The Journal of Organic Chemistry
Note
1
854, 822, 811; H NMR (400.0 MHz; CDCl3) δH = 7.66 (d, J = 8.4
mmol) and 2-bromobenzonitrile (273.0 mg, 1.5 mmol) as a light
brown oil (116.6 mg, 60%) after column chromatography on silica,
Hz, 2H, ArH), 7.61 (d, J = 8.4 Hz, 2H, ArH), 7.51 (d, J = 8.8 Hz, 2H,
ArH), 6.98 (d, J = 8.8 Hz, 2H, ArH), 3.84 (s, 3H, CH3); 13C NMR
(100.6 MHz; CDCl3) δC = 160.3 (ArC), 145.3 (ArC), 132.7 (2 ×
ArCH), 131.5 (ArC), 128.5 (2 × ArCH), 127.2 (2 × ArCH), 119.2
(CN), 114.7 (2 × ArCH), 110.2 (ArC), 55.5 (CH3); m/z (EI) 209
[M]+., 194, 166, 140.
4-Methoxy-4′-nitrobiphenyl (3f). Following the general procedure
C, 3f was obtained from 4-nitroaniline (138.1 mg, 1.0 mmol) and p-
bromoanisole (187.0 μL, 280.5 mg, 1.5 mmol) as a yellow solid (46.2
mg, 28%) after column chromatography on silica, eluting with
pentane/CH2Cl2 (80:20 to 70:30). The 1H and 13C data were
consistent with those reported in the literature:39 mp 102−104 °C;
νmax (film)/cm−1 2924, 1600, 1593, 1505, 1480, 1341, 1249, 1184,
1
eluting with pentane/CH2Cl2 (90:10 to 70:30). The H and 13C data
were consistent with those reported in the literature:43 νmax (film)/
cm−1 3018, 2921, 2223, 1613, 1596, 1517, 1477, 1442, 1285, 1265,
1186, 1046, 1030, 820, 758, 745, 732; 1H NMR (400.0 MHz; CDCl3)
δH = 7.74 (dd, J = 7.7, 1.1 Hz, 1H, ArH), 7.61 (td, J = 7.7, 1.1 Hz, 1H,
ArH), 7.49 (d, J = 7.7 Hz, 1H, ArH), 7.47 (d, J = 8.2 Hz, 2H, ArH),
7.40 (td, J = 7.7, 1.1 Hz, 1H, ArH), 7.30 (d, J = 8.2 Hz, 2H, ArH), 2.41
(s, 3H, CH3); 13C NMR (100.6 MHz; CDCl3) δC = 145.5 (ArC),
138.7 (ArC), 135.4 (ArC), 133.7 (ArCH), 132.8 (ArCH), 130.0
(ArCH), 129.5 (2 × ArCH), 128.7 (2 × ArCH), 127.4 (ArCH), 118.9
(CN), 111.2 (ArC), 21.4 (CH3); m/z (EI) 193[M]+., 177, 165, 151,
140, 127.
1
1106, 1033, 1015, 838, 828, 815, 756, 722, 696; H NMR (400.0
1-(4′-Methylbiphenyl-4-yl)ethanone (3k). Following the general
procedure C, 3k was obtained from p-toluidine (107.2 mg, 1.0 mmol)
and p-bromoacetophenone (199.1 mg, 1.0 mmol) as a light brown
solid (84.2 mg, 40%) after column chromatography on silica, eluting
MHz; CDCl3) δH = 8.23 (d, J = 8.9 Hz, 2H, ArH), 7.66 (d, J = 8.9 Hz,
2H, ArH), 7.55 (d, J = 8.9 Hz, 2H, ArH), 7.00 (d, J = 8.9 Hz, 2H,
ArH), 3.85 (s, 3H, CH3); 13C NMR (100.6 MHz; CDCl3) δC = 160.6
(ArC), 147.3 (ArC), 146.6 (ArC), 131.1 (ArC), 128.7 (2 × ArCH),
127.2 (2 × ArCH), 124.3 (2 × ArCH), 114.7 (2 × ArCH), 55.6
(CH3); m/z (EI) 229 [M]+., 199, 183, 168, 156, 139, 128.
1
with pentane/CH2Cl2 (70:30). The H and 13C data were consistent
with those reported in the literature:44 mp 118−120 °C; νmax (film)/
1
cm−1 1675, 1599, 1422, 1397, 1360, 1263, 1199, 958, 805, 636; H
4′-Methoxybiphenyl-3-carboxylic acid (3g). Following the general
procedure C, 3g was obtained from 3-aminobenzoic acid (137.2 mg,
1.0 mmol) and p-bromoanisole (187.0 μL, 280.5 mg, 1.5 mmol) as a
light yellow solid (83.9 mg, 37%) after column chromatography on
NMR (400.0 MHz; CDCl3) δH = 8.00 (d, J = 8.5 Hz, 2H, ArH), 7.65
(d, J = 8.5 Hz, 2H, ArH), 7.52 (d, J = 8.1 Hz, 2H, ArH), 7.26 (d, J =
8.1 Hz, 2H, ArH), 2.61 (s, 3H, CH3), 2.39 (s, 3H, CH3); 13C NMR
(100.6 MHz; CDCl3) δC = 197.8 (CO), 145.8 (ArC), 138.3 (ArC),
137.1 (ArC), 135.7 (ArC), 129.8 (2 × ArCH), 129.0 (2 × ArCH),
127.2 (2 × ArCH), 127.0 (2 × ArCH), 26.7 (CH3), 21.3 (CH3); m/z
(EI) 210 [M]+., 195, 167, 115.
silica, eluting with pentane/EtOAc/AcOH (70:28:2). The 1H and 13
C
data were consistent with those reported in the literature:40 mp 204−
205 °C; νmax (film)/cm−1 2955 (br), 1679, 1606, 1515, 1452, 1439,
1
1315, 1247, 1184, 1024, 836, 813, 792, 757, 722, 687, 663; H NMR
4′-Methyl-3-(trifluoromethyl)biphenyl (3l). Following the general
procedure C, 3l was obtained from p-toluidine (107.2 mg, 1.0 mmol)
and 3-bromobenzotrifluoride (209.2 μL, 337.5 mg, 1.5 mmol) as a
colorless oil (54.3 mg, 23%) after column chromatography on silica,
(400.0 MHz; MeOD-d4) δH = 8.21 (s, 1H, ArH), 7.95 (d, J = 7.7 Hz,
1H, ArH), 7.80 (d, J = 7.7 Hz, 1H, ArH), 7.58 (dd, J = 8.6, 1.5 Hz, 2H,
ArH), 7.51 (td, J = 7.7, 1.9 Hz, 1H, ArH), 7.02 (dd, J = 8.6, 1.5 Hz,
2H, ArH), 3.84 (s, 3H, CH3); 13C NMR (100.6 MHz; MeOD-d4) δC =
170.0 (CO2H), 161.3 (ArC), 142.6 (ArC), 133.9 (ArC), 132.6 (ArC),
132.1 (ArCH), 130.1 (ArCH), 129.1 (2 × ArCH), 128.9 (ArCH),
128.8 (ArCH), 115.6 (2 × ArCH), 55.0 (CH3); m/z (ESI) 227 [M −
H]−, 195, 177, 97.
1
eluting with pentane/CH2Cl2 (95:5 to 80:20). The H, 13C and 19F
data were consistent with those reported in the literature:45 νmax
(film)/cm−1 1486, 1438, 1331, 1260, 1162, 1120, 1096, 1073, 1036,
902, 795, 700; 1H NMR (400.0 MHz; CDCl3) δH = 7.81 (s, 1H, ArH),
7.74 (d, J = 7.7 Hz, 1H, ArH), 7.57 (d, J = 7.7 Hz, 1H, ArH), 7.53 (t, J
= 7.7 Hz, 1H, ArH), 7.49 (d, J = 7.9 Hz, 2H, ArH), 7.27 (d, J = 7.9 Hz,
4′-Methoxy-2-methylbiphenyl (3h). Following the general proce-
dure C, 3h was obtained from o-toluidine (107.2 mg, 1.0 mmol) and p-
bromoanisole (187.0 μL, 280.5 mg, 1.5 mmol) as an orange oil (82.9
mg, 42%) after column chromatography on silica, eluting with
pentane/CH2Cl2 (90:10 to 80:20). The 1H and 13C data were
consistent with those reported in the literature:41 νmax (film)/cm−1
2933, 2834, 1611, 1514, 1482, 1452, 1293, 1266, 1240, 1175, 1037,
2H, ArH), 2.40 (s, 3H, CH3); 13C NMR (100.6 MHz; CDCl3) δC
=
142.1 (s, ArC), 138.2 (s, ArC), 137.1 (s, ArC), 131.4 (q, J = 32.2 Hz,
ArC), 130.2 (d, J = 1.2 Hz, ArCH), 129.9 (s, 2 × ArCH), 129.4 (s,
ArCH), 127.2 (s, 2 × ArCH), 124.4 (q, J = 272.0 Hz, Cq), 123.9 (q, J
= 3.8 Hz, ArCH), 123.8 (q, J = 3.7 Hz, ArCH), 21.3 (s, CH3). 19F
NMR (376.4 MHz; CDCl3) δF = −62.6 (s); m/z (EI) 236 [M]+., 217,
201, 183, 167, 153, 139, 126, 115.
1
1017, 831, 759, 730; H NMR (400.0 MHz; CDCl3) δH = 7.31−7.26
(m, 6H, ArH), 6.99 (d, J = 8.8 Hz, 2H, ArH), 3.88 (s, 3H, CH3), 2.32
(s, 3H, CH3); 13C NMR (100.6 MHz; CDCl3) δC = 158.7 (ArC),
142.7 (ArC), 135.6 (ArC), 134.5 (ArC), 130.5 (ArCH), 130.4 (2 ×
ArCH), 130.1 (ArCH), 127.1 (ArCH), 125.9 (ArCH), 113.1 (2 ×
ArCH), 55.4 (CH3), 20.7 (CH3); m/z (EI) 198 [M]+., 183, 169, 155,
141, 128, 115.
2,4′-Dimethylbiphenyl (3m). Following the general procedure C,
3m was obtained from p-toluidine (107.2 mg, 1.0 mmol) and 2-
bromotoluene (180.4 μL, 256.5 mg, 1.5 mmol) as a colorless oil (51.0
mg, 28%) after column chromatography on silica, eluting with
pentane/CH2Cl2 (90:10 to 80:20). The 1H and 13C data were
consistent with those reported in the literature:46 νmax (film)/cm−1
1
2-Fluoro-4′-methoxybiphenyl (3i). Following the general proce-
dure C, 3i was obtained from 2-fluoroaniline (111.2 mg, 1.0 mmol)
and p-bromoanisole (187.0 μL, 280.5 mg, 1.5 mmol) as a light orange
solid (70.0 mg, 34.5%) after column chromatography on silica, eluting
3020, 1515, 1482, 1452, 1158, 1109, 1007, 821, 755, 727; H NMR
(400.0 MHz; CDCl3) δH = 7.26−7.20 (m, 8H, ArH), 2.40 (s, 3H,
CH3), 2.28 (s, 3H, CH3); 13C NMR (100.6 MHz; CDCl3) δC = 142.0
(ArC), 139.2 (ArC), 136.6 (ArC), 135.6 (ArC), 130.5 (ArCH), 130.0
(ArCH), 129.3 (2 × ArCH), 128.9 (2 × ArCH), 127.3 (ArCH), 125.9
(ArCH), 21.4 (CH3), 20.7 (CH3); m/z (EI) 182 [M]+., 167, 152, 141,
128, 115.
6-(4-Methoxyphenyl)chroman-4-one (3n). Following the general
procedure C, 3n was obtained from 6-aminochroman-4-one4 (146.9
mg, 0.9 mmol) and p-bromoanisole (171.0 μL, 252.7 mg, 1.35 mmol)
as an orange solid (24.2 mg, 9.5%) after column chromatography on
silica, eluting with pentane/EtOAc (70:30): mp 93−95 °C; νmax
(film)/cm−1 2925, 1688, 1610, 1487, 1463, 1434, 1300, 1249, 1234,
1214, 1173, 1028, 815, 792; 1H NMR (400.0 MHz; CDCl3) δH = 8.06
(d, J = 2.4 Hz, 1H, ArH), 7.66 (dd, J = 8.6, 2.4 Hz, 1H, ArH), 7.48 (d,
J = 8.8 Hz, 2H, ArH), 7.01 (d, J = 8.6 Hz, 1H, ArH), 6.94 (d, J = 8.8
Hz, 2H, ArH), 4.55 (t, J = 6.5 Hz, 2H, CH2), 3.82 (s, 3H, CH3), 2.82
(t, J = 6.5 Hz, 2H, CH2); 13C NMR (100.6 MHz; CDCl3) δC = 192.1
(CO), 161.0 (ArC), 159.3 (ArC), 134.6 (ArCH), 134.4 (ArC),
1
with pentane/CH2Cl2 (90:10 to 80:20). The H and 13C data were
consistent with those reported in the literature:42 mp 45−47 °C; νmax
(film)/cm−1 2840, 1607, 1518, 1482, 1448, 1296, 1247, 1208, 1175,
1101, 1028, 1016, 1002, 819, 794, 748; 1H NMR (400.0 MHz;
CDCl3) δH = 7.52 (dd, J = 8.8, 1.8 Hz, 2H, ArH), 7.43 (dt, J = 7.8, 1.7
Hz, 1H, ArH), 7.29 (m, 1H, ArH), 7.22−7.13 (m, 2H, ArH), 7.01 (dt,
J = 8.8, 1.8 Hz, 2H, ArH), 3.86 (s, 3H, CH3); 13C NMR (100.6 MHz;
CDCl3) δC = 159.9 (d, J = 247.5 Hz, ArC), 159.4 (s, ArC), 130.7 (d, J
= 3.6 Hz, ArCH), 130.3 (d, J = 3.1 Hz, 2 × ArCH), 128.9 (d, J = 13.3
ArC), 128.6 (d, J = 8.1 Hz, ArCH), 128.5 (d, J = 3.8 Hz, ArCH), 128.3
(d, J = 0.8 Hz, ArC), 116.2 (d, J = 22.8 Hz, ArCH), 114.1 (s, 2 ×
ArCH), 55.4 (s, CH3). 19F NMR (376.4 MHz; CDCl3) δF = −118.2
(s); m/z (EI) 202 [M]+., 187, 159, 133.
4′-Methylbiphenyl-2-carbonitrile (3j). Following the general
procedure C, 3j was obtained from p-toluidine (107.2 mg, 1.0
G
dx.doi.org/10.1021/jo501665e | J. Org. Chem. XXXX, XXX, XXX−XXX