10.1002/adsc.201800462
Advanced Synthesis & Catalysis
the reaction, the mixture was cooled to room temperature,
2-Methoxyethyl
4-hydroxy-[1,1'-biphenyl]-3-
1
and the product 3a was obtained by isolation with carboxylate (3h): 69.4 mg, 85%; light brown liquid; H
°
preparative TLC (84.5 mg, yield
=
80%, elutent: (400 Hz, CDCl3, 25 C, TMS): δ = 3.43 (s, 3H), 3.74–3.76
(m, 2H), 4.53-4.55 (m, 2H), 7.06 (d, J = 8.8 Hz, 1H), 7.32-
7.35 (m, 1H), 7.42–7.45 (m, 2H), 7.55 (d, J = 8.0 Hz, 2H),
7.70 (dd, J = 2.0, 8.8 Hz, 1H), 8.10 (d, J = 2.0 Hz, 1H),
pertroleum ether/ethyl acetate = 5/1 (v/v)).
Spectroscopic data of the obtained products
10.74 ppm (s, 1H); 13C (100 Hz, CDCl3, 25 C, TMS): δ =
59.3, 64.5, 70.4, 112.7, 118.2, 126.9, 127.2, 128.5, 129.0,
°
Methyl 4-hydroxy-[1,1'-biphenyl]-3-carboxylate (3a):[28]
132.7, 134.7, 140.1, 161.2, 170.2 ppm; IR: v = 3398, 3194,
3063, 3033, 2924, 1724, 1678, 1601, 1479, 1449, 1380,
1332, 1273, 1244, 1206, 1129, 1092, 1027, 905, 839, 794,
763, 700, 583, 541, 495, 443 cm-1; HRMS (EI): m/z calcd
for C16H16NaO4: 295.0941 [M + Na] +; found: 295.0945.
Allyl 4-hydroxy-[1,1'-biphenyl]-3-carboxylate (3i):
°
1
63.6 mg, 93%; white solid, mp: 95–96 C; H (400 Hz,
°
CDCl3, 25 C, TMS): δ = 3.99 (s, 3H), 7.07 (d, J = 8.4 Hz,
1H), 7.32–7.35 (m, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.54–7.56
(m, 2H), 7.71 (dd, J = 2.0, 8.4 Hz, 1H), 8.08 (d, J = 2.0 Hz,
1H), 10.78 ppm (s, 1H); 13C (100 Hz, CDCl3, 25 °C, TMS):
δ = 52.5, 112.7, 118.2, 126.8, 127.2, 128.3, 129.0, 132.6,
134.6, 140.1, 161.2, 170.7 ppm.
1
61.7 mg, 81%; light yellow liquid; H (400 Hz, CDCl3,
25 °C, TMS): δ = 4.88 (d, J = 5.6 Hz, 2H), 5.33 (d, J = 6.4
Hz, 1H), 5.44 (d, J = 8.8 Hz, 1H), 6.00–6.10 (m, 1H), 7.06
(d, J = 7.6 Hz, 1H), 7.31–7.35 (m, 1H), 7.43 (t, J = 7.6 Hz,
2H), 7.54 (d, J = 7.2 Hz, 2H), 7.70 (dd, J = 2.0, 8.4 Hz, 1H),
8.10 (d, J = 2.0 Hz, 1H), 10.80 ppm (s, 1H); 13C (100 Hz,
Ethyl
4-hydroxy-[1,1'-biphenyl]-3-carboxylate
°
(3b):[45] 65.3 mg, 90%; white solid, mp: 50–51 C; 1H (400
Hz, CDCl3, 25 °C, TMS): δ = 1.44 (t, J = 7.2 Hz, 3H), 4.45
(q, J = 7.2 Hz, 2H), 7.07 (d, J = 8.8 Hz, 1H), 7.32–7.36 (m,
1H), 7.42–7.46 (m, 2H), 7.56 (d, J = 7.2 Hz, 2H), 7.70 (dd,
J = 2.0, 8.4 Hz, 1H), 8.08 (d, J = 2.0 Hz, 1H), 10.89 ppm (s,
°
CDCl3, 25 C, TMS): δ = 66.1, 112.7, 118.2, 119.3, 126.8,
127.2, 128.3, 129.0, 131.7, 132.7, 134.7, 140.1, 161.3,
169.9 ppm; IR: v = 3212, 3084, 3033, 2924, 2853, 1678,
1603, 1513, 1480, 1377, 1332,, 1272, 1243, 1205, 1144,
1090, 966, 934, 836, 795, 699, 582, 543, 461, 421 cm-1;
HRMS (EI): m/z calcd for C16H14NaO3: 277.0835 [M + Na]
+; found: 277.0839.
1H); 13C (100 Hz, CDCl3, 25 C, TMS): δ = 14.4, 61.7,
°
112.9, 118.2, 126.8, 127.2, 128.3, 129.0, 132.6, 134.5,
140.2, 161.2, 170.3 ppm.
Isopropyl
4-hydroxy-[1,1'-biphenyl]-3-carboxylate
(3c): 65.3 mg, 85%; light yellow liquid; 1H (400 Hz, CDCl3,
°
25 C, TMS): δ = 1.42 (d, J = 6.4 Hz, 6H), 5.29–5.38
Prop-2-yn-1-yl
4-hydroxy-[1,1'-biphenyl]-3-
(m,1H), 7.06 (d, J = 8.4 Hz, 1H), 7.32–7.36 (m, 1H), 7.43–
7.47 (m, 2H), 7.56 (d, J = 7.6 Hz, 2H), 7.69 (dd, J = 2.0,
9.4 Hz, 1H), 8.05 (d, J = 2.0 Hz, 1H), 10.98 ppm (s, 1H);
13C (100 Hz, CDCl3, 25°C, TMS): δ = 22.0, 69.6, 113.2,
118.1, 126.9, 127.2, 128.3, 129.0, 132.5, 134.4, 140.3,
161.3, 169.9 ppm; IR: v = 3160, 3066, 3035, 2983, 2931,
1673, 1601, 1479, 1373, 1322, 1275, 1244, 1211, 1146,
1097, 921, 837, 798, 762, 739, 699, 583, 543, 498, 431 cm-
1; HRMS (EI): m/z calcd for C16H16NaO3: 279.0992 [M +
Na] +; found: 279.0998.
carboxylate (3j): 65.8 mg, 87%; light yellow solid: 92–93
oC; 1H (400 Hz, CDCl3, 25 C, TMS): δ = 2.88 (d, J = 2.0
°
Hz, 1H), 5.28 (d, J = 2.4 Hz, 2H), 7.38 (d, J = 8.8 Hz, 1H),
7.65 (d, J = 7.6 Hz, 1H), 7.74 (t, J = 7.6 Hz, 2H), 7.85 (d, J
= 7.6 Hz, 2H), 8.03 (dd, J = 2.0, 7.6 Hz, 1H), 8.40 (d, J =
2.0 Hz, 1H), 10.86 ppm (s, 1H); 13C (100 Hz, CDCl3, 25 °C,
TMS): δ = 52.8, 75.7, 112.0, 118.2, 126.7, 128.3, 128.9,
132.7, 135.0, 139.8, 161.2, 169.4 ppm; IR: v = 3446, 3263,
3033, 2920, 2851, 2127, 1957, 1898, 1904, 1678, 1618,
1477, 1445, 1384, 1329, 1270, 1239, 1197, 1137, 1086,
989, 950, 905, 837, 792, 764, 701, 669, 581, 516, 476, 434
cm-1; HRMS (EI): m/z calcd for C16H12NaO3: 275.0679 [M
+ Na] +; found: 275.0674.
Benzyl 4-hydroxy-[1,1'-biphenyl]-3-carboxylate (3d):
1
80.3 mg, 88%; light yellow liquid; H (400 Hz, CDCl3,
°
25 C, TMS): δ = 5.44 (s, 2H), 7.08 (d, J = 8.8 Hz, 1H),
7.32–7.35 (m, 1H), 7.38–7.48 (m, 7H), 7.54 (d, J = 7.6 Hz,
2H), 7.71 (dd, J = 2.0, 8.4 Hz, 1H), 8.11 (d, J = 2.0 Hz, 1H),
Methyl
4-hydroxy-5-methyl-[1,1'-biphenyl]-3-
carboxylate (3k): 59.5 mg, 82%; light grey solid: 95–
°
10.81 ppm (s, 1H); 13C (100 Hz, CDCl3, 25 C, TMS): δ =
°
°
96 C; 1H (400 Hz, CDCl3, 25 C, TMS): δ = 2.34 (s, 3H),
3.97 (s, 3H), 7.32–7.34 (m, 1H), 7.41–7.44 (m, 2H), 7.54–
7.58 (m, 3H), 7.93 (d, J = 2.0 Hz, 1H), 11.03 ppm (s, 1H);
67.2, 112.7, 118.2, 126.9, 127.2, 128.3, 128.5,128.7,128.9,
129.0, 132.7, 134.8, 135.4, 140.1, 161.3, 170.1ppm; IR: v =
3200, 3064, 3034, 2926, 1952, 1676, 1599, 1479, 1390,
1334, 1298, 1272, 1242, 1205, 1144, 1088, 950, 910, 837,
794, 758, 697, 585, 550, 477 cm-1; HRMS (EI): m/z calcd
for C20H16NaO3: 327.0992 [M + Na] +; found: 327.0996.
1-(4-Hydroxy-[1,1'-biphenyl]-3-yl)ethanone (3e):[46]
13C (100 Hz, CDCl3, 25 C, TMS): δ = 16.0, 52.5, 112.0,
°
125.8, 126.8, 127.1, 127.2, 128.9, 131.9, 135.4, 140.3,
159.7, 171.2 ppm; IR: v = 3443, 3109, 3011, 2955, 2921,
2852, 1671, 1610, 1442, 1351, 129, 1227, 1188, 1142,
1072, 1017, 983, 889, 797, 761, 689, 629, 595, 524, 475,
439 cm-1; HRMS (EI): m/z calcd for C16H16NaO3: 279.0992
[M + Na] +; found: 279.0997.
°
1
38.2 mg, 60%; pink solid, mp: 59–60 C; H (400 Hz,
CDCl3, 25 oC, TMS): δ = 2.70 (s, 3H), 7.07 (d, J = 8.8 Hz,
1H), 7.34–7.41 (m, 1H), 7.44–7.48 (m, 2H), 7.54 (d, J =
7.2 Hz, 2H), 7.72 (dd, J = 6.8, 8.8 Hz, 1H), 7.92 (d, J = 2.0
Ethyl
5-ethyl-4-hydroxy-[1,1'-biphenyl]-3-
1
carboxylate (3l): 74.4 mg, 93%; light yellow liquid; H
(400 Hz, CDCl3, 25 °C, TMS): δ = 1.30 (t, J = 7.6 Hz, 3H),
1.44 (t, J = 7.2 Hz, 3H), 2.77 (q, J = 7.6 Hz, 2H), 4.45 (q, J
= 7.2 Hz, 2H), 7.32–7.36 (m, 1H), 7.45 (t, J = 7.6 Hz, 2H),
7.56–7.60 (m, 3H), 7.95 (d, J = 2.0 Hz, 1H), 11.17 (s, 1H);
°
Hz, 1H), 12.27 ppm (s, 1H); 13C (100 Hz, CDCl3, 25 C,
TMS): δ = 26.7, 118.9, 119.8, 126.7, 127.2, 129.0, 129.1,
132.4, 135.4, 140.0, 161.8, 204.6 ppm.
(4-Hydroxy-[1,1'-biphenyl]-3-yl)(phenyl)methanone
°
(3f):[47] 60.8 mg,74%; yellow solid: 91–92 C; 1H (400 Hz,
13C (100 Hz, CDCl3, 25 C, TMS): δ = 14.0, 14.4, 23.2,
°
°
CDCl3, 25 C, TMS): δ = 7.18 (d, J = 8.8Hz, 1H), 7.30–
112.3, 125.8, 126.9, 127.0, 128.9, 131.9, 133.1, 133.8,
140.6, 159.5, 170.8 ; IR: v = 3151, 3063, 3033, 2971, 2926,
2876, 1802, 1671, 1606, 1457, 1399, 1375, 1343, 1279,
1237, 1148, 1091, 1026, 892, 800, 760, 698, 630, 597, 545,
482, 412 cm-1; HRMS (EI): m/z calcd for C17H18NaO3:
293.1148 [M + Na] +; found: 293.1145.
7.34 (m, 1H), 7.39–7.43 (m, 2H), 7.46–7.47 (m, 2H), 7.52–
7.55 (m, 2H), 7.60–7.64 (m,1H), 7.74–7.79 (m, 3H), 7.82
(d, J = 2.0 Hz, 1H), 12.03 ppm (s, 1H); 13C (100 Hz, CDCl3,
°
25 C, TMS): δ = 119.0, 119.4, 126.8, 127.3, 128.6, 129.0,
129.4, 131.9, 132.1, 132.2, 135.2, 138.0, 140.0, 162.8,
201.8 ppm.
Diethyl 4-hydroxy-[1,1'-biphenyl]-3,5-dicarboxylate
(3m):[48] 85.7 mg, 91%; yellow solid: 69–70 °C; 1H (400 Hz,
CDCl3, 25 °C, TMS): δ = 1.43 (t, J = 7.2 Hz, 6H), 4.45 (q, J
= 7.2 Hz, 4H), 7.34–7.38 (m, 1H), 7.44–7.47 (m, 2H),
7.56–7.58 (m, 2H), 8.27 (s, 2H), 11.87 ppm (s,1H); 13C
(100 Hz, CDCl3, 25 °C, TMS): δ = 14.4, 61.8, 117.3, 126.8,
127.6, 129.1, 131.8, 134.5, 139.2, 161.0, 167.8 ppm.
(2-Bromophenyl)(4-hydroxy-[1,1'-biphenyl]-3-
yl)methanone (3g): 65.5 mg, 62%; white solid: 140–
°
°
141 C; 1H (400 Hz, CDCl3, 25 C, TMS): δ = 7.16 (d, J =
8.4 Hz, 1H), 7.30–7.33 (m, 1H), 7.39–7.48 (m, 8H), 7.69 (d,
J = 7.6 Hz, 1H), 7.75 (d, J = 8.8 Hz, 1H), 11.96 ppm (s,
1H); 13C (100 Hz, CDCl3, 25 C, TMS): δ = 119.0, 119.3,
°
119.4, 126.8, 127.4, 127.5, 128.8, 129.0, 131.6, 131.9,
132.7, 133.5, 136.3, 139.5, 139.8, 162.9, 201.5 ppm; IR: v
= 3443, 3056, 3025, 2922, 2853, 1791, 1731, 1628, 1585,
1468, 1434, 1335, 1236, 1206, 1148, 1041, 1022, 942, 895,
840, 790, 754, 695, 670, 637, 569, 525, 471 cm-1; HRMS
(EI): m/z calcd for C19H13NaBrO2: 374.9991 [M + Na] +;
found: 374.9996.
Methyl
4'-hydroxy-[1,1':3',1''-terphenyl]-5'-
carboxylate (3n):[49] 79.3 mg, 87%; yellow solid: 109–
110 °C; 1H (400 Hz, CDCl3, 25 C, TMS): δ = 4.01 (s, 3H),
°
7.34-7.39 (m, 2H), 7.41–7.49 (m, 4H), 7.59–7.66 (m, 4H),
7.79 (d, J = 2.0 Hz, 1H), 8.11 (d, J = 2.0 Hz, 1H), 11.32
ppm (s, 1H); 13C (100 Hz, CDCl3, 25 C, TMS): δ = 52.7,
°
8
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