PAPER
Symmetrical Triphenylene-Based Discotic Liquid-Crystalline Dimers
3805
4.28–4.20 (m, 24 H, NCH2, OCH2), 2.48 (quint, J = 6.5 Hz, 2 H,
CH2), 1.95 (m, 20 H, CH2), 1.57 (m, 20 H, CH2), 1.39 (m, 40 H,
CH2), 0.93 (m, 30 H, CH3).
tion (grants 200021_121846 and 200020_124696) and the Univer-
sity of Neuchâtel.
13C NMR (100 MHz, CDCl3): d = 149.3, 149.2, 148.9, 148.83,
148.79 (C3, C6, C7, C10, C11), 147.5 (C2), 144.7 (Ctrz), 124.3,
123.9 (CAr), 123.6 (CtrzH), 123.56, 123.38, 123.17, 123.15 (CAr),
109.4 (C1), 107.5, 107.4, 107.1, 106.7, 106.5 (C4, C5, C8, C9,
C12), 69.83, 69.77, 69.57, 69.36, 69.28 (OCH2), 63.8 (OCH2), 46.6
(NCH2), 31.6 [O(CH2)3CH2], 30.5 (CH2), 29.4, 29.3 (OCH2CH2),
25.8 [O(CH2)2CH2], 22.6 [O(CH2)4CH2], 14.0 (CH3).
References
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HRMS: m/z [M + H]+ calcd for C105H155N6O12: 1692.17030; found:
1692.17066.
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1,4-Bis[(4-{[3,6,7,10,11-pentakis(hexyloxy)triphenylen-2-
yloxy]methyl}-1H-1,2,3-triazol-1-yl)methyl}benzene (2)
Compound 2 (213 mg, 0.27 mmol) and 1,4-bis(azidomethyl)ben-
zene (23 mg, 0.12 mmol) were dissolved in CH2Cl2 (3 mL) at r.t. A
soln of sodium ascorbate (14.7 mg, 0.07 mmol) in H2O (1.5 mL)
was added followed by addition of a soln of CuSO4·5 H2O (6.2 mg,
0.02 mmol) in H2O (1.5 mL). The mixture was stirred at r.t. for 15
h under an argon atmosphere. CHCl3 (10 mL) was added and the
soln was washed with 1 M aq NH3 soln (2 × 10 mL) and brine
(2 × 10 mL), and dried (MgSO4). The solvent was evaporated off
and the crude product was purified by column chromatography (sil-
ica gel, CH2Cl2 and CH2Cl2–MeOH, 99.5:0.5) and preparative TLC
(silica gel, CH2Cl2–MeOH, 99.5:0.5) followed by recrystallization
(EtOAc–EtOH, 1:1) to afford 2 (24 mg, 11%) as a white solid.
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IR (KBr): 2955, 2930, 2858, 1618, 1518, 1467, 1438, 1389, 1262,
1174, 1048, 837 cm–1.
1H NMR (400 MHz, CDCl3): d = 8.04 (s, 2 H, H1), 7.84–7.80 (5 s,
10 H, H4, H5, H8, H9, H12), 7.52 (s, 2 H, Htrz), 7.03 (s, 4 H, HAr),
5.48 (s, 4 H, OCH2), 5.41 (s, 4 H, NCH2), 4.23 (m, 20 H, OCH2),
1.93 (m, 20 H, CH2), 1.58 (m, 20 H, CH2), 1.39 (m, 40 H, CH2), 0.92
(m, 30 H, CH3).
13C NMR (100 MHz, CDCl3): d = 149.5, 149.4, 149.0, 148.9 (C3,
C6, C7, C10, C11), 147.6 (C2), 145.3 (Ctrz), 135.3 (CPh), 128.6
(CPhH), 124.4, 124.1, 123.8, 123.6, 123.4, 123.3 (CAr), 123.1
(CtrzH), 109.6 (C1), 107.7, 107.6, 107.3, 106.9, 106.6 (C4, C5, C8,
C9, C12), 70.1, 70.0, 69.8, 69.6, 69.4 (OCH2), 64.1 (OCH2), 53.7
(NCH2), 31.8, 31.7 [O(CH2)3CH2], 29.6, 29.5, 29.4 (OCH2CH2),
26.0, 25.9 [O(CH2)2CH2], 22.8, 22.7 [O(CH2)4CH2], 14.2 (CH3).
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HRMS: m/z [M + H]+ calcd for C110H157N6O12: 1754.18595; found:
1754.18534.
Supporting Information for this article is available online at
Acknowledgment
We thank Dr. Armelle Vallat-Michel (SAF UniNE) for assistance
with mass spectrometry and Dr. Julien Furrer (SAF UniNE) for
NMR spectroscopic assistance and Sebastiano Guerra (Prof.
Deschenaux group UniNE) for DSC and POM analysis. This work
was financially supported by the Swiss National Science Founda-
(11) Pérez, D.; Guitián, E. Chem. Soc. Rev. 2004, 33, 274.
Synthesis 2011, No. 23, 3801–3806 © Thieme Stuttgart · New York