Study of a novel reaction between N,N ′-diphenylthiourea and p-chloranil through a charge-transfer intermediate

Abstract

The well-known electron acceptor, p-chloranil (A) and donor, N,N ′-diphenylthiourea (B) have been observed to form a labile charge-transfer (CT) complex (AB), which decays slowly into two products viz. 2,3,5-trichloro-6-(N,N ′-diphenylthioureido)benzo-1,4-quinone (P) and 5,6-dichloro-2,3-(N,N ′-diphenylthioureylene)benzo-1,4-quinone (Q). The final products have been isolated in pure form and one of them, P, has been shown to exhibit sensitive solvatochromism. A detailed kinetic study of the decay process of the CT complex has been carried out and based on kinetic data, the following steps have been suggested for the decay process.

References

1. S. D. Bella, I. L. Fragala, M. A. Ratner and T. J. Marks, J. Am. Chem. Soc., 1993, 115, 682.
2. R. C. Ahuja, M. Matasumoto and D. Mobius, J. Phys. Chem., 1992, 96, 1855.
3. R. C. Ahuja, M. Matasumoto and D. Mobius, Thin Solid Films, 1992, 210/211, 60.
4. B. K. Paul, D. C. Mukherjee and S. P. Moulik, J. Photochem. Photobiol. A: Chem., 1996, 94, 53.
5. R. Foster, Organic Charge-transfer complexes, Academic Press, New York, 1969.
6. R. S. Mulliken and W. B. Person, Molecular Complexes, Wiley Interscience, New York, 1969.
7. L. J. Andrews and R. M. Keefer, Molecular complexes in Organic Chemistry, Holden-Day Inc., New York, 1964.
8. M. A. Slifkin, Charge Transfer Interaction in Biomolecules, Academic Press, London, 1971.
9. E. M. Kosower, in Progress in Physical Organic Chemistry, vol. 3, eds. S. G. Kohen, A. Streitwieser, Jr. and R. N. Taft, Interscience, New York, 1965, p. 81.
10. Z. Rappoport, J. Chem. Soc., 1963, 4498.
11. Z. Rappoport and A. Horowitz, J. Chem. Soc., 1964, 1348.
12. T. Nogami, A. Yoshihara, H. Hosoya and S. Nagakura, J. Phys. Chem., 1969, 73, 2670.
13. P. C. Dwivedi, A. Bansal, A. Srivastava and A. K. Banga, Indian J. Chem., Sect. A, 1987, 26, 389.
14. P. C. Dwivedi, A. Bansal, A. Srivastava and A. K. Banga, Indian J. Chem., Sect. A, 1988, 27, 753.
15. M. Krishnamurty, K. Surendrababu and U. Muralikrishna, Indian J. Chem., Sect. A, 1988, 27, 669.
16. S. Karmakar and S. Basu, J. Indian Chem. Soc., 1991, 68, 442 (Indian J. Chem., Sect. A, 1991, 30, 25).
17. A. K. Mukherjee and K. Datta, J. Chem. Soc., Faraday Trans., 1992, 88, 563.
18. T. Roy, K. Datta, A. K. Mukherjee, M. Banerjee and B. K. Seal, Indian J. Chem., Sect. A, 1997, 36, 585 (Indian J. Chem., Sect. A, 1998, 37, 1007).
19. F. P. Pla, J. Palou, R. Valero, C. D. Hall and P. Speers, J. Chem. Soc., Perkin Trans. 2, 1991, 1925.
20. K. Datta, A. K. Mukherjee, M. Banerjee and B. K. Seal, Spectrochim. Acta, Part A, 1997, 53, 2587.
21. A. Weissberger, Technique of Organic Chemistry, Interscience, New York, vol. 7, 1955.
22. J. C. Coetzee and C. D. Ritchie, in Solute-Solvent Interactions, ed. Marcel Dekker, New York, 1969.
23. H. Kainer and W. Otting, Chem. Ber., 1955, 88, 1921.
24. K. J. Laidler and H. Eyring, Ann. N. Y. Acad. Sci., 1940, 39, 303.
25. E. M. Kosower and E. P. Klindenist, J. Am. Chem. Soc., 1956, 78, 3493.
26. E. M. Kosower, J. Am. Chem. Soc., 1958, 80, 3253 (ibid, 1958, 80, 3261).
27. E. M. Kosower and G. S. Wu, J. Am. Chem. Soc., 1961, 83, 3142.
28. E. M. Kosower, G. S. Wu and T. S. Sorensen, J. Am. Chem. Soc., 1961, 83, 3147.
29. E. M. Kosower, W. D. Closson, H. L. Goering and J. R. Grass, J. Am. Chem. Soc., 1961, 83, 2013.
30. C. Reichardt, Angew. Chem., 1965, 77, 30 (Angew. Chem., Int. Ed. Engl., 1965, 4, 29).
31. C. Reichardt, Chem. Rev., 1994, 94, 2319.