Abstract
The behaviour of 1-(2-bromoethyl) 4-nitrobenzene (1), N,N,N-triethyl-2-(4-nitrophenyl)ethanaminium bromide (2) and N,N-diethyl-N-[2-(4-nitrophenyl)ethyl]octan-1-aminium bromide (3) in the OH−-induced elimination reactions with formation of 1-nitro-4-vinylbenzene in mixtures of DMSO/H2O or CH3CN/H2O has been investigated. With all three substrates an increase in dipolar aprotic solvent content implies a limited increase of the second-order rate constant k OH up to ≅605, and then an exponential increase is observed. The variation of activation parameters ΔH # and dGS #, measured in DMSO/H2O mixtures, is parallel for 1 and 2. This similar behaviour of 1 and 2 with respect to variation in solvent composition is evidence that it is not possible to use this technique of solvent effect for the mechanistic diagnosis of elimination reactions.
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References
C. Reichardt, Chem. Rev. 94, 2319 (1994).
C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, 2nd edn. VCH, Weinheim (1990).
A. R. Katrizky, D. C. Fara, H. Yang, K. Tämm, T. Tamm and M. Karelson, Chem. Rev. 104, 175 (2004).
J. H. Chipperfield, Non-aqueous Solvents, Oxford Chemistry Primers. Oxford University Press, Oxford (1999).
R. A. Ransdell and C. C. Wamser, J. Phys. Chem. 96, 10572 (1992).
I. M. Herfort and H. Schneider, Liebigs Ann. Chem., 27 (1991).
W. Karzijn and J. B. F. N. Engberts, Recueil J. Roy. Neth. Chem. Soc. 96, 95 (1977).
C. Reichardt, Chem. Soc. Rev. 147 (1992).
J. L. M. Abbound and R. Notario, Pure Appl. Chem. 71, 645 (1999).
K. Remerie and J. B. F. N. Engberts, J. Phys. Chem. 87, 5449 (1983).
C. Reichardt, A. Blum and M. Wilk, Pure Appl. Chem. 65, 2593 (1993).
W. H. Saunders and A. F. Cockerill, Mechanisms of Elimination Reactions. Wiley-Interscience, New York, NY (1973).
D. V. Banthorpe, Elimination Reactions. Elsevier, Amsterdam (1963).
E. Baciocchi, in: The Chemistry of Halides, Pseudo-Halides and Azides, Part 2, Supplement D, S. Patai and Z. Raport (Eds), p. 1173, Wiley, Chichester (1983).
J. R. Gandler, in: The Chemistry of Double-Bonded Functional Groups, Vol. 2, Part 1, S. Patai (Ed.), p. 734. Wiley, Chichester (1989).
J. W. Bunting and J. P. Kanter, J. Am. Chem. Soc. 113, 6950 (1991).
J. R. Gandler and T. Yokoyama, J. Am. Chem. Soc. 106, 130 (1984).
R. H. Abeles, P. A. Frey and W. P. Jencks, Biochemistry. Jones and Bartlett, Boston, MA (1992).
J. R. Gandler and W. P. Jencks, J. Am. Chem. Soc. 104, 1937 (1982).
J. R. Keeffe and W. P. Jencks, J. Am. Chem. Soc. 105, 265 (1983).
S. Alunni and P. Tijskens, J. Org. Chem. 60, 8371 (1995).
S. Alunni and W. P. Jencks, J. Am. Chem. Soc. 102, 2052 (1980).
A. J. Parker, Chem. Rev. 69, 1 (1969).
P. Haberfield, J. Friedman and M. F. Pinkston, J. Am. Chem. Soc. 94, 71 (1972).
M. T. Hanna, F. Y. Khlil and S. M. Beder, Bull. Soc. Belg. 94, 27 (1987).
R. Cattana, J. J. Silber and J. Anunziata, Can. J. Chem. 70, 2677 (1992).
M. J. Blandamer, N. J. Blundell, H. J. Cowles and M. Horn, J. Chem. Soc. Faraday Trans. 86, 227 (1990).
R. A. Cox, Adv. Phys. Org. Chem. 35, 1 (2000).
C. H. Rochester, Acidity Function. Academic Press, New York, NY (1970).
R. A. Cox and K. Yates, Can. J. Chem. 61, 2225 (1983).
K. L. Handoo, Y. Lu, Y. Zhao and V. D. Parker, Org. Biomol. Chem. 1, 24 (2003).
S. Alunni, F. De Angelis, L. Ottavi, M. Papavasileiou and F. Tarantelli, J. Am. Chem. Soc. 127, 15151 (2005).
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Alunni, S., Melis, R. & Ottavi, L. OH−-induced β-elimination reactions with 1-(2-Xethyl)-4-nitrobenzene substrates in solvent mixture H2O/CH3CN and H2O/DMSO: Reactivity and mechanism. Res Chem Intermed 32, 827–836 (2006). https://doi.org/10.1163/156856706778938509
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DOI: https://doi.org/10.1163/156856706778938509