 91, 77, 51. Anal. calcd for
C17H17FO: C, 79.66; H, 6.69; found: C, 79.51; H, 6.81%.
1
(E)-1-Bromo-4-(1-ethoxy-3-phenylallyl)benzene (3i): Oil. H NMR
(E)-3-Ethoxy-1,3-diphenylprop-1-ene (3b):17 Oil. 1H NMR
(500 MHz, CDCl3): δ 7.44–7.37 (m, 6H), 7.33–7.29 (m, 3H), 7.28–7.23
(m, 1H), 6.64 (d, J=15.9 Hz, 1H), 6.34 (dd, J=7.1, 15.9 Hz, 1H), 4.95
(d, J=7.0 Hz, 1H), 3.65–3.59 (m, 1H), 3.54–3.48 (m, 1H), 1.29 (t,
J=7.0 Hz, 3H) ppm.
(E)-3-Isopropoxy-1,3-diphenylprop-1-ene (3c):17 Oil. 1H NMR
(500 MHz, CDCl3): 7.44–7.36 (m, 6H), 7.32–7.28 (m, 3H), 7.23 (t,
J=7.3 Hz, 1H), 6.60 (d, J=15.9 Hz, 1H), 6.32 (dd, J=7.0, 15.9 Hz, 1H),
5.07 (d, J=7.0 Hz, 1H), 3.78–3.73 (m, 1H), 1.26 (d, J=6.1 Hz, 3H), 1.21
(d, J=6.1 Hz, 3H) ppm.
(E)-3-tert-Butoxy-1,3-diphenylprop-1-ene (3d):17 Oil. 1H NMR
(500 MHz, CDCl3): 7.43 (d, J=7.4 Hz, 2H), 7.38–7.20 (m, 8H), 6.53 (d,
J=15.9 Hz, 1H), 6.33 (dd, J=6.3, 15.9 Hz, 1H), 5.21 (d, J=6.2 Hz, 1H),
1.28 (s, 9H) ppm.
(E)-3-Cyclohexyloxy-1,3-diphenylprop-1-ene (3e):17 Oil. 1H NMR
(500 MHz, CDCl3): δ 7.44–7.35 (m, 6H), 7.33–7.22 (m, 4H), 6.60 (d,
J=15.9 Hz, 1H), 6.33 (dd, J=6.9, 15.9 Hz, 1H), 5.13 (d, J=6.9 Hz, 1H),
3.46–3.40 (m, 1H), 2.01–1.89 (m, 2H), 1.81–1.73 (m, 2H), 1.54–1.53 (m,
1H), 1.47–1.38 (m, 2H), 1.30–1.22 (m, 3H) ppm.
(500 MHz, CDCl3): δ 7.50 (d, J=8.4 Hz, 1H), 7.43–7.37 (m, 4H),
7.33–7.28 (m, 2H), 7.26–7.24 (m, 2H), 6.61, 6.55 (dd, J=15.9, 15.9 Hz,
1H), 6.35–6.24 (m, 1H), 4.92, 4.89 (dd, J=6.8, 7.1 Hz, 1H), 3.64–3.55
(m, 0.5×2H), 3.52–3.45 (m, 0.5×2H), 1.28 (t, J=7.0 Hz, 3H) ppm. 13
C
NMR (125 MHz, CDCl3): 141.3, 140.7, 136.4, 135.7, 131.63, 131.60,
131.59 129.7, 128.57, 128.55, 128.1, 127.8, 127.7, 126.9, 126.6, 121.42,
121.40, 82.3, 81.8, 64.13, 64.10, 15.34, 15.32 ppm. IR (KBr): 2974, 2929,
2869, 1727, 1602, 1508, 1451, 1227, 1091, 835, 748, 699 cm–1. EI‑MS
(m/z): 77, 91, 105, 115, 118, 131, 165, 178, 189, 192, 237, 287, 289, 315,
315, 318. Anal. calcd for C17H17BrO: C, 64.37; H, 5.40; found: C, 64.42;
H, 5.29%.
(E)-1-Bromo-4-(3-(4-chlorophenyl)-1-ethoxyallyl)benzene
(3j):
1
Oil. H NMR (500 MHz, CDCl3): δ 7.50 (d, J=8.4 Hz, 1H), 7.43 (d,
J=8.5 Hz, 1H), 7.36–7.23 (m, 6H), 6.54, 6.53 (dd, J=15.9, 15.9 Hz,
1H), 6.27–6.21 (m, 1H), 4.89, 4.87 (t, J=6.1, 6.1 Hz, 1H), 3.61–3.54 (m,
0.5×2H), 3.50–3.44 (m, 0.5×2H), 1.29–1.25 (m, 3H) ppm. 13C NMR
(125 MHz, CDCl3): 140.4, 139.8, 135.4, 135.0, 133.4, 131.7, 131.0, 130.8,
130.2, 128.7, 128.5, 128.2, 128.1, 127.8, 121.6, 121.5, 81.7, 81.6, 64.2,
15.3 ppm. IR (KBr): 2973, 2927, 2865, 1706, 1588, 1487, 1399, 1087,
1011, 823 cm–1. EI‑MS (m/z): 94, 139, 179, 180, 183, 185, 189, 226, 227,
243, 271, 273, 323, 351,352. Anal. calcd for C17H16BrClO: C, 58.06; H,
4.59; found: C, 58.18; H, 4.75%.
(E)-3-Allyloxy-1,3-diphenylprop-1-ene (3f):17 Oil. 1H NMR
(500 MHz, CDCl3): δ 7.45–7.38 (m, 6H), 7.34–7.30 (m, 3H), 7.28–7.24
(m, 1H), 6.65 (d, J=15.9 Hz, 1H), 6.34 (dd, J=7.1, 15.9 Hz, 1H),
6.03–5.98 (m, 1H), 5.35 (dd, J=1.6, 17.2 Hz, 1H), 5.24 (d, J=1.4,
10.4 Hz, 1H), 5.02 (d, J=7.1 Hz, 1H), 4.11–4.03 (m, 2H) ppm.
(E)-3-Benzyloxy-1,3-diphenylprop-1-ene (3g):21 Oil. 1H NMR
(500 MHz, CDCl3): δ 7.49–7.48 (m, 2H), 7.43–7.38 (m, 8H), 7.36–7.32
(m, 4H), 7.28–7.25 (m, 1H), 6.67 (d, J=15.9 Hz, 1H), 6.39 (dd, J=7.1,
15.9 Hz, 1H), 5.06 (d, J=7.0 Hz, 1H), 4.63 (s, 2H) ppm.
(E)-1-(3-Ethoxy-3-phenylprop-1-enyl)-4-methoxybenzene (3k):22 Oil.
1H NMR (500 MHz, CDCl3): δ 7.43–7.22 (m, 7H), 6.92 (d, J=8.7 Hz,
1H), 6.85 (d, J=8.7 Hz, 1H), 6.59, 6.55 (dd, J=16.0, 16.0 Hz, 1H), 6.33
(dd, J=6.9, 15.9 Hz, 0.5×1H), 6.19 (dd, J=7.3, 15.9 Hz, 0.5×1H), 4.91,
4.90 (dd, J=8.0, 7.9 Hz, 1H), 3.82, 3.81 (s, 3H), 3.63–3.46 (m, 2H),
1.29–1.25 (m, 3H) ppm.
(E)-1-(1-Ethoxy-3-phenylallyl)-4-methoxybenzene (3l):22 Oil. 1H NMR
(500 MHz, CDCl3): δ 7.42–7.21 (m, 7H), 6.91 (d, J=8.7 Hz, 0.66×2H),
6.84 (d, J=8.8 Hz, 0.34×2H), 6.59, 6.55 (dd, J=16.0, 18.9 Hz, 1H), 6.32
(dd, J=7.0, 15.9 Hz, 0.66×1H), 6.18 (dd, J=7.2, 15.9 Hz, 0.34×1H),
4.91, 4.88 (dd, J=8.6, 7.4 Hz, 1H), 3.82 (s, 0.66×3H), 3.81 (s, 0.34×3H),
3.63–3.45 (m, 2H), 1.29–1.25 (m, 3H) ppm.
1
(E)-1-Fluoro-4-(3-ethoxy-3-phenylprop-1-enyl)benzene (3h): Oil. H
NMR (500 MHz, CDCl3): δ 7.42–7.23 (m, 7H), 7.06 (t, J=8.7 Hz, 1H),
6.99 (t, J=8.7 Hz 1H), 6.61, 6.58 (dd, J=15.4, 15.3 Hz, 1H), 6.31–6.22
(m, 1H), 4.93–4.91 (m, 1H), 3.64–3.56 (m, 0.5×2H), 3.53–3.46 (m,
0.5×2H), 1.28 (t, J=7.0 Hz, 3H) ppm. 13C NMR (125 MHz, CDCl3):
163.3, 163.2, 161.34, 161.26, 141.4, 137.4, 137.3, 136.5, 132.9, 132.8,
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