The Journal of Organic Chemistry
Note
1
hexanes: H NMR (300 MHz, CDCl3) δ 7.34 (dd, J = 8.1, 8.1 Hz, 1
tert-Butyl-5-[2-methoxy-6-(2-oxopropyl)phenyl]-1H-indole-1-car-
boxylate (entry 10). Isolated as a yellow oil (92%) using a 10%
H), 7.18−7.08 (m, 4 H), 6.93 (d, J = 8.1 Hz, 1 H), 6.87 (d, J = 8.1 Hz,
1
1 H), 3.74 (s, 3 H), 3.53 (s, 2 H), 1.97 (s, 3 H); 13C NMR (75 MHz,
solution of ethyl acetate in hexanes: H NMR (300 MHz, CDCl3) δ
1
8.20 (d, J = 8.1 Hz, 1 H), 7.66 (d, J = 3.6 Hz, 1 H), 7.38 (s, 1 H), 7.35
(dd, J = 8.1, 8.1 Hz, 1 H), 7.14 (d, J = 8.1 Hz, 1 H), 6.95 (d, J = 8.1
Hz, 1 H), 6.89 (d, J = 8.1 Hz, 1 H), 6.60 (d, J = 3.6 Hz, 1 H), 3.73 (s,
3 H), 3.55 (s, 2 H), 1.93 (s, 3 H), 1.72 (s, 9 H); 13C NMR (75 MHz,
CDCl3) δ 206.6, 157.5, 149.8, 134.8, 134.2, 131.6, 131.3, 130.6, 128.3,
126.2, 126.2, 122.5, 122.2, 114.9, 109.6, 107.4, 83.7, 55.8, 48.5, 29.7,
28.2; IR 1730, 1579, 1454, 1255, 1157, 1080, 1024, 735 cm−1; HRMS
(EI) m/z calcd for C23H25NO4 (M+) 379.1784, found 379.1773.
1-Cyclohexyl-2-(6-methoxy-4′-methylbiphenyl-2-yl)ethanone
(entry 11). Isolated as a clear oil (91%) using a 4% solution of ethyl
CDCl3) δ 206.2, 162.0 (d, JC−F = 244.5 Hz), 157.2, 134.6, 132.7 (d,
4JC−F = 3.0 Hz), 131.6 (d, JC−F = 7.5 Hz), 130.2, 128.6, 122.7, 115.1
3
(d, JC−F = 21.0 Hz), 109.7, 55.7, 48.4, 29.6; 19F NMR (282 MHz,
2
CDCl3) δ −114.9; IR 1720, 1468, 1257, 1220, 1159, 1078, 1008 cm−1
;
HRMS (EI) m/z calcd for C16H15FO2 (M+) 258.1056, found
258.1047.
2′-Methoxy-6′-(2-oxopropyl)biphenyl-4-carbonitrile (entry 3).
Isolated as a pale yellow crystalline solid (69%) using a 15% solution
of ethyl acetate in hexanes: mp 74 °C; 1H NMR (300 MHz, CDCl3) δ
7.71 (d, J = 8.4 Hz, 2 H), 7.37 (dd, J = 8.1, 8.1 Hz, 1 H), 7.31 (d, J =
8.4 Hz, 2 H), 6.94 (d, J = 8.1 Hz, 1 H), 6.87 (d, J = 8.1 Hz, 1 H), 3.73
(s, 3 H), 3.51 (s, 2 H), 1.99 (s, 3 H); 13C NMR (75 MHz, CDCl3) δ
205.7, 156.7, 142.3, 133.8, 131.9, 131.0, 129.4, 129.4, 122.8, 118.9,
1
acetate in hexanes: H NMR (400 MHz, CDCl3) δ 7.31 (dd, J = 8.0,
8.0 Hz, 1 H), 7.23 (d, J = 8.0 Hz, 2 H), 7.07 (d, J = 8.0 Hz, 2 H), 6.91
(d, J = 8.0 Hz, 1 H), 6.84 (d, J = 8.0 Hz, 1 H), 3.73 (s, 3 H), 3.57 (s, 2
H), 2.42 (s, 3 H), 2.12 (m, 1 H), 1.71 (m, 2 H), 1.61 (m, 3 H), 1.25−
1.17 (m, 5 H); 13C NMR (100 MHz, CDCl3) δ 211.1, 157.1, 136.5,
134.8, 133.9, 131.2, 129.8, 128.7, 128.0, 122.7, 109.4, 55.7, 50.2, 45.5,
28.3, 25.7, 25.5, 21.2; IR 2929, 1711, 1468, 1253, 1072 cm−1; HRMS
(EI) m/z calcd for C22H26O2 (M+) 322.1933, found 322.1944.
1-Cyclohexyl-2-(3′,4′,5′,6-tetramethoxybiphenyl-2-yl)ethanone
(entry 12). Isolated as a crystalline solid (84%) using a 27% solution
of ethyl acetate in hexanes: mp 117 °C; 1H NMR (300 MHz, CDCl3)
δ 7.31 (dd, J = 8.1, 8.1 Hz, 1 H), 6.91 (d, J = 8.1 Hz, 1 H), 6.82 (d, J =
8.1 Hz, 1 H), 6.38 (s, 2 H), 3.90 (s, 3 H), 3.82 (s, 6 H), 3.76 (s, 3 H),
3.57 (s, 2 H), 2.19 (m, 1 H), 1.70−1.61 (m, 5 H), 1.28−1.14 (m, 5
H); 13C NMR (75 MHz, CDCl3) δ 211.36, 157.0, 152.8, 136.7, 134.9,
132.7, 131.2, 128.3, 122.8, 109.5, 106.9, 60.8, 56.0, 55.8, 50.4, 45.6,
28.4, 25.7, 25.5; IR 2935, 1704, 1581, 1238, 1074 cm−1; HRMS (EI)
m/z calcd for C24H30O5 (M+) 398.2093, found 398.2081.
1-[4′-(2-Chloroethyl)-6-methoxybiphenyl-2-yl]-3-methylbutan-2-
one (entry 13). Isolated as a yellow oil (60%) using a 10% solution of
ethyl acetate in hexanes: 1H NMR (400 MHz, CDCl3) δ 7.30 (dd, J =
8.0, 8.0 Hz, 1 H), 7.10 (d, J = 8.8 Hz, 2 H), 6.96 (d, J = 8.8 Hz, 2 H),
6.87 (d, J = 8.0 Hz, 1 H), 6.84 (d, J = 8.0 Hz, 1 H), 4.28 (t, J = 6 Hz, 2
H), 3.85 (t, J = 6 Hz, 2 H), 3.72 (s, 3 H), 3.59 (s, 2 H), 2.43 (h, J = 6.8
Hz, 1 H), 0.94 (d, J = 6.8 Hz, 6 H); 13C NMR (100 MHz, CDCl3) δ
211.9, 157.2, 157.1, 134.8, 131.1, 130.7, 129.9, 128.1, 122.7, 114.3,
109.4, 67.9, 55.7, 45.3, 41.8, 40.2, 18.1; IR 1708, 1575, 1512, 1463,
1254 cm−1; HRMS (EI) m/z calcd for C20H23ClO3 (M+) 346.1336,
found 346.1325.
111.1, 109.7, 55.7, 48.3, 29.6; IR 2228, 1718, 1608, 1257, 1078 cm−1
;
HRMS (EI) m/z calcd for C17H15NO2 (M+) 265.1103, found
265.1109.
Methyl 2′-Methoxy-6′-(2-oxopropyl)biphenyl-4-carboxylate
(entry 4). Isolated as a brown powder (89%) using a 14% solution
of ethyl acetate in hexanes: mp 105 °C; 1H NMR (300 MHz, CDCl3)
δ 8.10 (d, J = 8.4 Hz, 2 H), 7.35 (dd, J = 8.1 Hz, 1 H), 7.27 (d, J = 8.4
Hz, 2 H), 6.93 (d, J = 8.1 Hz, 1 H), 6.87 (d, J = 8.1 Hz, 1 H), 3.95 (s,
3 H), 3.72 (s, 3 H), 3.51 (s, 2 H), 1.95 (s, 3 H); 13C NMR (75 MHz,
CDCl3) δ 206.0, 167.0, 156.9, 142.2, 134.0, 130.3, 130.1, 129.4, 128.9,
128.9, 122.7, 109.7, 55.7, 52.1, 48.3, 29.6; IR 1722, 1610, 1279, 1257,
1078, 1007 cm−1; HRMS (EI) m/z calcd for C18H18O4 (M+)
298.1205, found 298.1215.
1-(4′,6-Dimethoxybiphenyl-2-yl)propan-2-one (entry 5). Isolated
as a yellow oil (88%) using a 10% solution of ethyl acetate in hexanes:
1H NMR (300 MHz, CDCl3) δ 7.32 (dd, J = 8.1, 8.1 Hz, 1 H), 7.11
(d, J = 8.7 Hz, 2 H), 6.97 (d, J = 8.7 Hz, 2 H), 6.92 (d, J = 8.1 Hz, 1
H), 6.87 (d, J = 8.1 Hz, 1 H), 3.87 (s, 3 H), 3.74 (s, 3 H), 3.55 (s, 2
H), 1.96 (s, 3 H); 13C NMR (75 MHz, CDCl3) δ 206.6, 158.6, 157.4,
134.9, 131.0, 130.9, 129.0, 128.3, 122.6, 113.6, 109.7, 55.8, 55.2, 48.5,
29.6; IR 1714, 1579, 1288, 1248, 1078, 1018 cm−1; HRMS (EI) m/z
calcd for C17H18O3 (M+) 270.1256, found 270.1266.
1-(6-Methoxy-2′-methylbiphenyl-2-yl)propan-2-one (entry 6).
Isolated as a slightly yellow crystalline solid (99%) using a 5%
solution of ethyl acetate in hexanes: mp 53 °C; H NMR (300 MHz,
1
1-[3-Methoxy-2-(naphthalen-2-yl)phenyl]-3-methylbutan-2-one
CDCl3) δ 7.35 (dd, J = 8.1, 8.1 Hz, 1 H), 7.29 (m, 2 H), 7.25 (dd, J =
7.8, 7.8 Hz, 1 H), 7.04 (d, J = 7.8 Hz, 1 H), 6.93 (d, J = 8.1 Hz, 1 H),
6.90 (d, J = 8.1 Hz, 1 H), 3.74 (s, 3 H), 3.54 (d, J = 16.2 Hz, 1 H), 3.34
(d, J = 16.2 Hz, 1 H), 2.03 (s, 3 H), 1.89 (s, 3 H); 13C NMR (75
MHz, CDCl3) δ 206.3, 157.0, 137.0, 136.6, 134.5, 130.4, 129.8, 129.8
128.4, 127.5, 125.6, 122.7, 109.5, 55.7, 48.0, 29.7, 19.5; IR 1720, 1641,
1255, 1078, 1007 cm−1; HRMS (EI) m/z calcd for C17H18O2 (M+)
254.1307, found 254.1315.
1-(2′,6-Dimethoxybiphenyl-2-yl)propan-2-one (entry 7). Isolated
as a clear oil (86%) using a 13% solution of ethyl acetate in hexanes:
1H NMR (300 MHz, CDCl3) δ 7.37 (dt, J = 8.1, 2.1 Hz, 1 H), 7.34
(dd, J = 7.8, 7.8 Hz, 1 H), 7.08 (dd, J = 8.1, 2.1 Hz, 1 H), 7.04 (dd, J =
8.1 Hz, 1 H), 7.00 (d, J = 8.1 Hz, 1 H), 6.94 (d, J = 7.8 Hz, 1 H), 6.92
(d, J = 7.8 Hz, 1 H), 3.74 (s, 3 H), 3.48 (d, J = 16.2 Hz, 1 H), 3.42 (d,
J = 16.2 Hz, 1 H), 2.03 (s, 3 H), 1.89 (s, 3 H); 13C NMR (75 MHz,
CDCl3) δ 206.7, 157.5, 156.8, 135.2, 131.7, 129.0, 128.5, 127.7, 125.5,
122.4, 120.5, 110.9, 109.8, 55.9, 55.3, 48.6, 29.2; IR 1711, 1581, 1253,
1078, 1051 cm−1; HRMS (EI) m/z calcd for C17H18O3 (M+)
270.1256, found 270.1250.
(entry 14). Isolated as a yellow oil (78%) using a 12% solution of
1
ethyl acetate in hexanes: H NMR (400 MHz, CDCl3) δ 7.87 (m, 2
H), 7.81 (m, 1 H), 7.62 (s, 1 H), 7.50 (m, 2 H), 7.34 (m, 2 H), 6.95
(d, J = 8 Hz, 1 H), 6.88 (d, J = 8 Hz, 1 H), 3.72 (s, 3 H), 3.62 (d, J =
17.0 Hz, 1 H), 3.56 (d, J = 17.0 Hz, 1 H), 2.35 (h, J = 6.8 Hz, 1 H),
0.85 (d, J = 5.0 Hz, 3 H), 0.82 (d, J = 5.0 Hz, 3 H); 13C NMR (100
MHz, CDCl3) δ 211.9, 157.2, 134.7, 134.6, 133.2, 132.4, 131.1, 128.5,
128.4, 128.3, 127.9, 127.6, 127.4, 125.9, 125.7, 122.8, 109.5, 55.7, 45.4,
40.2, 18.0; IR 2963, 2928, 1708, 1575, 1464, 1254, 1085, 1067 cm−1
;
HRMS (EI) m/z calcd for C22H22O2 (M+) 318.1620, found 318.1611.
1-(4-Methoxyphenyl)-2-[4′-(trifluoromethyl)biphenyl-2-yl]-
ethanone (entry 15). Isolated as a clear oil (81%) using a 10%
1
solution of ethyl acetate in hexanes: H NMR (400 MHz, CDCl3) δ
7.80 (d, J = 8.8 Hz, 2 H), 7.62 (d, J = 8.0 Hz, 2 H), 7.43 (d, J = 8.0 Hz,
2 H), 7.39 (m, 2 H), 7.35 (d, J = 8.0 Hz, 1 H), 7.31 (t, J = 8.0 Hz, 1
H), 6.89 (d, J = 8.8 Hz, 2 H), 4.20 (s, 2 H), 3.87 (s, 3 H); 13C NMR
(100 MHz, CDCl3) δ 196.3, 163.5, 145.0, 140.9, 132.6, 130.9, 130.4,
130.0 (q, 2JC−F = 32.0 Hz), 129.8, 129.4, 128.1, 127.0, 125.0 (q, 3JC−F
=
4.0 Hz), 124.1 (q, 1JC−F = 271.0 Hz), 113.6, 55.3, 42.5; 19F NMR (282
MHz, CDCl3) δ −62.4; IR 1675, 1600, 1324, 1263, 1168, 1068 cm−1
;
1-[3-Methoxy-2-(thiophen-3-yl)phenyl]propan-2-one (entry 9).
Isolated as a clear oil (99%) using an 11% solution of ethyl acetate in
HRMS (EI) m/z calcd for C22H17F3O2 (M+) 370.1181, found
370.1169.
1
hexanes: H NMR (400 MHz, CDCl3) δ 7.39 (dd, J = 4.8, 2.4 Hz, 1
H), 7.32 (t, J = 8.0 Hz, 1 H), 7.10 (d, J = 2.4 Hz, 1 H), 6.99 (d, J = 4.8
Hz, 1 H), 6.91 (d, J = 8.0 Hz, 1 H), 6.86 (d, J = 8.0 Hz, 1 H), 3.76 (s,
3 H), 3.60 (s, 2 H), 2.00 (s, 3 H); 13C NMR (282 MHz, CDCl3) δ
206.5, 157.6, 136.4, 135.2, 129.5, 128.5, 126.1, 124.8, 123.5, 122.6,
109.6, 55.7, 48.5, 29.5; IR 1712, 1643, 1360, 1223, 1076 cm−1; HRMS
(EI) m/z calcd for C14H14O2S (M+) 246.0715, found 246.0721.
2-[2-(Benzo[b]thiophen-3-yl)phenyl]-1-(4-methoxyphenyl)-
ethanone (entry 16). Isolated as a yellow oil (76%) using a 10%
1
solution of ethyl acetate in hexanes: H NMR (300 MHz, CDCl3) δ
7.91 (d, J = 7.8 Hz, 1 H), 7.67 (d, J = 8.7 Hz, 2 H), 7.49 (d, J = 7.8 Hz,
1 H), 7.44−7.29 (m, 7 H), 6.78 (d, J = 8.7 Hz, 2 H), 4.13 (s, 2 H),
3.83 (s, 3 H); 13C NMR (75 MHz, CDCl3) δ 196.7, 163.3, 139.9,
9160
dx.doi.org/10.1021/jo201632c|J. Org. Chem. 2011, 76, 9157−9162