Job/Unit: O50353
/KAP1
Date: 21-04-15 11:45:00
Pages: 11
J. L. Nallasivam, R. A. Fernandes
FULL PAPER
128.16, 128.2, 128.7, 129.0, 130.4, 130.8, 138.8, 140.5, 156.4 ppm.
150.5 ppm. IR (CHCl ): ν = 3433, 3020, 1603, 1532, 1466, 1416,
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IR (CHCl ): ν = 3399, 3016, 2939, 2835, 1599, 1499, 1464, 1424, 1362, 1045, 999, 928, 850, 705, 669 cm–1. HRMS (ESI–TOF):
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1240, 1180, 1122, 1056, 1028, 668 cm–1. HRMS (ESI–TOF): calcd. calcd. for [C14H13NO4 + Na]+ 282.0737; found 282.0736.
for [C14H14O2 + Na]+ 237.0886; found 237.0887.
2-(4-Methylphenyl)benzonitrile (1a):[23] White solid (96%,
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185.3 mg), m.p. 53–55 °C, ref.[23] = 50–52 °C. H NMR (500 MHz,
CDCl3): δ = 2.43 (s, 3 H), 7.30 (d, J = 7.8 Hz, 2 H), 7.41 (t, J =
7.6 Hz, 1 H), 7.47 (d, J = 7.5 Hz, 2 H), 7.50 (d, J = 7.9 Hz, 1 H),
7.62 (t, J = 7.2 Hz, 1 H), 7.75 (d, J = 7.8 Hz, 1 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 21.2, 111.1, 118.8, 127.2, 128.5, 129.4,
4-Methoxybiphenyl (1h):[22] White solid (quant., 184 mg), m.p. 90–
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92 °C. H NMR (400 MHz, CDCl3): δ = 3.86 (s, 3 H), 6.97 (d, J =
8.8 Hz, 2 H), 7.29 (d, J = 7.4 Hz, 1 H), 7.40 (t, J = 7.6 Hz, 2 H),
7.52 (t, J = 8.2 Hz, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
55.2, 114.1, 126.6, 126.7, 128.1, 128.7, 133.7, 140.7, 159.1 ppm. IR
129.9, 132.7, 133.6, 135.2, 138.6, 145.4 ppm. IR (CHCl ): ν = 3021,
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(KBr): ν = 3056, 2962, 2937, 2836, 1606, 1582, 1522, 1488, 1464,
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1287, 1270, 1250, 1201, 1184, 1035, 834, 715, 687 cm–1.
2923, 2868, 2226, 1613, 1597, 1518, 1478, 1444, 1265, 1187, 1047,
1006, 928, 822, 669 cm–1. HRMS (ESI–TOF): calcd. for [C14H11
+ Na]+ 216.0784; found 216.0784.
N
4Ј-Methylbiphenyl-3-ol (1i): White solid (quant., 184 mg), m.p. 74–
76 °C. 1H NMR (400 MHz, CDCl3): δ = 2.39 (s, 3 H), 4.91 (s, 1
H, OH), 6.78–6.81 (m, 1 H), 7.04 (t, J = 2.1 Hz, 1 H), 7.14–7.17
(m, 1 H), 7.25–7.31 (m, 3 H), 7.46 (d, J = 8.2 Hz, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 21.1, 113.85, 113.9, 119.6, 126.9,
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Biphenyl-2-carbaldehyde (1o):[24] Colorless oil (98%, 178.3 mg). H
NMR (400 MHz, CDCl3): δ = 7.35–7.66 (m, 8 H), 8.04 (d, J =
7.8 Hz, 1 H), 10.0 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 127.0, 127.5, 127.7, 128.0, 128.3, 130.0, 130.7, 133.5, 137.6, 145.9,
129.4, 129.9, 137.3, 137.8, 142.9, 155.7 ppm. IR (KBr): ν = 3300,
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192.3 ppm. IR (CHCl ): ν = 3021, 2853, 2755, 1692, 1598, 1475,
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3028, 2915, 2853, 1588, 1568, 1478, 1446, 1324, 1299, 1214, 1192,
1164, 1127, 1039, 884, 816, 690 cm–1. HRMS (ESI–TOF): calcd.
for [C13H12O + H]+ 185.0961; found 185.0955.
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1394, 1255, 1197, 1074, 829, 703, 669 cm–1.
3Ј-(Hydroxymethyl)biphenyl-2-carbaldehyde (1p): Colorless oil
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(quant., 212 mg). H NMR (400 MHz, CDCl3): δ = 1.89 (br. s, 1
(4Ј-Methylbiphenyl-3-yl)methanol (1j): White solid (quant.,
198 mg), m.p. 72–74 °C. 1H NMR (400 MHz, CDCl3): δ = 1.75 (br.
s, 1 H, OH), 2.40 (s, 3 H), 4.76 (s, 2 H), 7.24–7.25 (m, 2 H), 7.32–
7.36 (m, 1 H), 7.41 (t, J = 7.6 Hz, 1 H), 7.50–7.59 (m, 3 H), 7.59–
7.61 (m, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.1, 65.3,
125.5, 126.2, 126.9, 128.9, 129.5, 137.1, 138.0, 141.3, 141.4 ppm.
H, OH), 4.78 (s, 2 H), 7.29 (dt, J = 4.2, 2.0 Hz, 1 H), 7.39–7.52
(m, 5 H), 7.62 (td, J = 7.5, 1.4 Hz, 1 H), 8.02 (dd, J = 7.8, 1.1 Hz,
1 H), 9.97 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 64.5,
126.5, 127.5, 127.7, 128.3, 128.4, 129.1, 130.6, 133.4, 133.6, 137.7,
141.2, 145.7, 192.7 ppm. IR (CHCl ): ν = 3442, 3020, 2977, 2933,
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2875, 2758, 1690, 1653, 1598, 1524, 1474, 1449, 1425, 1394, 1333,
1258, 1104, 1044, 928, 878, 849, 824, 708, 669 cm–1. HRMS (ESI–
TOF): calcd. for [C14H12O2 + Na]+ 235.0730; found 235.0718.
IR (CHCl ): ν = 3372, 3016, 2923, 2872, 1607, 1518, 1483, 1438,
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1187, 1021, 908, 823, 706, 668 cm–1. HRMS (ESI–TOF): calcd. for
[C14H14O + Na]+ 221.0937; found 221.0937.
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Biphenyl-4-carbaldehyde (1q):[25] Colorless oil (quant., 182 mg). H
2-Methoxy-3,5-dimethylbiphenyl (1k): Colorless oil (76%, 161 mg).
1H NMR (400 MHz, CDCl3): δ = 2.31 (s, 6 H), 3.34 (s, 3 H), 6.98
(s, 2 H), 7.34 (d, J = 7.4 Hz, 1 H), 7.40 (t, J = 7.2 Hz, 2 H), 7.55
(d, J = 7.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 16.2,
20.7, 59.9, 126.9, 128.1, 129.1, 129.3, 131.0, 131.2, 133.2, 134.5,
NMR (400 MHz, CDCl3): δ = 7.42 (d, J = 7.4 Hz, 1 H), 7.47 (t, J
= 7.3 Hz, 2 H), 7.64 (d, J = 7.6 Hz, 2 H), 7.75 (d, J = 8.3 Hz, 2
H), 7.95 (d, J = 8.4 Hz, 2 H), 10.06 (s, 1 H) ppm. 13C NMR
(100 MHz CDCl3): δ = 127.3, 127.6, 128.4, 128.9, 130.2, 135.1,
139.6, 147.1, 191.9 ppm.
138.9, 153.7 ppm. IR (CHCl ): ν = 3013, 2934, 1501, 1475, 1415,
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1248, 1163, 1014, 930, 864, 699 cm–1. HRMS (ESI–TOF): calcd.
3Ј-(Hydroxymethyl)biphenyl-4-carbaldehyde (1r): Colorless oil
(quant., 212 mg). H NMR (400 MHz, CDCl3): δ = 1.75 (br. s, 1
for [C15H16O + H]+ 213.1274; found 213.1268.
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H, OH), 4.80 (d, J = 4.6 Hz, 2 H), 7.41 (dt, J = 7.6, 1.4 Hz, 1 H),
7.47 (t, J = 7.6 Hz, 1 H), 7.56 (dt, J = 7.6, 1.5 Hz, 1 H), 7.66 (s, 1
H), 7.76 (d, J = 8.2 Hz, 2 H), 7.95 (d, J = 8.4 Hz, 2 H), 10.06 (s, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 64.6, 125.6, 126.3,
126.9, 127.5, 129.0, 130.1, 134.9, 139.6, 141.7, 146.8, 192.2 ppm.
(2Ј-Methoxy-3Ј,5Ј-dimethylbiphenyl-3-yl)methanol (1l): Colorless oil
(68%, 164.5 mg). H NMR (400 MHz, CDCl3): δ = 1.75 (br. s, 1
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H, OH), 2.31 (s, 6 H), 3.35 (s, 3 H), 4.76 (d, J = 3.8 Hz, 2 H), 6.99
(s, 2 H), 7.34–7.36 (m, 1 H), 7.39 (t, J = 7.5 Hz, 1 H), 7.50 (dt, J
= 7.6, 1.5 Hz, 1 H), 7.55 (d, J = 0.6 Hz, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 16.1, 20.7, 60.0, 65.4, 125.6, 127.7, 128.35,
128.4, 129.2, 131.1, 131.2, 133.3, 134.2, 139.1, 140.7, 153.6 ppm.
IR (CHCl ): ν = 3433, 3019, 2928, 2741, 1701, 1605, 1568, 1482,
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1409, 1388, 1306, 1172, 1017, 929, 834, 669 cm–1. HRMS (ESI–
TOF): calcd. for [C14H12O2 + Na]+ 235.0730; found 235.0718.
IR (CHCl ): ν = 3399, 3005, 2927, 2868, 1604, 1471, 1407, 1374,
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1252, 1226, 1111, 1015, 908, 735, 651 cm–1. HRMS (ESI–TOF):
calcd. for [C16H18O2 + Na]+ 265.1199; found 265.1199.
4-Acetylbiphenyl (1s):[22] White solid (quant., 196 mg), m.p. 115–
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117 °C. H NMR (400 MHz, CDCl3): δ = 2.64 (s, 3 H), 7.41 (d, J
= 7.3 Hz, 1 H), 7.45 (t, J = 7.6 Hz, 2 H), 7.62 (d, J = 7.0 Hz, 2 H),
7.68 (d, J = 8.0 Hz, 2 H), 8.03 (d, J = 8.5 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 26.7, 127.2, 127.24, 128.2, 128.9, 128.93,
(2Ј,6Ј-Dimethoxybiphenyl-3-yl)methanol (1m): White solid (62%,
151.3 mg), m.p. 72–74 °C. H NMR (400 MHz, CDCl3): δ = 3.73
(s, 6 H), 4.73 (s, 2 H), 6.65 (d, J = 8.4 Hz, 2 H), 7.26–7.41 (m, 5
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.8, 65.5, 104.1, 119.1,
125.5, 127.9, 128.7, 129.5, 130.2, 134.4, 140.2, 157.6 ppm. IR
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135.8, 139.8, 145.8, 197.8 ppm. IR (CHCl ): ν = 3154, 3033, 1677,
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1604, 1560, 1467, 1403, 1358, 1267, 1189, 1096, 912, 845, 741,
650 cm–1.
(CHCl ): ν = 3419, 3011, 2937, 2838, 1590, 1471, 1429, 1275, 1247,
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1034, 910, 706, 668 cm–1. HRMS (ESI–TOF): calcd. for [C15H16O3
4-Nitrobiphenyl (1t):[22] White solid (99%, 197 mg), m.p. 110–
112 °C. 1H NMR (400 MHz, CDCl3): δ = 7.43–7.61 (m, 3 H), 7.62–
7.64 (m, 2 H), 7.72 (d, J = 8.9 Hz, 2 H), 8.30 (d, J = 8.9 Hz, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 124.0, 127.3, 127.7, 128.9,
+ Na]+ 267.0992; found 267.0991.
(2Ј-Methoxy-3Ј-nitrobiphenyl-3-yl)methanol (1n): Colorless oil
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(quant., 259 mg). H NMR (400 MHz, CDCl3): δ = 1.90–2.01 (br.
129.1, 138.7, 147.0, 147.6 ppm. IR (CHCl ): ν = 3019, 2975, 2929,
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s, 1 H, OH), 3.53 (s, 3 H), 4.77 (s, 2 H), 7.24 (t, J = 7.9 Hz, 1 H),
7.41–7.51 (m, 3 H), 7.55–7.57 (m, 2 H), 7.72 (dd, J = 8.1, 1.7 Hz,
1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 61.8, 64.7, 123.97,
124.0, 126.6, 127.3, 127.9, 128.7, 135.1, 136.4, 137.3, 141.3, 144.9,
1598, 1578, 1518, 1482, 1348, 1318, 1106, 1046, 856, 771, 697 cm–1.
(4Ј-Nitrobiphenyl-3-yl)methanol (1u): Yellow solid (quant., 229 mg),
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m.p. 68–70 °C. H NMR (400 MHz, CDCl3): δ = 1.88–1.98 (br. s,
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