7798
R. M. El-Shishtawy, P. Almeida / Tetrahedron 62 (2006) 7793–7798
5. Elhabiri, M.; Siri, O.; Sornosa-Tent, A.; Albrecht-Gary, A.-M.;
Braunstein, P. Chem.—Eur. J. 2004, 10, 134.
6. Callan, J. F.; de Silva, A. P.; Ferguson, J.; Huxley, A. J. M.;
O’Brien, A. M. Tetrahedron 2004, 60, 11125.
dye 5a as a dark red crystal in 48% yield. The second frac-
tion so obtained was the corresponding symmetric indocar-
bocyanine dye 6a as a dark red crystal in 10% yield, mp
273–276 ꢂC (260–263 ꢂC).19a Using the same procedure
and starting from protonated benzothiazole IVb (0.234 g,
1.02 mmol) and salt I0b (0.315 g, 1.02 mmol), the unique
dye so obtained was the symmetric thiacarbocyanine 6b as
a violet crystal in 8% yield, mp 267–268 ꢂC (269 ꢂC).19a
´
7. Baruah, M.; Qin, W.; Basaric, N.; De Borggraeve, W. M.;
Boens, N. J. Org. Chem. 2005, 70, 4152.
€
8. Schroder, C. R.; Weidgansa, B. M.; Klimant, I. Analyst 2005,
130, 907.
9. Haugland, R. P. Handbook of Fluorescent Probes and Research
Products, 9th ed.; Molecular Probes: Eugene, OR, 2002.
10. Busch, W.; Martin, R.; Herrmann, R. G. Chromosome Res.
1994, 2, 15.
11. Briggs, M. S.; Burns, D. D.; Cooper, M. E.; Gregory, S. J.
Chem. Commun. 2000, 2323.
4.3.2.1.
2-[3-(3,3-Dimethyl-1,3-dihydroindol-2-yli-
dene)-propenyl]-1-ethyl-3,3-dimethyl-3H-indolium iodide
(5a). Mp 140–142 ꢂC; from CHCl3/petroleum ether. IR
(KBr) n (cmꢀ1): 2967, 1562, 1491, 1464, 1379, 1194,
1
1115, 1079, 928, 752. H NMR (250.13 MHz, DMSO-d6)
d (ppm): 1.29 (3H, t, J¼6.7 Hz, CH2CH3), 1.47 (6H, s, 300-
(CH3)2), 1.71 (6H, s, 3-(CH3)2), 4.17 (2H, q, J¼7.4 Hz, 1-
NCH2), 6.19 (1H, d, J¼13.0 Hz, 30-CH), 6.44 (1H, d,
J¼13.9 Hz, 10-CH), 7.20 (1H, t, J¼7.4 Hz, 500-CH), 7.28–
7.46 (5H, m, 5-CH, 6-CH, 7-CH, 600-CH, 700-CH), 7.55
(1H, d, J¼7.2 Hz, 400-CH), 7.68 (1H, d, J¼7.5 Hz, 4-CH),
8.50 (1H, t, J¼13.2 Hz, 20-CH), 12.76 (1H, br s, 100-NH).
(CH2CH3), 25.8 (300-(CH3)2), 27.3 (3-(CH3)2), 38.5
(1-NCH2), 49.2 (300-C), 49.4 (3-C), 100.5 (30-CH), 101.9
(10-CH), 111.3 (7-CH), 111.8 (700-CH), 122.6 (4-CH),
123.1 (400-CH), 124.1 (500-CH), 125.2 (5-CH), 128.5
(6-CH, 600-CH), 139.3 (3a00-C), 141.4 (3a-C, 7a-C, 7a00-C),
149.7 (20-CH), 173.9 (200-C), 176.9 (2-C). UV–visible (etha-
nol): lmax¼552 nm and 3max¼82,511 Mꢀ1 cmꢀ1. HRMS
(FAB, 3-NBA): M+, found 357.2325; C25H29N2 requires
357.2330.
12. Su, M.; Liu, Y.; Ma, H.; Ma, Q.; Wang, Z.; Yang, J.; Wang, M.
Chem. Commun. 2001, 960.
13. Cooper, M. E.; Gregory, S.; Adie, E.; Kalinka, S. J. Fluoresc.
2002, 12, 425.
14. (a) Vilsmeier, A.; Haack, A. Ber. Dtsch. Chem. Ges. 1927, 60,
119; (b) Jones, G.; Stanforth, S. P. Organic Reactions;
Paquette, L. A., Ed.; Wiley: New York, NY, 1997; Vol. 49,
pp 1–330; (c) Downie, I. M.; Earle, M. J.; Heaney, H.;
Shuhaibar, K. F. Tetrahedron 1993, 49, 4015.
15. The Vilsmeier formylation has also been applied to alkenes,
acetals, and ketals, see: Smith, M. B.; March, J. Advanced
Organic Chemistry, 5th ed.; Wiley: New York, NY, 2001;
p 785 and references therein.
13C NMR (62.90 MHz, DMSO-d6)
d (ppm): 12.3
16. Reidlinger, C.; Dworczak, R.; Junek, H. Dyes Pigments 2000,
44, 219.
17. Wang, J.; Cao, W.; Su, J.; Tian, H.; Huang, Y.; Sun, Z. Dyes
Pigments 2003, 57, 171.
18. Mujumdar, S. R.; Mujumda, R. B.; Grant, C. M.; Waggoner,
A. S. Bioconjugate Chem. 1996, 7, 356.
Acknowledgements
19. (a) Hamer, F. M. The Cyanine Dyes and Related Compounds-
the Chemistry of Heterocyclic Compounds; Weissberger, A.,
Ed.; Interscience: New York, NY, 1971; Vol. 18; (b)
Mujumdar, R. B.; Ernst, L. A.; Mujumdar, S. R.; Lewis,
C. J.; Waggoner, A. S. Bioconjugate Chem. 1993, 4, 105.
20. Dye 4a was independently synthesized by another way.
El-Shishtawy, R. M.; Oliveira, A. S.; Vieira Ferreira, L. F.;
Almeida P. J. Photochem. Photobiol., A, submitted for publica-
tion.
~
^
Thanks are due to Fundac¸ao para a Ciencia e Tecnologia,
Portugal, POCTI and FEDER, for the funding of the Project
‘Development of New Supports for Dye-Affinity Chromato-
graphy’ (POCTI/2002/QUI/44776) and for granting Reda
M. El-Shishtawy a Post-doctoral fellowship (SFRH/BPD/
14618/2003).
21. Fischer, E.; Steche, A. Liebigs Ann. Chem. 1887, 242, 353.
22. Reidlinger, C.; Dworczak, R.; Junek, H. Dyes Pigments 1994,
24, 185.
References and notes
1. Mishra, A.; Behera, R. K.; Behera, P. K.; Mishra, B. K.; Behera,
G. B. Chem. Rev. 2000, 100, 1973.
23. Deligeorgiev, T.; Vasilev, A.; Drexhage, K.-H. Dyes Pigments
2005, 67, 21.
2. (a) Spichiger-Keller, U. E. Chemical Sensors and Biosensors
for Medical and Biological Applications; Wiley-VCH:
Weinheim, 1998; (b) Eggins, B. R. Chemical Sensors and
Biosensors; Wiley-VCH: London, 2002; (c) de Silva, A. P.;
Gunaratne, H. Q. N.; Gunnlaugsson, T.; Huxley, A. J. M.;
McCoy, C. P.; Rademacher, J. T.; Rice, T. R. Chem. Rev.
1997, 97, 1515; (d) Chemosensors of Ion and Molecule
Recognition; Desvergne, J.-P., Czarnik, A. W., Eds.; Kluwer:
Dordrecht, 1997; (e) Fabbrizzi, L., Ed.; Coord. Chem. Rev.
2000, 1; (f) Valeur, B. Molecular Fluorescence; Wiley:
Weinheim, 2002; (g) Rurack, K.; Resch-Genger, U. Chem.
Soc. Rev. 2002, 31, 116.
24. Pardal, C. A.; Ramos, S. S.; Santos, P. F.; Reis, V. L.; Almeida,
P. Molecules 2002, 7, 320.
25. Good, V. pH Measurements: Their Theory and Practice;
Methuen: London, 1956.
26. de Silva, A. P.; Gunaratne, H. Q. N.; Lynch, P. L. M.; Patty,
A. L.; Spence, G. L. J. Chem. Soc., Perkin Trans. 2 1993, 1611.
27. Bissell, R. A.; de Silva, A. P.; Gunaratne, H. Q. N.; Lynch,
P. L. M.; Maguire, G. E. M.; Sandanayake, K. R. A. S.
Chem. Soc. Rev. 1992, 21, 187.
28. Connors, K. Binding Constants: The Measurement of
Molecular Complex Stability; Wiley: New York, NY, 1987.
29. Blance, J.; Ross, D. L. J. Phys. Chem. 1968, 72, 2819.
30. (a) Perrin, D. D.; Dempsey, B. Buffers for pH and Metal Ion
Control; Chapman and Hall: London, New York, NY, 1987;
(b) Vogel, A. A Textbook of Quantitative Inorganic Analysis;
Longmans: London, 1944.
3. de Silva, A. P.; Eilers, J.; Zlokarnik, G. Proc. Natl. Acad. Sci.
U.S.A. 1999, 96, 8336.
4. Alves, S.; Pina, F.; Albelda, M. T.; Garcia-Espana, E.; Soriano,
C.; Luis, S. V. Eur. J. Inorg. Chem. 2001, 405.