Bis(oligophenylylamino)terephthalates
Dioctyl 2,5-Bis(biphenyl-4-ylamino)terephthalate (3h): In analogy to
the procedure reported for compound 3g, dioctyl ester 3d (500 mg,
65.36 (OCH2), 114.19 (2 CH), 118.62 (CH), 119.19 (C), 119.61 (2
CH), 127.50 (2 CH), 127.57 (2 CH), 133.45 (C), 134.42 (C), 137.63
606 µmol), PhB(OH)2 (7a) (163 mg, 1.33 mmol), Na2CO3 (257 mg, (C), 140.86 (C), 158.77 (C), 167.54 (C=O) ppm. IR (ATR): ν =
˜
2.42 mmol) and [Pd(PPh3)4] (35 mg, 30 µmol) were allowed to react
in degassed solvent (10 mL toluene, 10 mL EtOH, 5 mL H2O). The
precipitated product was isolated by filtration, washed with EtOAc
(50 mL) and H2O (30 mL) and dried in vacuo. Compound 3h
(215 mg, 297 µmol, 49%) was obtained as an orange solid, m.p.
3311 (s), 3010 (m), 2957 (s), 2918 (s), 2847 (s), 1683 (vs), 1607 (s),
1586 (s), 1575 (m), 1543 (vs), 1496 (s), 1456 (s), 1434 (s), 1397 (m),
1330 (vs), 1276 (s), 1212 (vs), 1175 (s), 1107 (s), 822 (s), 783 (s),
689 (s) cm–1. MS (EI, 70 eV): m/z (%) = 784 (100) [M]+, 392 (3),
392 (4), 198 (4). HRMS: calcd. for C50H60N2O6 [M]+ 784.4451;
found 784.4451.
1
206 °C. H NMR (CDCl3, 500 MHz): δ = 0.84 (t, J = 6.6 Hz, 6 H,
CH3), 1.22–1.27 (m, 12 H, CH2), 1.29–1.33 (m, 4 H, CH2), 1.41
(quint, J = 7.2 Hz, 4 H, CH2), 1.73 (quint, J = 7.0 Hz, 4 H, CH2),
4.29 (t, J = 6.5 Hz, 4 H, OCH2), 7.23–7.29 (m, 4 H, 3Ј,5Ј-H), 7.29–
7.35 (m, 2 H, 4ЈЈ-H), 7.39–7.46 (m, 4 H, 3ЈЈ,5ЈЈ-H), 7.52–7.63 (m,
8 H, 2Ј,6Ј-H, 2ЈЈ,6ЈЈ-H), 8.13 (s, 2 H, 3,6-H), 8.92 (s, 2 H, NH) ppm.
13C{1H} NMR (CDCl3, 125 MHz): δ = 14.06 (CH3), 22.59 (CH2),
26.09 (CH2), 28.56 (CH2), 29.24 (2 CH2), 31.78 (CH2), 65.41
(OCH2), 118.78 (CH), 119.33 (C), 119.41 (2 CH), 126.55 (2 CH),
126.72 (CH), 127.95 (2 CH), 128.74 (2 CH), 134.62 (C), 137.53 (C),
Diethyl 2,5-Bis[4Ј-(trifluoromethyl)biphenyl-4-ylamino]terephthalate
(3k): In analogy to the procedure reported for compound 3g, di-
ethyl ester 3c (150 mg, 229 µmol), 4-F3CC6H4B(OH)2 (7c) (96 mg,
504 µmol), Na2CO3 (97 mg, 916 µmol) and [Pd(PPh3)4] (13 mg,
11 µmol) were allowed to react in degassed solvent (6 mL toluene,
3 mL EtOH, 4.5 mL H2O). The precipitated product was isolated
by filtration, washed with CH2Cl2 (20 mL) and H2O (10 mL) and
dried in vacuo. Compound 3k (87 mg, 126 µmol, 55%) was ob-
tained as a brownish-yellow solid, m.p. 286–287 °C. 1H NMR
(CDCl3, 500 MHz): δ = 1.38 (t, J = 7.1 Hz, 6 H, CH3), 4.30 (q, J
= 7.1 Hz, 4 H, OCH2), 7.28–7.38 (m, 4 H, 3Ј,5Ј-H), 7.50–7.62 (m,
4 H, 3ЈЈ,5ЈЈ-H), 7.62–7.75 (m, 8 H, 2Ј,6Ј-H, 2ЈЈ,6ЈЈ-H), 8.14 (s, 2 H,
3,6-H), 8.98 (s, 2 H, NH) ppm. 13C{1H} NMR (CDCl3, 125 MHz):
δ = 14.25 (CH3), 61.47 (OCH2), 119.06 (2 CH), 119.27 (CH), 119.77
(C), 125.71 (q, 3J = 3.2 Hz, 2 CH, C-3ЈЈ, C-5ЈЈ), 126.08 (q, 1J =
140.75 (C), 141.42 (C), 167.51 (C=O) ppm. IR (ATR): ν = 3309
˜
(s), 3063 (m), 3031 (s), 2954 (s), 2921 (s), 2848 (s), 1685 (vs), 1607
(s), 1585 (s), 1572 (s), 1538 (vs), 1486 (s), 1463 (s), 1426 (s), 1398
(s), 1250 (s), 1209 (vs), 1105 (s), 834 (s), 785 (s), 758 (s), 690
(s) cm–1. MS (EI, 70 eV): m/z (%) = 724 (100) [M]+, 464 (10), 437
(4), 362 (3), 168 (3). C48H56N2O4 (724.98): calcd. C 79.52, H 7.79,
N 3.86; found C 79.78, H 7.92, N 3.58.
2
247.7 Hz, 1 C, CF3), 126.67 (2 CH), 128.20 (2 CH), 130.11 (q, J
Diethyl 2,5-Bis(4Ј-methoxybiphenyl-4-ylamino)terephthalate (3i): In
analogy to the procedure reported for compound 3g, diethyl ester
3c (150 mg, 229 µmol), 4-MeOC6H4B(OH)2 (7b) (77 mg,
504 µmol), Na2CO3 (97 mg, 916 µmol) and [Pd(PPh3)4] (13 mg,
11 µmol) were allowed to react in degassed solvent (3 mL toluene,
3 mL EtOH, 4.5 mL H2O). The precipitated product was isolated
by filtration, washed with EtOAc (20 mL) and H2O (10 mL) and
dried in vacuo. Compound 3i (59 mg, 96 µmol, 42%) was obtained
= 30.7 Hz, 1 C, C-4ЈЈ), 134.03 (C), 135.65 (C), 142.39 (C), 144.47
(C), 167.35 (C=O) ppm. IR (ATR): ν = 3343 (s), 3042 (m), 2983
˜
(s), 1685 (vs), 1602 (s), 1585 (s), 1567 (s), 1527 (vs), 1501 (s), 1475
(s), 1431 (s), 1399 (m), 1324 (vs), 1278 (s), 1256 (s), 1210 (s), 1169
(s), 1113 (s), 1071 (vs), 1012 (s), 827 (s), 784 (s), 726 (s) cm–1. MS
(EI, 70 eV): m/z (%) = 692 (100) [M]+, 673 (4), 600 (25), 572 (4),
346 (4). HRMS: calcd. for C38H30F6N2O4 [M]+ 692.2110; found
692.2111.
1
as a brown solid, m.p. 265–269 °C. H NMR (CDCl3, 500 MHz):
Dioctyl 2,5-Bis[4Ј-(trifluoromethyl)biphenyl-4-ylamino]terephthalate
(3l): In analogy to the procedure reported for compound 3g, dioctyl
ester 3d (300 mg, 364 µmol), 4-F3CC6H4B(OH)2 (7c) (152 mg,
801 µmol), Na2CO3 (154 mg, 1.46 mmol) and [Pd(PPh3)4] (21 mg,
18 µmol) were allowed to react in degassed solvent (4 mL toluene,
4 mL EtOH, 5 mL H2O). The precipitated product was isolated by
filtration, washed with CH2Cl2 (30 mL) and H2O (30 mL) and
dried in vacuo. Compound 3l (177 mg, 206 µmol, 57%) was ob-
tained as a reddish-brown solid, m.p. 222–223 °C. 1H NMR
(CDCl3, 500 MHz): δ = 0.86 (t, J = 6.8 Hz, 6 H, CH3), 1.18–1.28
(m, 12 H, CH2), 1.28–1.38 (m, 4 H, CH2), 1.45 (quint, J = 7.4 Hz,
4 H, CH2), 1.77 (quint, J = 7.0 Hz, 4 H, CH2), 4.30 (t, J = 6.4 Hz,
4 H, OCH2), 7.28–7.32 (m, 4 H, 3Ј,5Ј-H), 7.57–7.64 (m, 4 H, 3ЈЈ,5ЈЈ-
H), 7.65–7.77 (m, 8 H, 2Ј,6Ј-H, 2ЈЈ,6ЈЈ-H), 8.19 (s, 2 H, 3,6-H), 9.03
(s, 2 H, NH) ppm. 13C{1H} NMR (CDCl3, 125 MHz): δ = 14.46
(CH3), 23.03 (CH2), 26.57 (CH2), 29.02 (CH2), 29.72 (2 CH2), 32.23
(CH2), 65.96 (OCH2), 119.46 (CH), 119.63 (2 CH), 120.02 (C),
δ = 1.36 (t, J = 7.1 Hz, 6 H, CH3), 3.86 (s, 6 H, CH3), 4.35 (q, J
= 7.1 Hz, 4 H, OCH2), 6.92–7.01 (m, 4 H, 3Ј,5Ј-H), 7.20–7.28 (m,
4 H, 3ЈЈ,5ЈЈ-H), 7.48–7.57 (m, 8 H, 2Ј,6Ј-H, 2ЈЈ,6ЈЈ-H), 8.09 (s, 2 H,
3,6-H), 8.87 (s, 2 H, NH) ppm. 13C{1H} NMR (CDCl3, 125 MHz):
δ = 14.24 (CH3), 55.37 (CH3), 61.31 (OCH2), 114.12 (2 CH), 118.86
(CH), 119.40 (C), 119.51 (2 CH), 127.55 (2 CH), 127.60 (2 CH),
133.44 (C), 134.36 (C), 137.61 (C), 140.98 (C), 158.77 (C), 167.49
(C=O) ppm. IR (ATR): ν = 3311 (s), 3030 (m), 2985 (s), 2941 (s),
˜
2836 (s), 1682 (vs), 1604 (s), 1584 (m), 1572 (m), 1538 (s), 1495
(vs), 1431 (s), 1367 (s), 1320 (s), 1275 (s), 1240 (s), 1205 (vs), 1174
(m), 1093 (s), 819 (s), 784 (s), 689 (s) cm–1. MS (EI, 70 eV): m/z
(%) = 616 (100) [M]+, 524 (6), 262 (11). HRMS: calcd. for
C38H36N2O6 [M]+ 616.2573; found 616.2572.
Dioctyl 2,5-Bis(4Ј-methoxybiphenyl-4-ylamino)terephthalate (3j): In
analogy to the procedure reported for compound 3g, dioctyl ester
3d (300 mg, 364 µmol), 4-MeOC6H4B(OH)2 (7b) (122 mg,
801 µmol), Na2CO3 (154 mg, 1.46 mmol) and [Pd(PPh3)4] (21 mg,
18 µmol) were allowed to react in degassed solvent (4 mL toluene,
4 mL EtOH, 5 mL H2O). The precipitated product was isolated by
filtration, washed with CH2Cl2 (30 mL) and H2O (30 mL) and
dried in vacuo. Compound 3j (120 mg, 153 µmol, 42%) was ob-
tained as a red solid, m.p. 208–209 °C. 1H NMR (CDCl3,
500 MHz): δ = 0.77 (t, J = 6.9 Hz, 6 H, CH3), 1.00–1.27 (m, 16 H,
CH2), 1.28–1.38 (m, 4 H, CH2), 1.65 (quint, J = 6.9 Hz, 4 H, CH2),
3.78 (s, 6 H, OCH3), 4.21 (t, J = 6.5 Hz, 4 H, OCH2), 6.80–7.00
(m, 4 H, 3Ј,5Ј-H), 7.08–7.26 (m, 4 H, 3ЈЈ,5ЈЈ-H), 7.30–7.62 (m, 8
H, 2Ј,6Ј-H, 2ЈЈ,6ЈЈ-H), 8.04 (s, 2 H, 3,6-H), 8.82 (s, 2 H, NH) ppm.
1
3
124.80 (q, J = 271.4 Hz, 1 C, CF3), 126.14 (q, J = 3.8 Hz, 2 CH,
C-3ЈЈ, C-5ЈЈ), 127.07 (2 CH), 128.59 (2 CH), 129.15 (q, 2J =
32.3 Hz, 1 C, C-4ЈЈ), 133.26 (C), 137.76 (C), 142.73 (C), 144.59 (C),
167.83 (C=O) ppm. IR (ATR): ν = 3313 (s), 3009 (m), 2955 (s),
˜
2917 (s), 2848 (s), 1683 (vs), 1607 (s), 1588 (s), 1574 (s), 1541 (vs),
1503 (s), 1460 (s), 1435 (s), 1397 (m), 1325 (vs), 1247 (s), 1218 (m),
1165 (s), 1072 (vs), 1014 (s), 824 (s), 787 (s), 723 (s) cm–1. MS (EI,
70 eV): m/z (%) = 860 (100) [M]+, 731 (2), 600 (9), 366 (3). HRMS:
calcd. for C50H54F6N2O4 [M]+ 860.3988; found 860.3987.
Diethyl 2,5-Bis(1,1Ј:4Ј,1ЈЈ-terphenyl-4-ylamino)terephthalate (3m):
13C{1H} NMR (CDCl3, 125 MHz): δ = 14.08 (CH3), 22.60 (CH2), In analogy to the procedure reported for compound 3g, diethyl
26.09 (CH2), 28.56 (CH2), 29.26 (2 CH2), 31.80 (CH2), 55.35 (CH3), ester 3c (300 mg, 457 µmol), 4-PhC6H4B(OH)2 (7d) (200 mg,
Eur. J. Org. Chem. 2008, 3488–3495
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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