10.1002/ejoc.201900464
European Journal of Organic Chemistry
FULL PAPER
reduced pressure. The residue was purified by column chromatography
or recrystallization.
(d, J = 7.3 Hz, 2H, Ar-H,), 7.94 (d, J = 8.9 Hz, 2H), 7.87 (d, J = 7.8 Hz,
2H), 7.80 (d, J = 8.3 Hz, 2H), 7.67 (s, 2H), 7.53 (t, J = 7.6 Hz, 2H), 7.47 (t,
J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ = 142.4 (C), 141.3 (C),
134.1 (CH), 133.3 (C), 129.1 (C), 128.5 (CH), 127.1 (CH), 127.0 (CH),
126.2 (CH), 125.4 (C), 123.8 (CH), 120.0 (CH), 118.4 (C), 110.3 (C),
104.0 (CH); IR (KBr) νmax: 2360 cm-1 (C≡N); LRMS (EI) m/z 368 (M+,
100%), 266 (10%); HRMS: m/z [M]+ calcd for C27H16N2: 368.1313.
Found: 368.1315.
4-(6H-dibenzo[b,h]carbazo-6-yl)-N,N-dimethylaniline (5c): Yield 113
mg (59%); yellow needle; mp 277-279 °C (from n-hexane/CH2Cl2); Rf =
0.2 (n-hexane/CH2Cl2 = 2:3). 1H NMR (400 MHz, CDCl3) δ = 8.70 (s, 2H),
8.08 (d, J = 7.8 Hz, 2H), 7.85 (d, J = 7.8 Hz, 2H), 7.56 (s, 2H), 7.53 (d, J
= 8.8 Hz, 2H), 7.48 (td, J = 8.3, 6.3 Hz, 2H), 7.42 (t, J = 7.3 Hz, 2H), 7.00
(s, 2H), 3.12 (s, 6H, NMe); 13C NMR (100 MHz, CDCl3) δ = 143.6 (C),
133.6 (C), 128.5 (CH), 128.38 (C), 128.37 (CH), 128.36 (C), 127.0 (CH),
125.6 (CH), 125.2 (C), 122.8 (CH), 119.6 (CH), 113.3 (CH), 103.7 (CH),
40.7 (CH3); LRMS (EI) m/z 386 (M+, 100%), 370 (20%); HRMS: m/z [M]+
calcd for C28H22N2: 386.1783. Found: 386.1791.
CCDC 1868302 (for 4) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre.
6-(4-Methoxyphenyl)-6H-dibenzo[b,h]carbazole (5d): Yield 103 mg
(55%); yellow needle; mp 224.5-226.5 °C (from n-hexane/CH2Cl2); Rf =
0.3 (n-hexane/CH2Cl2 = 3:2); 1H NMR (400 MHz, CDCl3) δ = 8.69 (s, 2H),
8.59 (d, J = 7.8 Hz, 2H, Ar-H,), 7.86 (d, J = 7.8 Hz, 2H), 7.58 (dt, J = 9.3,
2.4 Hz, 2H), 7.56 (s, 2H), 7.50 (td, J = 6.8, 1.5 Hz, 2H), 7.44 (td, J = 6.8,
1.5 Hz, 2H), 7.20 (dt, J = 8.8, 2.4 Hz, 2H), 3.97 (s, 3H, OMe); 13C NMR
(100 MHz, CDCl3) δ = 158.9 (C), 143.2 (C), 133.5 (C), 130.5 (C), 128.7
(CH), 128.50 (CH), 128.48 (C), 127.0 (CH), 125.7 (CH), 125.2 (C), 123.0
(CH), 119.7 (CH), 115.3 (CH), 103.6 (CH), 55.6 (CH3); LRMS (EI) m/z
373 (M+, 100%), 328 (15%); HRMS: m/z [M]+ calcd for C27H19NO:
373.1467. Found: 373.1472.
Acknowledgments
This research was supported by a research grant from Institute
of Pharmaceutical Life Sciences, Aichi Gakuin University. The
calculations were performed on the RIKEN Integrated Cluster of
Clusters (RICC) and HOKUSAI GreatWave. We gratefully
acknowledge the Advanced Center for Computing and
Communication, RIKEN for providing computational resources.
Keywords: 6H-Dibenzo[b,h]carbazole • Petaracyclic
heteroacene • Molecular structure • Optical properties • DFT
calculation
6-(p-Tolyl)-6H-dibenzo[b,h]carbazole (5e): Yield 132 mg (74%); yellow
needle; mp 217-219 °C (from n-hexane/CH2Cl2); Rf
= 0.3 (n-
hexane/CH2Cl2 = 3:1); 1H NMR (400 MHz, CDCl3) δ = 8.65 (s, 2H), 8.05
(d, J = 8.3 Hz, 2H), 7.82 (d, J = 7.8 Hz, 2H), 7.58 (s, 2H), 7.55 (d, J = 8.3
Hz, 2H), 7.48–7.44 (m, 4H), 7.40 (td, J = 7.8, 6.8 Hz, 2H), 2.52 (s, 3H,
Me); 13C NMR (100 MHz, CDCl3) δ = 142.9 (C), 137.5 (C), 135.3 (C),
133.5 (C), 130.8 (CH), 128.54 (C), 128.50 (CH), 127.1 (CH), 127.0 (CH),
125.7 (CH), 125.3 (C), 123.0 (CH), 119.7 (CH), 103.8 (CH), 21.3 (CH3);
LRMS (EI) m/z 357 (M+, 100%), 83 (40%); HRMS: m/z [M]+ calcd for
C27H19N: 357.1517. Found: 357.1512.
[1]
a) J.-F. Morin, M. Leclerc, D. Adès, A. Siove, Macromol. Rapid
Commun. 2005, 26, 761–778; b) S. Wakim, B.-R. Aïch, T. Ye, M.
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Mater. Chem. C 2017, 5, 8622–8653.
6-(p-Tolyl)-6H-dibenzo[b,h]carbazole (5f): Yield 94 mg (55%); yellow
needle; mp 121-122.5 °C (n-hexane/CH2Cl2); Rf = 0.2 (n-hexane/CH2Cl2
= 3:2); 1H NMR (400 MHz, CDCl3) δ = 8.69 (s, 2H), 8.09 (d, J = 7.8 Hz,
2H), 7.87 (d, J = 8.3 Hz, 2H), 7.72–7.69 (m, 4H), 7.65 (s, 2H), 7.56 (td, J
= 7.8, 3.4 Hz, 1H), 7.51 (td, J = 7.8, 1.0 Hz, 2H), 7.45 (td, J = 7.8, 1.0 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ = 142.7 (C), 138.1 (C), 133.5 (C),
130.1 (CH), 128.6 (C), 128.5 (CH), 127.5 (CH), 127.2 (CH), 127.1 (CH),
125.8 (CH), 125.3 (C), 123.1 (CH), 119.7 (CH), 103.8 (CH); LRMS (EI)
m/z 343 (M+, 100%), 268 (20%), 83 (35%); HRMS: m/z [M]+ calcd for
C26H17N: 343.1361. Found: 343.1366.
[2]
a) X. Shan, X. Li, J. Han, S. Jia, J. Zhang, X. Xu, Inorg. Chem.
Commun. 2012, 16, 37–42; b) C. W. Lee, J. Y. Lee, Dyes Pigments
2014, 103, 34–38; c) X. Mei, K. Wei, G. Wen, Z. Liu, Z. Lin, Z. Zhou, L.
Huang, E. Yang, Q. Lin, Dyes Pigments 2016, 133, 345–353; d) M.
Más-Montoya, D. Curiel, C. Ramírez de Arellano, A. Tárraga, P. Molina,
Eur. J. Org. Chem. 2016, 2016, 3878–3883.
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N. P. Buu-Hoï, G. Saint-Ruf, J. Chem. Soc. C 1966, 924–925.
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18188.
[5]
[6]
6-[4-(Trifluoromethyl)phenyl]-6H-dibenzo[b,h]carbazole (5g): Yield
88 mg (43%); yellow needle; mp 276-278 °C (from n-hexane/CH2Cl2); Rf
= 0.3 (n-hexane/CH2Cl2 = 5:1); 1H NMR (400 MHz, CDCl3) δ = 8.64 (s,
2H), 8.05 (d, J = 7.8 Hz, 2H, Ar-H,), 7.95 (d, J = 8.3 Hz, 2H), 7.87 (d, J =
8.3 Hz, 2H), 7.82 (d, J = 8.3 Hz, 2H), 7.66 (s, 2H), 7.52 (td, J = 7.8, 6.8
Hz, 2H), 7.47 (t, J = 6.8 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ = 141.9
[7]
[8]
[9]
M. J. Turner, J. J. McKinnon, S. K. Wolff, D. J. Grimwood, P. R.
Spackman, D. Jayatilaka, M. A. Spackman, CrystalExplorer17, 2017,
2
(C), 141.5 (C), 133.4 (C), 129.1 (q, JC,F = 33 Hz, C), 128.9 (C), 128.5
a) M. A. Spackman, J. J. McKinnon, D. Jayatilaka, CrystEngComm
2008, 10, 377–388; b) M. A. Spackman, D. Jayatilak, CrystEngComm,
2009, 11, 19–32.
3
(CH), 127.3 (q, JC,F = 3.3 Hz, CH), 127.1 (CH), 127.0 (CH), 126.1 (CH),
1
125.4 (C), 124.0 (q, JC,F = 272 Hz, C), 123.5 (CH), 119.9 (CH), 103.9
(CH); LRMS (EI) m/z 411 (M+, 100%), 266 (10%), 149 (10%); HRMS: m/z
a) A. S.Chimpri, M. Gryl, L. H. R. Dos Santos, A. Krawczuk, P. Macchi,
Cryst. Growth Des. 2013, 13, 2995–3010; b) R. Usman, A. Khan, H.
Sun, M. Wang, J. Solid State Chem. 2018, 266, 112–120.
[M]+ calcd for C27H16F3N: 411.1235. Found: 411.1230.
[10] J. J. McKinnon, M. A. Spackman, A. S. Mitchell, Acta Cryst. B 2004, 60,
627–668.
4-(-6H-dibenzo[b,h]carbazo-6-yl)benzonitrile (5h): Yield 57 mg (31%);
Yellow needle; mp 225-226.5 °C (from n-hexane/CH2Cl2); Rf = 0.3 (n-
hexane/CH2Cl2 = 6:5); 1H NMR (400 MHz, CDCl3) δ = 8.60 (s, 2H), 8.06
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