The Journal of Organic Chemistry
ARTICLE
(hexane/AcOEt = 20/1) to give anthracene in 94% yield (2a, 25.9 mg,
0.141 mmol).
(s, 2H), 7.89(dd,J= 8.0 and 1.2 Hz, 2H), 8.69 (d, J=8.0Hz,2H);13CNMR
(100 MHz, CDCl3) δ 122.6, 126.5 (3C), 126.9, 128.6, 130.3, 132.0.
Tetraphene (9). Purification by silica gel column chromatography
(hexane/AcOEt = 50/1): TLC (hexane/AcOEt = 50/1) Rf = 0.50; solid;
mp = 162À163 °C; 1H NMR (400 MHz, CDCl3) δ 7.52À7.55 (m, 2H),
7.58À7.62 (m, 2H), 7.66 (td, J = 8.0 and 1.2 Hz, 1H), 7.77 (d, J = 9.6 Hz,
1H), 7.82 (d, J = 8.0 Hz, 1H), 8.01À8.04 (m, 1H), 8.09À8.12
(m, 1H), 8.34 (s, 1H), 8.81 (d, J = 8.4 Hz, 1H), 9.14 (s, 1H); 13C NMR
(100 MHz, CDCl3) δ 121.5, 122.9 (2C), 125.7, 125.8, 126.75, 126.82,
127.0, 127.3, 127.7, 128.4, 128.6 (2C), 128.8, 130.5, 130.6, 131.89, 131.93.
Acridine (11). Purification by silica gel column chromatography
(hexane/AcOEt = 20/1): TLC (hexane/AcOEt = 20/1) Rf = 0.30; solid;
mp = 111À113 °C; 1H NMR (400 MHz, CDCl3) δ 7.50 (t, J = 7.2 Hz,
2H), 7.76 (t, J = 6.8 Hz, 2H), 7.96 (d, J = 8.4 Hz, 2H), 8.24 (d, J = 8.8 Hz,
2H), 8.71 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 125.6, 126.5, 128.1,
129.3, 130.3, 136.0, 148.9.
Dibenzo[b,j][4,7]phenanthroline (13). Purification by silica gel
column chromatography (hexane/AcOEt = 5/1): TLC (hexane/AcOEt =
5/1) Rf = 0.20; solid; mp = 244À245 °C; 1H NMR (400 MHz, CDCl3) δ
7.68 (t, J = 7.2 Hz, 2H), 7.86 (t, J = 8.0 Hz, 2H), 8.12 (d, J = 8.4 Hz, 2H),
8.21 (s, 2H), 8.30 (d, J = 8.4 Hz, 2H), 9.43 (s, 2H); 13C NMR (100 MHz,
CDCl3) δ 123.4, 126.4, 126.8, 128.0, 129.1, 130.3, 130.4, 134.1, 148.1,
148.7; IR (KBr, ν/cmÀ1) 3051, 2924, 1341, 1321, 1261, 1190, 1130, 1096,
1013, 957, 905, 860, 835, 804, 783, 746, 741; HRMS (FAB+) calcd for
C20H12N2 (M+) 280.1000, found 280.1009.
Anthracene (2a): solid; mp = 210À215 °C; 1H NMR (400 MHz,
CDCl3) δ 7.45À7.47 (m, 4H), 8.00À8.02 (m, 4H), 8.43 (s, 2H);
13C NMR (100 MHz, CDCl3) δ 125.3, 126.2, 128.1, 131.6.
2-Methylanthracene (2b). Purification by silica gel column
chromatography (hexane/AcOEt = 50/1): TLC (hexane/AcOEt =
50/1) Rf = 0.63; solid; mp = 205À206 °C; 1H NMR (400 MHz,
CDCl3) δ 2.51 (s, 3H), 7.27 (d, J = 8.8 Hz, 1H), 7.38À7.43 (m, 2H),
7.70 (s, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.93À7.95 (m, 2H), 8.27 (s, 1H),
8.33 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 22.0, 124.9, 125.1, 125.2,
125.9, 126.3, 127.9, 128.0, 128.15, 128.20, 130.3, 131.2, 131.8, 132.0, 134.9.
1-Methylanthracene (2c). Purification by silica gel column
chromatography (hexane/AcOEt = 50/1): TLC (hexane/AcOEt = 50/1)
Rf = 0.60; 1H NMR (400 MHz, CDCl3) δ 2.80 (s, 3H), 7.28 (d, J = 7.2 Hz,
1H), 7.34 (td, J = 8.4 and 2.8 Hz, 1H), 7.45À7.48 (m, 2H), 7.85 (d, J = 7.6
Hz, 1H), 7.97À7.99 (m, 1H), 8.01À8.03 (m, 1H), 8.40 (s, 1H), 8.53 (s,
1H); 13C NMR (100 MHz, CDCl3) δ 19.7, 122.7, 125.1, 125.26, 125.31,
125.6, 126.7, 126.8, 127.9, 128.5, 131.3, 131.4, 131.5, 131.8, 134.2.
2-Methoxyanthracene (2d) and 1-Methoxyanthracene
(2e). Purification by silica gel column chromatography (hexane/AcOEt =
1
50/1): TLC (hexane/AcOEt = 50/1) Rf = 0.53; H NMR (400 MHz,
CDCl3) δ 3.97 (s, 3H, 2d), 4.09 (s, 3H, 2e), 7.17 (dd, J = 8.8 and 2.4 Hz,
1H, 2d + 2e), 7.20 (d, J = 2.4 Hz, 1H, 2d + 2e) 7.39À7.48 (m, 2H, 2d +
2e), 7.90 (d, J = 8.8 Hz, 1H, 2d + 2e), 7.97 (t, J = 8.0 Hz, 2H, 2d + 2e),
8.28 (s, 1H, 2d), 8.35 (s, 1H, 2d), 8.38 (s, 1H, 2e), 8.86 (s, 1H, 2e); 13C
NMR (100 MHz, CDCl3, 2d) δ 55.2, 103.5, 119.3, 120.5, 124.1, 124.4,
124.9, 125.5, 126.2, 127.6, 128.2, 129.8, 130.3, 132.2, 132.7.
2-Chloroanthracene (2f). Purification by silica gel column chro-
matography (hexane/AcOEt = 50/1): TLC (hexane/AcOEt = 50/1)
Rf = 0.63; solid; mp = 221À223 °C; 1H NMR (400 MHz, CDCl3) δ 7.38
(d, J = 8.8 Hz, 1H), 7.47À7.49 (m, 2H), 7.93À7.99 (m, 4H), 8.32
(s, 1H), 8.40 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 125.4, 125.7,
126.0, 126.3 (2C), 126.5, 126.6, 128.0, 128.2, 129.9, 131.0, 131.69,
131.73, 132.2.
’ ASSOCIATED CONTENT
Supporting Information. 1H and 13C NMR spectra of
S
b
polycyclic aromatic hydrocarbons 2, 5, 7, and 9 and polycyclic
aza-aromatic compounds 11 and 13. This material is available
’ AUTHOR INFORMATION
Corresponding Authors
*E-mail: kuninobu@cc.okayama-u.ac.jp; ktakai@cc.okayama-u.
ac.jp.
Naphtho[2,3-b]thiophene (2g). Purification by silica gel col-
umn chromatography (hexane/AcOEt = 20/1): TLC (hexane/AcOEt =
20/1) Rf = 0.73; solid; mp = 192À193 °C; 1H NMR (400 MHz, CDCl3)
δ 7.40 (d, J = 5.6 Hz, 1H), 7.42À7.48 (m, 3H), 7.88À7.90 (m, 1H),
7.94À7.96 (m, 1H), 8.30 (s, 1H), 8.35 (s, 1H); 13C NMR (100 MHz,
CDCl3) δ 120.6, 121.8, 123.4, 124.9, 125.2, 127.2, 128.1, 128.2, 130.86,
130.89, 138.2, 138.8.
9-Methylanthracene (2h). Purification by silica gel column
chromatography (hexane/AcOEt = 50/1): TLC (hexane/AcOEt = 50/1)
Rf = 0.60; solid; mp = 81À82 °C; 1H NMR (400 MHz, CDCl3) δ 3.13
(s, 3H), 7.50 (d, J = 6.8 Hz, 2H), 7.55 (d, J = 6.4 Hz, 2H), 8.03
(d, J = 8.0 Hz, 2H), 8.32 (d, J = 8.4 Hz, 2H), 8.37 (s, 1H); 13C NMR (100
MHz, CDCl3) δ 13.9, 124.6, 124.8 (3C), 125.2, 125.3, 129.0,
130.1, 131.4.
’ ACKNOWLEDGMENT
This work was supported by the Ministry of Education,
Culture, Sports, Science, and Technology of Japan and Okayama
University.
’ REFERENCES
(1) (a) Katz, H. E.; Bao, Z.; Gilat, S. L. Acc. Chem. Res. 2001, 34, 359.
(b) Ling, M. M.; Bao, Z. Chem. Mater. 2004, 16, 4824. (c) Anthony, J. E.
Angew. Chem., Int. Ed. 2008, 47, 452.
9-Phenylanthracene (2i). Purification by silica gel column chro-
matography (hexane/AcOEt = 50/1): TLC (hexane/AcOEt = 50/1)
Rf = 0.58; solid; mp = 155À157 °C; 1H NMR (400 MHz, CDCl3) δ 7.33
(d, J = 6.8 Hz, 1H), 7.35 (dd, J = 6.4 and 1.2 Hz, 1H), 7.42À7.46 (m,
4H), 7.51À7.59 (m, 3H), 7.60 (d, J = 8.8 Hz, 2H), 8.04 (d, J = 8.4 Hz,
2H), 8.49 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 125.1, 125.3, 126.5,
126.8, 127.4, 128.28, 128.34, 130.2, 131.2, 131.3, 137.0, 138.7.
Naphthalene (5). Purification by silica gel column chromatography
(hexane/AcOEt = 50/1): TLC (hexane/AcOEt = 50/1) Rf = 0.75; solid;
mp = 218À219 °C; 1H NMR (400 MHz, CDCl3) δ 7.47À7.49 (m, 4H),
7.84À7.86 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 125.8, 127.8, 133.4.
Phenanthrene (7). Purification by silica gel column chromatogra-
phy (hexane/AcOEt = 50/1): TLC (hexane/AcOEt = 50/1) Rf = 0.63;
solid; mp = 224À225 °C; 1H NMR (400 MHz, CDCl3) δ 7.60
(td, J = 8.0 and 1.6 Hz, 2H), 7.66 (td, J = 8.0 and 1.6 Hz, 2H), 7.74
(2) For examples, see: (a) Mallouli, A.; Lepage, Y. Synthesis 1980,
9, 689. (b) Bowles, D. M.; Anthony, J. E. Org. Lett. 2000, 2, 85.
(c) Odom, S. A.; Parkin, S. R.; Anthony, J. E. Org. Lett. 2003, 5, 4245.
(d) Vets, N.; Smet, M.; Dehaen, W. Synlett 2005, 217. (e) Miao, Q.; Chi,
X.; Xiao, S.; Zeis, R.; Lefenfeld, M.; Siegrist, T.; Steigerwald, M. L.;
Nuckolls, C. J. Am. Chem. Soc. 2006, 128, 1340. (f) Lin, C.-H.; Lin, K.-H.;
Pal, B.; Tsou, L.-D. Chem. Commun. 2009, 803.
(3) Frost, C. G.; Hartley, J. P. Mini-Rev. Org. Chem. 2004, 1, 1.
(4) There have been several reports that rhenium(I) carbonyl
complexes work as Lewis acid catalysts. See: (a) Kusama, H.; Narasaka,
K. Bull. Chem. Soc. Jpn. 1995, 68, 2379. (b) Nishiyama, Y.; Kakushou, F.;
Sonoda, N. Bull. Chem. Soc. Jpn. 2000, 73, 2779. (c) Hua, R.-M.; He, J.-Y.;
Sun, H.-B. Chin. J. Chem. 2007, 25, 132. (d) Kuninobu, Y.; Ishii, E.; Takai,
K. Angew. Chem., Int. Ed. 2007, 46, 3296. (e) Kuninobu, Y.; Ueda, H.;
Takai, K. Chem. Lett. 2008, 37, 878.
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dx.doi.org/10.1021/jo200861s |J. Org. Chem. 2011, 76, 7005–7009