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Bull. Chem. Soc. Jpn. Vol. 83, No. 7 (2010)
© 2010 The Chemical Society of Japan
J = 8.3 Hz, 1H); 13C NMR (75 MHz, CDCl3): ¤ 13.9, 22.4,
31.4, 33.1, 126.9, 127.1, 128.2, 129.5, 131.1, 137.2, 141.5,
146.3; IR (NaCl, cm¹1): 3051, 3034, 2953, 2926, 2868, 1558,
1541, 1506, 1456, 1339, 1219, 1132, 1038, 901, 870, 772, 758,
669; MS (EI) m/z (relative intensity): 219 (M+, 100), 221 (33),
220 (13), 222 (2).
13C NMR spectra for 2-halogenated quinoline derivatives.
This material is available free of charge on the web at http://
References
1
Procedure for the Triethylamine-Mediated Intramolecu-
lar Brominating Cyclization of o-Alkynylaryl Isocyanide.
To the mixture of 2-(phenylethynyl)phenyl isocyanide (1a,
0.10 mmol) in bromoform (1.0 mL) was added triethylamine
(1.0 mL), and the mixture was stirred for 4 h at room temper-
ature. After the reaction, the resulting mixture was concentrated
in vacuo and purified by PTLC (hexane:EtOAc = 9:1) to give
2-bromo-3-phenylquinoline (3a, 23.1 mg, 0.081 mmol, 81%) as
slight yellow oil.
Comprehensive Heterocyclic Chemistry, ed. by A. R. Katritzky,
A. R. Rees, Pergamon, New York, 1984, Vol. 2, p. 395.
2
For recent reports of the synthesis of quinolines, see for
example: a) C. S. Cho, B. H. Oh, J. S. Kim, T.-J. Kim, S. C. Shim,
e) P. G. Dormer, K. K. Eng, R. N. Farr, G. R. Humphrey, J. C.
McWilliams, P. J. Reider, J. W. Sager, R. P. Volante, J. Org. Chem.
2003, 68, 467. f) S. S. Palimkar, S. A. Siddiqui, T. Daniel, R. J.
2-Bromo-3-phenylquinoline (3a):
1H NMR (300 MHz,
CDCl3): ¤ 7.54-7.75 (m, 5H), 7.60 (t like, J = 7.4 Hz, 1H),
7.75 (t like, J = 7.6 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 8.06 (s,
1H), 8.10 (d, J = 8.8 Hz, 1H); 13C NMR (75 MHz, CDCl3): ¤
127.4, 127.6, 127.8, 128.2, 128.3, 128.4, 128.5, 129.7, 130.4,
137.9, 138.4, 139.9, 144.4, 146.5; IR (NaCl, cm¹1): 3057,
3031, 1556, 1539, 1506, 1487, 1456, 1389, 1360, 1339, 1219,
1130, 1080, 959, 775, 698; MS (EI) m/z (relative intensity):
283 (M+, 100), 285 (88), 284 (13), 286 (15); HRMS (FAB)
calcd for C15H11BrN [M + H]+ 284.0075, found 284.0049.
Procedure for the Intramolecular Fluorinating Cycliza-
tion of Isocyanide 1a with Tetrabutylammonium Fluoride.
In a 30 mL round bottom flask were placed 2-(phenylethynyl)-
phenyl isocyanide (1a, 20 mg, 0.10 mmol) and tetrabutyl-
ammonium fluoride (1.0 M in hexane solution, 0.20 mmol,
0.20 mL) in chloroform (1.0 mL), and the mixture was stirred
for 4 h at room temperature under ambient atmosphere. The
resulting mixture was concentrated in vacuo and purified by
PTLC (hexane:EtOAc = 9:1) to give 2-fluoro-3-phenylquino-
line (4a, 21.8 mg, 0.098 mmol, 98%) as colorless oil.
3
For the synthesis of quinolines containing halogen atoms,
4
For the reaction of aryl isocyanides with nucleophiles to
afford quinoline derivatives, see: a) M. Suginome, T. Fukuda, Y.
K. Yoneda, K. Miyamoto, O. Morikawa, H. Konishi, Tetrahedron
5
For the synthesis of quinoline derivatives by radical
reaction of aryl isocyanides, see: T. Mori, J. Ichikawa, Synlett
2-Fluoro-3-phenylquinoline (4a):
1H NMR (400 MHz,
6
7
CDCl3): ¤ 7.42-7.60 (m, 3H), 7.57 (t like, J = 7.3 Hz, 1H),
7.67 (d, J = 7.3 Hz, 2H), 7.74 (t like, J = 7.6 Hz, 1H), 7.89 (d,
J = 9.2 Hz, 1H), 7.99 (d, J = 9.2 Hz, 1H), 8.30 (d, J = 9.8 Hz,
1H); 13C NMR (100 MHz, CDCl3): ¤ 124.1, 124.7, 126.4,
127.5, 127.8, 128.5, 128.7, 129.0, 130.4, 134.8, 140.5, 144.9,
158.4; MS (EI) m/z (relative intensity): 223 (M+, 100), 224
(22), 225 (2).
For the synthesis of 2-aminoquinoline derivatives from
o-alkynylaryl isocyanides with diethylamine, see Ref. 4a.
For the generation of chloride ion and dichlorocarbene
8
by the reaction of chloroform with bases, see: a) E. Chinoporos,
This work is supported by Grant-in-Aid for Scientific
Research on Scientific Research (B, No. 19350095), from the
Ministry of Education, Culture, Sports, Science and Technol-
ogy, Japan, and the Iodine Utilization Support Program in
the 2009 fiscal year from the Society of Iodine Science. T. M.
thanks JSPS for the Research Fellowship for Young Scientists.
9
When, in place of CHBr3/Et3N, TBABr was employed for
the brominating cyclization, 3a was obtained in 88% isolated
yield.
10 L. Liu, Y. Wang, H. Wang, C. Peng, J. Zhao, Q. Zhu,
11 The use of TBACl as a chloride ion source produced 2a in
99% yield. This result strongly suggested the formation of Cl ion
from CHCl3 with Et3N.
Supporting Information
1
Experimental procedures, characterization data, and H and