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HETEROCYCLES, Vol. 68, No. 6, 2006
large εmax values and long wavelength absorption and emission. The presence of an amino group at the para-position of the
aryl group shifts the emission to longer wavelength. The 2-pyrone derivatives bearing an electron-donating group at the 4-
position and an electron-withdrawing group at the 3-position of the 2-pyronefluoresce in solution and in the solidstate.
REFERENCES AND NOTES
1.
a) C. W. Tang and S. A. Van Slyke, Appl. Phys. Lett., 1987, 51, 913. b) C. W. Tang, S. A. Van Slyke, and C. H. Chen, J. Appl.
Phy., 1989, 65, 3610. c) M. Matsuoka, J. Soc. Dyers and Colourists, 1989, 105, 167. d) K. Shirai, A. Yanagisawa, H. Takahashi,
K. Fukunishi, and M. Matsuoka, Dyes and Pigments, 1998, 39, 49. e) K. Shirai, M. Matsuoka, and K. Fukunishi, Dyes and
Pigments, 2000, 47, 107.
2.
3.
a) J. H. Burroghed, Nature, 1990, 347, 539. b) M. A. Baldo, M. E. Thompson, and S. R. Forrest, Nature, 2000, 403, 750.
a) K. Hirano, S. Minakata, and M. Komatsu, Chem. Lett., 2001, 8. b) K. Hirano, S. Minakata, and M. Komatsu, Bull. Chem. Soc.
Jpn., 2001, 74, 1567.
4.
a) Y. Tominaga, Y. Matsuda, and G. Kobayashi, Heterocycles, 1976, 4, 1493. b) Y. Tominaga, A. Ushirogouchi, Y. Matsuda,
and G. Kobayashi, Heterocycles, 1977, 8, 193. c) Y. Tominaga, Y. Matsuda, and G. Kobayashi, Chem. Pharm. Bull., 1984, 32,
1665. d) Y. Tominaga, A. Ushirogouchi, Y. Matsuda, and G. Kobayashi, Chem. Pharm. Bull., 1984, 32, 3384. e) Y. Tominaga,
A. Ushirogouchi, and Y. Matsuda, J. Heterocycl. Chem., 1987, 24, 1557. f) Y. Tominaga, J. Org. Synth. Chem., 1989, 47, 413.
5.
6.
7.
3a: red prisms (MeOH-toluene). 1H-NMR (CDCl3)δ 2.66 (3H, s, SMe), 3.11 (6H, s, 2xNMe2), 6.47 (1H, s, 5-H), 6.69(2H,
d, J=9.0 Hz, 3', 4'-H), 7.75 (2H, d, J=9.0 Hz, 2', 6'-H).
3b: black violet leaflets(MeOH-toluene). 1H-NMR(CDCl3) δ: 2.65(3H, s, SMe), 3.10(6H, s, 2xNMe2), 12(1H, s, 6-H),
6.44 (1H, d, J=15.7 Hz, =CH), 6.72 (2H, J=9.1 Hz, 3’, 5’-H), 7.48 (2H, d, J=9.1 Hz, 2’, 6’-H), 7.68 (2H, d, J=15.7 Hz, =CH).
3c: black violet leaflets (MeOH-toluene). 1H-NMR(CDCl3) δ: 1.21(6H, t, J=7.1 Hz, N-CH2-CH3), 2.61(3H, s, SMe),
3.43 (4H, q , J=7.1 Hz, N-CH2-), 6.07 (1H, s, 5-H), 6.37(1H, d, J=15.7 Hz, =CH), 6.65 (2H, d, J=9.1 Hz, 3’, 5’-H), 7.42(2H,
d, J=9.1 Hz, 2’, 6’-H), 7.63 (1H, d, J=15.7 Hz, =CH).
8.
9.
3d: red brown leaflets (MeOH-toluene). 1H-NMR(CDCl3) δ: 2.62(3H, s, SMe), 6.18(1H, s, 5-H), 6.48(1H, d, J=15.1 Hz,
=CH), 6.75-7.40 (14H, m, phenyl-H), 7.61(1H, d, J=15.1 Hz, =CH).
4a: lemon yellowneedles (MeOH). 4b: lemon yellowneedles (MeOH). 4c: yellowneedles (MeOH). 4d: orange needles
(MeOH). 5a: orange needles (MeOH). 5b: red needles (MeOH).
10. Crystal data of 4a: lemon yellowneedles (C16H17N3O2=283.33, 0.40 x 0.12 x 0.08 mm3), orthorhombic, space group=P212121,
Z=8, a=7.5938Å, b=14.0254Å, c=27.4606Å, V=2924.72 Å3, D(calcd)=1.28g/cm3, µ(Mo-Kα)=0.90 cm-1, F(000)=1200,
Reflection=11603, Residuals=0.044(R1), 0.106(wR2).
11. In the 6-phenyl-2-pyrone derivatives, the fluorescent intensity in which the derivatives on the phenyl group with an electron
donating group is stronger than other compounds was clarified.
12. These 2-oxo-2H-pyran-3-carbonitriles (3a-d, 4a-d) can use as a fluorescence reagent in an oxalate chemiluminscence system.