894
L. BRINCHI ET AL.
diphenylethanes in cationic micelles.20 Hence uncertain-
ties in the values of VM and K'OH [Eqns (2) and (4)] do not
cloud the overall conclusions.
P, Zana R. J. Colloid Interface Sci. 1982; 88: 594–598; (c) Bunton
CA, Ohmenzetter K, Sepulveda L. J. Phys. Chem. 1977; 81: 2000–
2004; (d) Chaudhuri A, Loughlin JA, Romsted LS, Yao J. J. Am.
Chem. Soc. 1993; 115: 8351–8361; (e) Cuccovia IM, da Silva IN,
Chaimovich H, Romsted LS. Langmuir 1997; 13: 647–652.
4. (a) Quina FH, Chaimovich H. J. Phys. Chem. 1979; 83: 1844–
1850; (b) Romsted LS. J. Phys. Chem. 1985; 89: 5107–5113; (c)
Rodenas E, Vera S. J. Phys. Chem. 1985; 89: 513–516; (d) Bunton
CA, Moffatt R. J. Phys. Chem. 1986; 90: 538–541; (e) Rodenas E,
Ortega F. J. Phys. Chem. 1987; 91: 837–840; (f) Blasko` A, Bunton
CA, Cerichelli G, McKenzie DC. J. Phys. Chem. 1993; 97: 11324–
11331.
5. (a) Bunton CA, Mhala MM, Moffatt R. J. Phys. Chem. 1989; 93:
854–858; (b) Da Silva Baptista M, Cuccovia IM, Chaimovich H,
Politi MJ, Reed WF. J. Phys. Chem., 1992; 96: 6442–6449; (c)
Kamenka N, Chorro M, Chevalier Y, Levy H, Zana R. Langmuir
1995; 11: 4234–4240.
6. Bunton CA, Gan L-H, Moffatt JR, Romsted LS, Savelli G. J. Phys.
Chem. 1981; 85: 4118–4125.
7. Di Profio P, Germani R, Savelli G, Chiarini M, Mancini G, Bunton
CA, Gillitt ND. Langmuir 1998; 14: 2662–2669, and references
cited therein.
8. Sepulveda L, Lissi E, Quina FH. Adv. Colloid Interface Sci. 1986;
25: 1–57.
9. Weers JG, Rathman JF, Axe FU, Crichlow CA, Foland LD,
Scheuing DR, Wiersema RJ, Zielske AG. Langmuir 1991; 7: 854–
867.
EXPERIMENTAL
Materials. Substrates and surfactants were materials
described earlier.2,20,21 Reaction solutions were prepared
in distilled, deionized, CO2-free water.
Kinetics. Reactions were followed spectrophotometri-
cally at 264 and 350 nm for reactions of 1a and b,
4
respectively, as described,2 with 10
M substrate
introduced in MeCN, so that the reaction solution
contained 1 vol.% MeCN. Values of kobs were calculated
by using the integrated first-order rate equation with
correlation coefficients of 0.999 or better. Fitting of the
kobs vs [surfactant] profiles, by using Eqn. (1),1 was
1
insensitive to values of Ks in the range 260 Æ 50 l mol
1
for 1a, and 450 Æ 100 l mol for 1b, based on visual
10. (a) Wilk K. J. Phys. Chem. 1989; 93: 7432–7435; (b) Wilk K,
Burczyk B. J. Phys. Chem. 1989; 93: 8219–8223.
fitting.
11. March J. Advanced Organic Chemistry (4th edn). Wiley–
Interscience: New York, 1992.
Substrate binding. The value of Ks for 1b in SBBu3-14
was determined by the saturation-solubility method,8 as
described.2
12. (a) Ingold CK. Structure and Mechanism in Organic Chemistry
(2nd edn). Cornell University Press: Ithaca, NY, 1969; (b) Lowry
TH, Richardson KS. Mechanism and Theory in Organic Chemistry
(3rd edn). Harper and Row: New York, 1987; (c) Reichardt C.
Solvent and Solvent Effects in Organic Chemistry (2nd edn). VCH:
Weinheim, 1988; (d) Saunders WH, Cockerill AF. Mechanism of
Elimination Reactions. Wiley–Interscience: New York, 1973; (e)
Stirling CJM. Acc. Chem. Res. 1979; 12: 198–203.
13. Ramachandran C, Pyter RA, Mukerjee P. J. Phys. Chem. 1982; 86:
3198–3205.
14. (a) Germani R, Ponti PP, Romeo T, Savelli G, Spreti N, Cerichelli
G, Luchetti L, Mancini G, Bunton CA. J. Phys. Org. Chem. 1989;
2: 553–558; (b) Di Profio P, Germani R, Savelli G, Cerichelli G,
Spreti N, Bunton CA. J. Chem. Soc., Perkin Trans. 1996; 2: 1505–
1509.
Acknowledgements
Support of this work by Consiglio Nazionale delle
Ricerche, Rome, and the Ministero dell’Universita` e
Ricerca Scientifica e Tecnologica, Rome, is gratefully
acknowledged.
15. Brinchi L. Thesis, University of Perugia (1998).
16. Del Rosso F, Bartoletti A, Di Profio P, Germani R, Savelli G,
Blasko` A, Bunton CA. J. Chem. Soc., Perkin Trans. 1995; 2: 673–
678.
17. Bonan C, Germani R, Ponti PP, Savelli G, Cerichelli G, Bacaloglu
R, Bunton CA. J. Phys. Chem. 1990; 94: 5331–5336.
18. (a) Blasko` A, Bunton CA, Gillitt ND. Langmuir 1997; 13: 6439–
6446; (b) Bunton CA, Gillitt ND, Foroudian HJ. Langmuir 1998;
14: 4415–4421.
19. Davies DM, Gillitt ND, Paradis PM. J. Chem. Soc., Perkin Trans.
1996; 2: 659–666.
20. Brinchi L, Germani R, Savelli G, Spreti N, Ruzziconi R, Bunton
CA. Langmuir 1998; 14: 2656–2661.
REFERENCES
1. (a) Romsted LS. In Surfactants in Solution, vol. 2, Mittal KL,
Lindman B (eds). Plenum Press: New York, 1984; 1015–1068; (b)
Bunton CA, Savelli G. Adv. Phys. Org. Chem. 1986; 22: 213–309;
(c) Bunton CA, Nome F, Romsted IS, Quina FH. Acc. Chem. Res.
1991; 24: 357–363; (d) Bunton CA. In Surfactants in Solution, vol.
11, Mittal KL, Shah DO (eds). Plenum Press: New York, 1991; 17–
39; (e) Bunton CA. J. Mol. Liq. 1997; 72: 231–249; (f) Romsted
LS, Bunton CA, Yao J. Curr. Opin. Colloid Interface Sci. 1997; 2:
622–628.
2. Brinchi L, Di Profio P, Germani R, Savelli G, Bunton CA.
Langmuir 1997; 13: 4583–4587.
3. (a) Zana R. J. Colloid Interface Sci. 1980; 78: 330–337; (b) Lianos
21. Brinchi L, Di Profio P, Germani R, Savelli G, Spreti N, Bunton
CA. J. Chem. Soc., Perkin Trans. 1998; 2: 361–364.
Copyright 2000 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 12, 890–894 (2000)