Beilstein J. Org. Chem. 2013, 9, 2852–2861.
(626 mg, 0.76 mmol, 76%). 1H NMR (CDCl3, TMS, 400 M) δ lized from ethanol affording a white solid (178 mg, 0.21 mmol,
7.84 (s, 6H, ArH), 4.23 (t, J = 6.4 Hz, 12H, CH2), 2.21–2.17 71%). 1H NMR (CDCl3, TMS, 600 MHz) δ 8.02–8.00 (m, 3H,
(m, 2H, CH2) 1.99–1.92 (m, 13H, CH2, C≡CH), 1.60–1.50 (m, ArH), 7.81–7.71 (m, 15H, ArH), 7.06 (d, J = 3.6 Hz, 1H, ArH),
14H, CH2), 1.49–1.36 (m, 18H, CH2), 0.99–0.96 (m, 15H, 6.97 (s, 1H, ArH), 6.95 (d, J = 3.9 Hz, 1H, ArH), 6.83 (the
CH3); 13C NMR (CDCl3, 100 MHz) δ 148.9, 123.6, 107.2, 1,3,5-trisubstituted benzene core), 4.23–4.18 (m, 30H, CH2),
84.7, 69.6, 68.1, 29.5, 29.1, 28.8, 28.5, 28.4, 26.2, 22.6, 18.4, 2.66 (t, J = 7.5 Hz, 6H, CH2), 2.61–2.55 (m, 6H, CH2),
14.2; anal. calcd for C54H80O6: C, 78.60; H, 9.77; found: C, 1.97–1.81 (m, 36H, CH2), 1.66–1.34 (m, 90H, CH2), 0.99–0.95
78.36; H, 9.68.
(m, 45H, CH3); 13C NMR (CDCl3, 100 MHz) δ 172.1, 149.5,
149.3, 149.0, 148.7, 148.6, 140.3, 140.2, 139.6, 137.6, 129.2,
Monomer 3b, C18H6(OC5H11)5(OC3H6-C≡CH): Monomer 129.0, 127.8, 125.8, 124.5, 123.3, 123.0, 122.9, 116.6, 107.7,
3b was synthesized in a similar way to literature [57]. A mix- 107.0, 106.6, 106.3, 105.8, 69.7, 69.3, 69.1, 68.7, 35.7, 34.2,
ture of 5-chloro-1-pentyne (230 mg, 2.25 mmol), K2CO3 32.9, 32.4, 31.7, 31.5, 30.0, 29.9, 29.6, 29.5, 29.4, 29.2, 29.1,
(621 mg, 4.50 mmol), and 2-hydroxy-3,6,7,10,11- 28.4, 28.3, 25.2, 22.6, 14.2; anal. calcd for C162H234O21: C,
pentakis(pentyloxy)triphenylene (1, 1011 mg, 1.5 mmol) in 77.29; H, 9.37; found: C, 77.61; H, 9.39.
DMF (20 mL) was stirred at 80 °C for 24 h under N2. The crude
product was purified through column chromatography and a Trimer 5a: Trimer 5a was synthesized by the same method as
white solid was obtained (959 mg, 1.3 mmol, 86%). 1H NMR 4, which afforded a colorless oily product (186 mg, 0.23 mmol,
(CDCl3, TMS, 400 MHz) δ 7.87–7.84 (m, 6H, ArH), 4.34 (t, J 56%). 1H NMR (CDCl3, TMS, 600 MHz) δ 7.82 (s, 18H, ArH),
= 6.0 Hz, 2H, CH2), 4.23 (t, J = 6.4 Hz, 10H, CH2), 2.54 (td, J 7.04 (d, J = 3.9 Hz, 1H, ArH), 6.95 (s, 1H, ArH), 6.93 (d, J =
= 7.2 Hz, J = 2.8 Hz, 2H, CH2), 2.18–2.14 (m, 2H, CH2), 2.00 3.9 Hz, 1H, ArH), 6.81 (the 1,3,5-trisubstituted benzene core),
(t, J = 2.8 Hz, 1H, C≡CH), 1.99–1.92 (m, 10H, CH2), 1.60–1.50 4.23–4.21 (m, 36H, CH2), 2.58–2.52 (m, 6H, CH2), 1.97–1.91
(m, 10H, CH2), 1.49–1.41 (m, 10H, CH2), 0.98 (t, J = 7.2 Hz, (m, 36H, CH2), 1.58–1.35 (m, 96H, CH2), 0.98–0.95 (m, 45H,
15H, CH3); 13C NMR (CDCl3, 100 MHz), δ 149.0, 148.9, CH3); 13C NMR (CDCl3, 100 MHz) δ 149.1, 149.0, 148.9,
148.6, 123.8, 123.6, 123.5, 107.6, 107.2, 107.1, 83.7, 69.6, 68.9, 148.8, 148,7, 140.3, 140.1, 137.6, 129.2, 128.9, 125.7, 123.7,
68.0, 29.1, 28.4, 22.6, 15.3, 14.1; anal. calcd for C48H68O6: C, 123.6, 123.5, 123.4, 107.3, 107.2, 107.1, 107.0, 69.6, 35.7, 32.8,
77.80; H, 9.25; found: C, 77.70; H, 9.33.
32.4, 31.7, 31.5, 31.4, 30.0, 29.9, 29.7, 29.6, 29.5, 29.1, 28.4,
26.3, 22.6, 14.1; anal. calcd for C162H240O18: C, 78.60; H, 9.77;
Monomer 3c, C18H6(OC5H11)5(OCH2-C≡CH): A mixture of found: C, 78.55; H, 9.79.
propargyl bromide (268 mg, 2.25 mmol), K2CO3 (621 mg,
4.5 mmol), and 2-hydroxy-3,6,7,10,11-pentakis(pentyl- Trimer 5b: 5b was synthesized by the same method as 4,
oxy)triphenylene (1, 1011 mg, 1.5 mmol) in DMF (20 mL) was which afforded a white solid (195 mg, 0.26 mmol, 66%). 1H
stirred at 80 °C for 24 h under N2. The crude product was puri- NMR (CDCl3, TMS, 600 MHz) δ 7.82–7.73 (m, 18H, ArH),
fied with column chromatography and a white solid was 7.22 (d, J = 3.9 Hz, 1H, ArH), 7.18 (s, 1H, ArH), 7.09 (dd, J =
collected (1013 mg, 1.42 mmol, 95%). 1H NMR (CDCl3, TMS, 3.9 Hz, J = 0.9 Hz, 1H, ArH), 7.03 (the 1,3,5-trisubstituted
400 MHz) δ 8.08 (s, 1 H, ArH), 7.85 (s, 1H, ArH), 7.83 (s, 4H, benzene core), 4.28–4.13 (m, 36H, CH2), 3.0 (t, J = 7.9 Hz, 4H,
ArH), 4.97 (d, J = 1.2 Hz, 2H, CH2), 4.27–4.22 (m, 10H, CH2), CH2), 2.88 (t, J = 8.0 Hz, 2H, CH2), 2.28–2.18 (m, 6H, CH2),
2.58 (t, J = 2.4 Hz, 1H, C≡CH), 1.99–1.92 (m, 10H, CH2), 1.97–1.85 (m, 30H, CH2), 1.59–1.35 (m, 60H, CH2), 0.99–0.87
1.60–1.53 (m, 10H, CH2), 1.50–1.43 (m, 10H, CH2), 0.98 (t, J (m, 45H, CH3); 13C NMR (CDCl3, 100 MHz) δ 148.9, 148.8,
= 7.6Hz, 15H, CH3); 13C NMR (CDCl3, 100 MHz) δ 149.2, 148.7, 148.6, 139.8, 139.7, 137.2, 129.8, 129.6, 126.4, 123.6,
149.0, 148.8, 146.7, 124.7, 123.9, 123.5, 123.4, 123.3, 123.2, 123.5, 123.4, 107.2, 107.1, 106.9, 106.8, 69.6, 69.5, 69.4, 69.3,
109.8, 107.4, 107.2, 107.0, 106.7, 106.5, 78.9, 75.9, 69.7, 69.5, 68.7, 68.5, 32.0, 31.9, 31.3, 31.2, 31.1, 29.7, 29.2, 29.0, 28.6,
69.3, 57.8, 29.1, 29.0, 28.4, 28.3, 22.6, 14.1; anal. calcd for 28.4, 22.6, 14.1; anal. calcd for C144H204O18: C, 77.80; H, 9.25;
C46H64O6: C, 77.49; H, 9.05; found: C, 77.41; H, 9.00.
found: C, 77.83; H, 9.26.
Trimer 4: A mixture of 2 (252 mg, 0.3 mmol) and Co2(CO)8 Trimer 5c: Trimer 5c was synthesized by the same method as
(10 mg, 0.03 mmol) in dioxane (20 mL) was stirred under 4, which afforded a white solid (117 mg, 0.16 mmol, 36%). 1H
reflux for 24 h under an argon atmosphere, then cooled to room NMR (CDCl3, TMS, 600 MHz) δ 7.95–7.60 (m, 21H, ArH),
temperature. The organic phase was extracted with CH2Cl2, 5.65 (s, 4H, CH2), 5.37 (s, 2H, CH2), 4.24–4.12 (m, 22H, CH2),
dried over MgSO4 and the solvent was removed. The crude 4.07–4.03 (m, 4H, CH2), 3.97–3.94 (m, 4H, CH2), 1.98–1.86
product was purified by column chromatography on silica gel (m, 22H, CH2), 1.80–1.73 (m, 4H, CH2), 1.70–1.65 (m, 4H,
eluted with CH2Cl2/hexane (3:1 in volume), and then re-crystal- CH2), 1.59–1.37 (m, 44H, CH2), 1.36–1.30 (m, 8H, CH2),
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