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New Journal of Chemistry
Page 4 of 10
DOI: 10.1039/C7NJ02695A
ARTICLE
Journal Name
NMR (400 MHz, CDCl3) δ (ppm): 7.75 (s, 4 H, ArH), 7.67 - 7.69 7.16 (d, J = 8.5 Hz, 4 H, ArH), 3.47 (t, J = 6.6 Hz, 4 H, CH2N3),
(m, 8 H, ArH), 7.61 (s, 12 H, ArH), 5.42 (s, 4 H, CH2COO), 5.27 (s, 2.71 (t, J = 7.2 Hz, 4 H, CH2COO), 2.01 - 2.08 (m, 4 H, CH2). 13C
4 H, CH2COO), 4.84 (s, 4 H, COOCH2), 4.79 (s, 4 H, COOCH2), NMR (CDCl3) δ (ppm): 171.38, 149.98, 138.14, 128.20, 121.85,
4.03 - 4.20 (m, 44 H, ArOCH2, N-CH2), 1.80 - 1.94 (m, 40 H, CH2), 50.54, 31.26, 24.20. HRMS (ESI-TOF): calculated for C20H20N6O4
1.66 - 1.68 (m, 4 H, CH2), 1.48 - 1.57 (m, 40 H, CH2), 1.33 - 1.40 [M+H]+, 409.1624; found:409.1821.
(m, 80 H, CH2), 1.09 - 1.11 (m, 4 H, CH2), 0.89 - 0.95 (m, 60 H, [1,1'-biphenyl]-4,4'-diyl bis(6-azidohexanoate) 10b
CH3). 13C NMR (CDCl3) δ (ppm): 169.05, 168.75, 149.11, 149.04, [1,1'-biphenyl]-4,4'-diyl bis(6-bromohexanoate) 9b (800 mg,
148.98, 148.93, 148.84, 148.68, 148.65, 148.61, 148.57, 146.64, 1.48 mmol), NaN3 (481 mg, 7.4 mmol) and DMF 2 mL. The
146.38, 141.89, 130.20, 124.99, 124.86, 123.81, 123.78, 123.22, product 10b (white powder) was obtained in 550 mg and yield
123.18, 123.11, 123.04, 123.01, 122.91, 122.81, 110.15, 109.92, 80% by the procedure is analogous to that described for 10a
107.06, 106.97, 106.82, 106.70, 106.65, 106.48, 106.39, 106.30, (Cr 36 ◦C SB 97 ◦C Iso). 1H NMR (400 MHz, CDCl3) δ (ppm): 7.56
106.22, 31.74, 31.66, 31.62, 29.64, 29.45, 29.24, 29.21, 25.90, (d, J = 8.4 Hz, 4 H, ArH), 7.15 (d, J = 8.4 Hz, 4 H, ArH), 3.32 (t, J =
25.79, 25.76, 22.70, 22.65, 14.11. MALDI-MS: calculated for 6.8 Hz, 4 H, CH2N3), 2.62 (t, J = 7.4 Hz, 4 H, CH2COO), 1.77 -
C214H312N6O32 [M+Na]+, 3503.2936; found: 3503.2938.
1.85 (m, 4 H, CH2), 1.65 - 1.72 (m, 4 H, CH2), 1.48 - 1.56 (m, 4 H,
CH2). 13C NMR (CDCl3) δ (ppm): 172.05, 150.07, 138.07, 128.16,
[1,1'-biphenyl]-4,4'-diyl bis(4-bromobutanoate) 9a
4,4′-Dihydroxybiphenyl 8 (1.5 g, 6 mmol), 4-bromobutyric acid 121.90, 51.20, 34.16, 28.58, 26.22, 24.43. HRMS (ESI-TOF):
(3.36 g, 20 mmol), DCC (1.66 g, 20 mmol) and DMAP (200mg) calculated for C24H28N6O4 [M+H]+, 465.2250; found: 465.2497.
were dissolved into 25 mL dry dichloromethane and then the Tetramer 11a
mixture was stirred at room temperature over 12 h. After The triphenylene dimer
4 (150 mg, 0.09 mmol), diazide 10a
removed the byproduct through filtering, the filtrate was (6.3 mg, 0.045 mmol) and xylene 2 mL. The product 11a (white
concentrated in vacuo, and the residue was purified by column solid) was obtained in 90 mg and yield 58% by the procedure is
chromatography (silica gel, eluting with DCM / petroleum, 2:1), analogous to that described for 7a. 1H NMR (400 MHz, CDCl3) δ
recrystallized from the mixed solvents of ethyl acetate and (ppm): 7.78 (s, 2H, ArH), 7.76 (s, 2 H, ArH), 7.72 (s, 6 H, ArH),
ethanol (V/V = 1:5) to give pure compound 9a as a white solid 7.70 (s, 2 H, ArH), 7.67 (s, 8 H, ArH), 7.63 (s, 2 H, ArH), 7.61 (s, 2
(1.55 g, yield 46%). 1H NMR (400 MHz, CDCl3) δ (ppm): 7.56 (d, H, ArH), 7.34 (d, J = 8.4 Hz, 4 H, ArH), 6.97 (d, J = 8.4 Hz, 4 H,
J = 8.4 Hz, 4 H, ArH), 7.16 (d, J = 8.4 Hz, 4 H, ArH), 3.56 (t, J = ArH), 5.46 (s, 4H, ArOCH2COO), 5.32 (s, 4 H, ArOCH2COO), 4.85
6.2 Hz, 4 H, CH2Br), 2.81 (t, J = 7.0 Hz, 4 H, CH2COO), 2.30 - 2.33 (s, 4 H, COOCH2), 4.80 (s, 4 H, COOCH2), 4.27 (t, J = 7.0 Hz, 4 H,
(m, 4 H, CH2). 13C NMR (CDCl3) δ (ppm): 171.23, 149.96, 138.15, N-CH2), 4.11 - 4.21 (m, 40 H, OCH2), 2.50 (t, J = 6.8 Hz, 4 H,
128.20, 121.86, 32.67, 32.53, 27.54. HRMS (ESI-TOF): CH2COOAr), 2.16 (t, J = 6.8 Hz, 4 H, CH2COOAr), 1.84 - 1.94 (m,
calculated for C20H20Br2O4 [M+H]+, 482.9801; found:482.9834.
40 H, CH2), 1.54 - 1.59 (m, 44 H, CH2), 1.34 - 1.39 (m, 80 H, CH2),
0.90 - 0.94 (m, 60 H, CH2). 13C NMR (CDCl3) δ (ppm): 170.77,
[1,1'-biphenyl]-4,4'-diyl bis(6-bromohexanoate) 9b
4,4′-Dihydroxybiphenyl
8 (3 g, 16 mmol), 6-bromohexanoic 169.11, 168.70, 149.76, 149.23, 149.16, 149.10, 149.05, 148.92,
acid (7.82 g, 40 mmol), DCC (3.32 g, 16 mmol) and DMAP 148.80, 148.75, 148.72, 148.67, 146.74, 146.47, 142.02, 137.88,
(400mg) and dry DCM 50 mL. The product 9b (white powder) 130.50, 127.91, 125.10, 124.93, 123.95, 123.84, 123.30, 123.22,
was obtained in 4.5 g and yield 51% by the procedure is 123.13, 123.04, 122.96, 122.89, 121.65, 110.30, 110.07, 107.23,
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analogous to that described for 9a (m. p. 44 ◦C). H NMR (400 107.17, 107.11, 107.05, 106.83, 106.58, 106.52, 106.28, 69.70,
MHz, CDCl3) δ (ppm): 7.55 (d, J = 8.8 Hz, 4H, ArH), 7.15 (d, J = 69.63, 69.60, 69.45, 69.42, 69.29, 69.20, 69.08, 67.43, 57.29,
8.8 Hz, 4 H, ArH), 3.45 (t, J = 6.6 Hz, 4 H, CH2Br), 2.61 (t, J = 7.4 53.39, 53.37, 47.43, 31.72, 31.72, 31.65, 31.60, 30.69, 29.44,
Hz, 4 H, CH2COO), 1.90-1.98 (m, 4 H, CH2), 1.77-1.84 (m, 4 H, 29.26, 29.20, 25.88, 25.79, 25.75, 24.68, 22.68, 22.63, 14.08.
CH2), 1.55 - 1.63 (m, 4 H, CH2). 13C NMR (CDCl3) δ (ppm): MALDI-MS: calculated for C228H320N6O36 [M+Na]+, 3743.3359;
172.05, 150.08, 138.06, 128.16, 121.92, 34.15, 33.63, 33.58, found: 3743.3355.
32.36, 27.61, 24.06. HRMS (ESI-TOF): calculated for Tetramer 11b
C24H28Br2O4 [M+H]+, 539.0427; found:539.0437.
The triphenylene dimer
4 (200 mg, 0.12 mmol), diazide 10b
[1,1'-biphenyl]-4,4'-diyl bis(4-azidobutanoate) 10a
(10.2 mg, 0.06 mmol) and xylene 2 mL. The product 11a (white
[1,1'-biphenyl]-4,4'-diyl bis(4-bromobutanoate) 9a (700 mg, solid) was obtained in 95 mg and yield 45% by the procedure is
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1.67 mmol), NaN3 (542 mg, 8.3 mmol) were added to 2 mL analogous to that described for 7a. H NMR (400 MHz, CDCl3)
DMF, and the mixture was stirred about 24 h at room δ (ppm): 7.79 (s, 2 H, ArH), 7.77 (s, 2 H, ArH), 7.72 (s, 8 H, ArH),
temperature. After full consumption of the starting material 9a 7.68 (s, 8 H, ArH), 7.64 (s, 2 H, ArH), 7.61 (s, 2 H, ArH), 7.44 (d, J
was detected by TLC, 100 mL H2O was added into the mixture, = 8.8 Hz, 4 H, ArH), 7.02 (d, J = 8.4 Hz, 4 H, ArH), 5.45 (s, 4 H,
and extracted by DCM (30 mL
×3), the organic extracts were ArOCH2COO), 5.28 (s, 4 H, ArOCH2COO), 4.86 (s, 4 H, COOCH2),
combined and washed with saturated brine, dried over 4.82 (s, 4 H, COOCH2), 4.10 - 4.21 (m, 40 H, OCH2), 4.05 (t, J =
anhydrous MgSO4, and concentrated in vacuum, and the 7.0 Hz, 4 H, N-CH2), 2.37 (t, J = 7.2 Hz, 4 H, CH2COOAr), 1.82 -
residue was purified by column chromatography (silica gel, 1.93 (m, 40 H, CH2), 1.73 - 1.76 (m, 4 H, CH2), 1.55 - 1.56 (m, 44
eluting with DCM / petroleum, 2:1), recrystallized from the H, CH2), 1.37 - 1.38 (m, 80 H, CH2), 1.20 - 1.25 (m, 4 H, CH2),
mixed solvents of ethyl acetate and ethanol (V/V = 1:5) to give 0.91 - 0.94 (m, 60 H, CH3). 13C NMR (CDCl3) δ (ppm): 171.69,
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pure compound 10a as a white solid (544 mg, yield 80%). H 169.12, 168.77, 149.23, 149.14, 149.08, 149.03, 148.93, 148.77,
NMR (400 MHz, CDCl3) δ (ppm): 7.56 (d, J = 8.5 Hz, 4 H, ArH), 148.69, 148.64, 146.70, 146.44, 141.87, 137.89, 130.15, 127.96,
4 | J. Name., 2012, 00, 1-3
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