1177
Scheme 2.
gation. Preliminary results show intense emission bands for compounds 8 and 9 between 400 to 820 nm
at room temperature.
References
1. Chen, C. H.; Fox, J. L. Proc. Int. Conf. Lasers (1988) 1987, 995–998.
2. Specht, D. P.; Martic, P. A.; Farid, S. Tetrahedron 1982, 38(9), 1203–1211.
3. Case, F. A.; Butte, W. A. J. Org. Chem. 1961, 26(11), 4415–4418.
4. Collin, J. P.; Beley, M.; Sauvage, J. P.; Barigelletti, F. Inorg. Chim. Acta 1991, 186, 91.
5. Beley, M.; Collin, J. P.; Sauvage, J. P. Inorg. Chem. 1993, 32, 4539.
6. Balzani, V.; Juris, A.; Venturi, M.; Campagna, S.; Serroni, S. Chem. Rev. 1996, 96, 759–833.
7. Constable, E. C.; Henney, R. P. G.; Leese, T. A.; Tocher, D. A. J. Chem. Soc., Dalton Trans. 1990, 443–449.
8. Knoevenagel, E. Ber. 1898, 31, 2593.
9. Kröhnke, F. Synthesis 1976, 1.
10. 5: 1H NMR: δ (ppm) CDCl3 9.62 (s, 1H), 8.94–8.91 (d, 4.9 Hz, 1H), 8.79–8.76 (ddd, 4.7, 1.7 and 1.0 Hz, 1H), 8.68–8.63
(ddd, 8.0, 1.0 and 1.0 Hz, 1H), 8.04–8.00 (d, 8.8 Hz, 1H), 8.00–7.76 (dd, 8.0 and 1.2 Hz, 1H), 7.90–7.81 (ddd, 8.0, 7.2 and
1.7 Hz, 1H), 7.86–7.77 (dd, 7.9 and 1.5 Hz, 1H), 7.77–7.72 (m, 2H), 7.65–7.58 (ddd, 8.0, 7.1 and 1.0 Hz, 1H), 7.56–7.53 (m,
3H), 7.49–7.45 (d, 8.8 Hz, 1H), 7.43–7.36 (ddd, 7.4, 4.7 and 1.2 Hz, 1H). 13C NMR: δ (ppm) CDCl3 163.8, 158.7, 157.8,
154.7, 152.0, 149.5, 145.0, 141.0, 137.0, 133.8, 131.4, 129.7, 129.4, 129.4, 128.9, 128.7, 127.8, 125.7, 124.8, 124.8, 122.4,
117.1, 115.5, 114.4, 111.4. EI/MS: 400.3 (M+·, 100%), 322.1 (M−C5H5N+, 57%), 200 (M++, 29%), 78.1 (C5H5N+, 4%).
Abs. λmax (nm), [ε (L mol−1 cm−1)] CH3CN: 364 (37 620); m.p. 224°C.
11. 6: 1H NMR: δ (ppm) CDCl3 8.86 (s, 1H), 8.76–8.75 (dd, 4.3 and 1.5 Hz, 1H), 8.62–8.58 (d, 7.8 Hz, 1H), 8.12–8.08 (d, 9.1
Hz, 1H), 7.87–7.80 (ddd, 7.8, 7.7 and 1.5 Hz, 1H), 7.67–7.63 (m, 2H), 7.50–7.47 (m, 3H), 7.40–7.35 (dd, 7.7 and 4.3 Hz,
1H), 6.70–6.66 (dd, 9.1 and 2.4 Hz, 1H), 6.52–6.51 (d, 2.4 Hz, 1H), 3.49–3.41 (q, 7.0 Hz, 4H), 1.27–1.22 (t, 7.0 Hz, 6H).
13C NMR: δ (ppm) CDCl3 163.7, 159.7, 157.1, 155.1, 155.0, 151.1, 149.1, 145.5, 141.4, 137.0, 128.9, 128.5, 127.7, 125.5,
124.5, 122.4, 111.7, 109.7, 108.8, 104.7, 97.8, 44.7, 12.5. Abs. λmax (nm), [ε (L mol−1 cm−1)] CH3CN: 353 (14 950); 402
(8210); m.p. 180°C.
12. Raboin, J. C.; Beley, M.; Kirsch, G. J. Heterocycl. Chem., submitted for publication.
13. 8: 1H NMR: δ (ppm) CD3CN 9.10 (s, 1H), 8.87 (s, 1H), 8.76–8.72 (d, 8.1 Hz, 1H), 8.61–8.57 (d, 8.1 Hz, 1H), 8.38–8.33
(d, 9.1 Hz, 1H), 8.29–8.25 (dd, 8.4 and 1.0 Hz, 1H), 8.16–8.11 (d, 8.6 Hz, 1H), 7.99–7.90 (ddd, 8.2, 7.6 and 1.4 Hz,
1H), 7.88–7.76 (m, 2H), 7.62–7.58 (d, 5.7 Hz, 1H), 7.53–7.50 (d, 5.7 Hz, 1H), 7.48–7.46 (d, 5.7 Hz, 1H), 7.21–7.09 (m,
3H), 6.97–6.91 (d, 2.5 Hz, 1H), 6.69–6.63 (m, 2H), 6.53–6.45 (ddd, 7.4, 7.4 and 1.5 Hz, 1H), 5.64–5.60 (dd, 7.6 and 1.2
Hz, 1H), 4.20 (s, 3H), 4.10 (s, 3H), 3.63–3.52 (q, 7.0 Hz, 4H), 1.31–1.24 (t, 7.0 Hz, 6H). FAB/MS: (m/z), 1016.3 ([M]+,
3%), 871.4 ([M−PF6]+, 100%), 841.3 ([M−PF6−C2H4]+, diacid, 7%), 823.1 ([M−PF6−C2H6O]+, anhydride, 8%), 813.3
([M−PF6−CO2CH3]+, 11%), 754.2 ([M−PF6−2CO2CH3]+, 5%), 521.9 ([M−(32)]+, 8%), 436.1 ([M]2+, 10%). Abs. λmax
(nm), [ε (L mol−1 cm−1)] CH3CN: 368 (72 810); 435 (70 070); 523 (70 990).
14. 9: 1H NMR: δ (ppm) CD3CN 9.37 (s, 1H), 9.12 (s, 1H), 9.07–9.04 (d, 8.6 Hz, 1H), 8.69–8.66 (d, 8.3 Hz, 1H), 8.61–8.58
(d, 8.2 Hz, 1H), 8.41–8.38 (d, 7.4 Hz, 1H), 8.27–8.24 (d, 9.0 Hz, 1H), 8.19–8.16 (d, 8.8 Hz, 1H), 8.16–8.12 (d, 8.9 Hz,
1H), 7.97–7.72 (m, 5H), 7.69–7.65 (d, 8.9 Hz, 1H), 7.62–7.60 (d, 5.3 Hz, 1H), 7.57–7.54 (d, 6.2 Hz, 1H), 7.54–7.52 (d, 6.5
Hz, 1H), 7.22–7.11 (m, 3H), 6.76–6.69 (dd, 7.6 and 7.6 Hz, 1H), 6.57–6.51 (dd, 7.4 and 7.2 Hz, 1H), 5.72–5.69 (d, 6.9 Hz,
1H), 4.19 (s, 3H), 4.09 (s, 3H). FAB/MS: (m/z), 850.3 ([M−PF6]+, 100%), 822.3 ([M−PF6−C2H4]+, diacid, 5%), 733.3
([M−PF6−2CO2CH3]+, 4%). Abs. λmax (nm), [ε (L mol−1 cm−1)] CH3CN: 391 (49 150); 515 (71 000).