Full Papers
2-((4-methoxyphenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylic
acid (8c): An aqueous solution of potassium hydroxide (258 mg,
4.60 mmol, 10 equiv./4 mL) was added to a solution of dimethyl 2-
((4-methoxy-phenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylate (5c)
(186 mg, 0.460 mmol, 1.00 equiv.) in THF (13 mL), following the
general procedure A. 2-((4-methoxyphenyl)diazenyl)-[1,1’-biphenyl]-
(164 mg, 0.328 mmol, 1.00 equiv.) in THF (10 mL), following the
general procedure A. 2-((3-iodophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-
dicarboxylic acid (8f) was obtained as a red solid in 99% yield
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(154 mg). m.p.: 341.3–344.6 C (decomposition). H NMR (300 MHz,
DMSO-d6, ppm) δ=13.25 (b-s, 2H, CO2H), 8.25 (s, 1H, CH), 8.20 (d,
1H, J=8.1 Hz, CH), 8.08À 8.02 (m, 3H, CH), 7.91 (d, 1H, J=7.7 Hz,
CH), 7.85À 7.79 (m, 2H, CH), 7.65À 7.63 (m, 2H, CH), 7.38 (t, 1H, J=
7.8 Hz, CH). 13C NMR (100 MHz, DMSO-d6, ppm) δ=167.1 (CO2H),
166.5 (CO2H), 152.9 (Cq), 148.3 (Cq), 143.5 (Cq), 141.4 (Cq), 140.0
(CH), 131.9 (CH), 131.5 (CH), 131.4 (CH), 131.3 (Cq), 130.9 (2 C, CH),
130.8 (CH), 130.3 (Cq), 128.7 (2 C, CH), 123.1 (CH), 116.6 (CH), 95.5
(Cq). IR (ATR, v˜)=2811, 2541, 1679, 1601, 1568, 1457, 1415, 1284,
1186, 1125, 1004, 992, 915, 866, 840, 781, 759, 738, 702, 675, 661,
606, 538, 476, 431 cmÀ 1. UV/Vis (MeOH), λmax =196, 272, 323 nm.
FAB (Matrix: 3-NBA), m/z (%): 473 (0) [M+H]+. HRMS
(C20H14127IN2O4): Calc.: 472.9993; Found: 473.0005.
4,4’-dicarboxylic acid (8c) was obtained as a brown-yellow solid in
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°
96% yield (166 mg). m.p.: 339.3–342.8 C (decomposition). H NMR
(400 MHz, DMSO-d6, ppm) δ=13.22 (b-s, 2H, CO2H), 8.25 (s, 1H, CH),
8.14 (d, 1H, J=8.1 Hz, CH), 8.03À 8.05 (m, 2H, CH), 7.81À 7.75 (m, 3H,
CH), 7.64À 7.62 (m, 2H, CH), 7.14À 7.12 (m, 2H, CH), 3.85 (s, 3H,
OCH3). 13C NMR (100 MHz, DMSO-d6, ppm) δ=167.1 (CO2H), 166.6
(CO2H), 162.4 (Cq), 148.7 (Cq), 146.5 (Cq), 142.8 (Cq), 141.9 (Cq),
131.3 (CH), 131.3 (Cq), 130.8 (3 C, CH), 130.1 (Cq), 128.8 (2 C, CH),
125.0 (2 C, CH), 116.6 (CH), 114.8 (2 C, CH), 55.7 (OCH3). IR (ATR, v˜)
=2834, 2542, 1681, 1600, 1580, 1501, 1418, 1292, 1255, 1182, 1138,
1027, 1004, 918, 870, 829, 758, 741, 698, 670, 602, 535, 500,
469 cmÀ 1. UV/Vis (MeOH), λmax =193, 248, 283, 356 nm. APCI (m/z):
377 (100) [M+H]+.
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2-((4-iodophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylic acid
(8g): An aqueous solution of potassium hydroxide (224 mg,
4.00 mmol, 10 equiv./4 mL) was added to a solution of dimethyl 2-
((4-iodophenyl)diazenyl)-[1,1’-biphenyl]- 4,4’-dicarboxylate (5g)
(200 mg, 0.400 mmol, 1.00 equiv.) in THF (11 mL), following the
general procedure A. 2-((4-iodophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-
2-((3,5-dimethylphenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylic
acid (8d): An aqueous solution of potassium hydroxide (90 mg,
1.62 mmol, 10 equiv./2 mL) was added to a solution of dimethyl 2-
((3,5-dimethylphenyl)diazenyl)-[1,1’-
biphenyl]-4,4’-dicarboxylate
dicarboxylic acid (8g) was obtained as a red solid in 99% yield
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°
(5d) (65 mg, 0.162 mmol, 1.00 equiv.) in THF (5 mL), following the
general procedure A. 2-((3,5-dimethylphenyl)diazenyl)-[1,1’-biphen-
yl]-4,4’-dicarboxylic acid (8d) was obtained as a brown-yellow solid
(187 mg). m.p.: 345.4–348.1 C (decomposition). H NMR (400 MHz,
DMSO-d6, ppm) δ=13.17 (b-s, 2H, CO2H), 8.26 (d, 1H, J=1.6 Hz,
CH), 8.20 (dd, 1H, J=8.0 Hz, J=1.7 Hz, CH), 8.06À 8.04 (m, 2H, CH),
7.98À 7.96 (m, 2H, CH), 7.82 (d, 1H, J=8.0 Hz, CH), 7.64À 7.62 (m, 2H,
CH), 7.55À 7.53 (m, 2H, CH). This spectrum contains around 20%
impurities due to isomerization under the conditions of the
measurement. 13C NMR (100 MHz, DMSO-d6, ppm) δ=167.1 (CO2H),
166.5 (CO2H), 151.4 (Cq), 148.6 (Cq), 143.4 (Cq), 141.5 (Cq), 138.6
(2 C, CH), 131.7 (CH), 131.5 (CH), 131.4 (Cq), 130.9 (2 C, CH), 130.2
(Cq), 128.8 (2 C, CH), 124.7 (2 C, CH), 116.6 (CH), 99.7 (Cq). This
spectrum contains around 20% impurities due to isomerization
under the conditions of the measurement. IR (ATR, v˜)=2527, 1679,
1602, 1577, 1474, 1418, 1286, 1126, 1052, 1003, 917, 871, 823, 758,
738, 684, 658, 602, 536, 486, 410 cmÀ 1. UV/Vis (MeOH), λmax =196,
273, 339, 653 nm. APCI (m/z): 473 (100) [M+H]+, 346 (13), 243 (13).
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°
in 86% yield (52 mg). m.p.: 337.4–339.2 C (decomposition). H NMR
(400 MHz, DMSO-d6, ppm) δ=13.20 (b-s, 2H, CO2H), 8.21 (d, 1H, J=
1.8 Hz, CH), 8.17 (dd, 1H, J=8.0 Hz, J=1.8 Hz, CH), 8.05À 8.03 (m,
2H, CH), 7.81 (d, 1H, J=8.0 Hz, CH), 7.64À 7.62 (m, 2H, CH), 7.38 (s,
2H, CH), 7.20 (s, 1H, CH), 2.33 (s, 6H, CH3). 13C NMR (100 MHz,
DMSO-d6, ppm) δ=167.1 (CO2H), 166.6 (CO2H), 152.4 (Cq), 148.8
(Cq), 143.0 (Cq), 141.6 (Cq), 138.8 (Cq, 2 C), 133.3 (CH), 131.4 (CH),
131.3 (Cq), 131.3 (CH), 130.9 (2 C, CH), 130.2 (Cq), 128.8 (2 C, CH),
120.8 (2 C, CH), 116.7 (CH), 20.8 (2 C, CH3). IR (ATR, v˜)=2860, 2658,
2529, 1678, 1602, 1552, 1491, 1418, 1282, 1236, 1184, 1120, 1005,
909, 852, 839, 801, 781, 759, 739, 700, 681, 661, 611, 537, 476,
430 cmÀ 1. UV/Vis (MeOH), λmax =195, 244, 277, 327, 440 nm. FAB
(Matrix: 3-NBA), m/z (%): 375 (100) [M+H]+. HRMS (C22H19N2O4):
Calcd. 375.1339; Found. 375.1338.
2-((2-bromophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylic acid
(8h): An aqueous solution of potassium hydroxide (61 mg,
1.08 mmol, 10 equiv./1 mL) was added to a solution of dimethyl 2-
((2-bromophenyl)diazenyl)-[1,1’-biphenyl]- 4,4’-dicarboxylate (5h)
(49 mg, 108 %mol, 1.00 equiv.) in THF (3 mL), following the general
procedure A. 2-((2-bromophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicar-
boxylic acid (8h) was obtained as a red solid in 87% yield (40 mg).
1H NMR (400 MHz, DMSO-d6, ppm) δ=13.25 (b-s, 2H, CO2H), 8.30 (s,
1H, CH), 8.23 (d, 1H, J=8.1 Hz, CH), 8.07À 8.05 (m, 2H, CH),
7.93À 7.89 (m, 1H, CH), 7.85 (d, 1H, J=8.1 Hz, CH), 7.68À 7.66 (m, 2H,
CH), 7.51À 7.48 (m, 2H, CH), 7.34À 7.31 (m, 1H, CH). 13C NMR
(100 MHz, DMSO-d6, ppm) δ=167.1 (CO2H), 166.5 (CO2H), 149.0
(Cq), 148.7 (Cq), 143.8 (Cq), 141.5 (Cq), 133.9 (CH), 133.3 (CH), 132.0
(CH), 131.6 (CH), 131.4 (Cq), 131.0 (2 C, CH), 130.3 (Cq), 128.9 (2 C,
CH), 128.8 (CH), 125.2 (Cq), 117.9 (CH), 117.0 (CH). IR (ATR, v˜)=
1686, 1603, 1419, 1288, 1127, 1043, 1005, 924, 841, 761, 739, 691,
549 cmÀ 1. APCI (m/z): 425/427 (1/1) [M+H]+, 365 (100).
2-((2-iodophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylic acid
(8e): An aqueous solution of potassium hydroxide (55 mg,
0.98 mmol, 10 equiv./1 mL) was added to a solution of dimethyl 2-
((2-iodophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylate
(5e)
(49 mg, 98 %mol, 1.00 equiv.) in THF (3 mL), following the general
procedure A. 2-((2-iodophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicar-
boxylic acid (8e) was obtained as a red solid in 65% yield (30 mg).
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m.p. 349.9–360.5 C (decomposition). H NMR (400 MHz, DMSO-d6,
ppm) δ=13.24 (b-s, 2H, CO2H), 8.36 (s, 1H, CH), 8.23 (d, 1H, J=
8.1 Hz, CH), 8.12 (d, 1H, J=7.8 Hz, CH), 8.07À 8.05 (m, 2H, CH), 7.84
(d, 1H, J=8.1 Hz, CH), 7.68À 7.66 (m, 2H, CH), 7.54À 7.47 (m, 1H, CH),
7.30 (t, 1H, J=7.6 Hz, CH), 7.26 (d, J=7.8 Hz, 1H, CH). 13C NMR
(100 MHz, DMSO-d6, ppm) δ=167.1 (CO2H), 166.5 (CO2H), 151.0
(Cq), 148.4 (Cq), 143.8 (Cq), 141.5 (Cq), 139.9 (Cq), 133.3 (Cq), 132.0
(CH), 131.6 (CH), 131.5 (Cq), 131.0 (2 C, CH), 130.3 (Cq), 129.4 (CH),
128.8 (2 C, CH), 117.4 (CH), 117.2 (CH), 103.1 (Cq). IR (ATR, v˜)=
2811, 2529, 1679, 1601, 1570, 1454, 1415, 1282, 1125, 1018, 1003,
2-((3-bromophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylic acid
(8i): An aqueous solution of potassium hydroxide (196 mg,
3.49 mmol, 10 equiv./3 mL) was added to a solution of dimethyl 2-
((3-bromophenyl)diazenyl)-[1,1’-biphenyl]- 4,4’-dicarboxylate (5i)
(158 mg, 0.349 mmol, 1.00 equiv.) in THF (10 mL), following the
general procedure A. 2-((3-bromophenyl)diazenyl)-[1,1’-biphenyl]-
915, 865, 840, 758, 737, 698, 682, 658, 609, 537, 477, 440, 415 cmÀ 1
.
UV/Vis (MeOH), λmax =195, 256, 323, 469 nm. FAB (Matrix: 3-NBA),
m/z (%): 473 (90) [M+H]+, 462 (100). HRMS (C20H14O4N2127I) Calc.:
472.9993; Found: 472.9995.
2-((3-iodophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylic acid
(8f): An aqueous solution of potassium hydroxide (184 mg,
3.28 mmol, 10 equiv./3 mL) was added to a solution of dimethyl 2-
4,4’-dicarboxylic acid (8i) was obtained as a red solid in 83% yield
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(123 mg). m.p.: 348.0–349.3 C (decomposition). H NMR (400 MHz,
DMSO-d6, ppm) δ=13.23 (b-s, 2H, CO2H), 8.26 (s, 1H, CH), 8.21 (d,
1H, J=8.1 Hz, CH), 8.06À 8.04 (d, 2H, J=8.1 Hz, CH), 7.86À 7.79 (m,
((3-iodophenyl)diazenyl)-[1,1’-biphenyl]-4,4’-dicarboxylate
(5f)
ChemistryOpen 2019, 8, 743–759
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