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the latter with piperidine in acetonitrile, and was identified
by its H NMR spectrum.
O
MeS
C N
8a
4.2. Kinetic measurements
These were carried out by means of a diode array ꢁspectro-
photometer, in an aqueous solution, at 25.0ꢀ0.1 C with
an ionic strength of 0.2 M (KCl). The reactions were initi-
ated by the addition (10 mL) of a stock solution of the sub-
strate in acetonitrile into the aqueous solution of the amine
(3 mL), at the appropriate pH, contained in a cell placed in
the thermostated compartment of the spectrophotometer.
The initial substrate concentration was 1–2ꢂ10ꢃ5 M. Usu-
ally the pH was maintained by the corresponding amine–
aminium pair, except in the reactions with 3-cyano and 4
cyano pyridines (where 0.005 M acetate buffer was used)
and those with piperidine (where 0.01 M borate buffer was
used). The reactions were followed at 220–500 nm and car-
ried out under an excess (10-fold at least) of the amine over
the substrate.
3. (a) Castro, E. A.; Moodie, R. B. J. Chem. Soc., Perkin Trans. 2
1974, 658–661; (b) Bond, P. M.; Castro, E. A.; Moodie, R. B.
J. Chem. Soc., Perkin Trans. 2 1976, 68–72; (c) Makarevich,
N. M.; Orlov, S. I.; Chimishkyan, A. L.; Kanygina, A. L.
Org. React. (Tartu) 1990, 27, 3–12; (d) Yew, K. H.; Koh,
H. J.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2
1995, 2263–2268; (e) Koh, H. J.; Han, K. L.; Lee, H. W.;
Lee, I. J. Org. Chem. 1998, 63, 9834–9839; (f) Castro, E. A.;
Ruiz, M. G.; Salinas, S.; Santos, J. G. J. Org. Chem. 1999, 64,
4817–4820; (g) Castro, E. A.; Ruiz, M. G.; Santos, J. G. Int. J.
Chem. Kinet. 2001, 33, 281–287.
4. (a) Queen, A.; Nour, T. A.; Paddon-Row, M. N.; Preston, K.
Can. J. Chem. 1970, 48, 522–527; (b) McKinnon, D. M.;
Queen, A. Can. J. Chem. 1972, 50, 1401–1406; (c) Kevill,
D. N.; D’Souza, M. J. J. Org. Chem. 1998, 63, 2120–2124;
(d) Kevill, D. N.; D’Souza, M. J. Can. J. Chem. 1999, 77,
1118–1122.
5. (a) Castro, E. A.; Cubillos, M.; Santos, J. G. J. Org. Chem.
1997, 62, 4395–4397; (b) Castro, E. A.; Cubillos, M.; Santos,
J. G. J. Org. Chem. 2004, 69, 4802–4807; (c) Oh, H. K.; Ha,
J. S.; Sung, D. D.; Lee, I. J. Org. Chem. 2004, 69, 8219–8223.
6. Castro, E. A.; Cubillos, M.; Santos, J. G. J. Org. Chem. 1998,
63, 6820–6823.
7. (a) Castro, E. A.; Aliaga, M.; Santos, J. G. J. Org. Chem. 2004,
69, 6711–6714; (b) Castro, E. A.; Aliaga, M.; Santos, J. G.
J. Org. Chem. 2005, 70, 2679–2685.
For the reactions with pyridines an intermediate was de-
tected spectrophotometrically (270–320 nm), as shown by
a fast absorbance increase followed by a slow decrease
(see Section 2). In the case of the reactions with 3-chloro-
pyridine we assume the intermediate to be 1-(S-methyl-
carbonyl)-3-chloropyridinium cation (7a). The kinetics for
all the reactions were measured under conditions where de-
composition of the intermediate was slower than its forma-
tion. Pseudo-first-order rate coefficients (kobsd) were found
for all the reactions by means of the kinetic software of
the spectrophotometer.
´
8. (a) Guillot-Edelheit, G.; Laloi-Diard, M.; Guibe-Jampel, E.;
4.3. Product studies
Wakselman, M. J. Chem. Soc., Perkin Trans. 2 1979, 1123–
1127; (b) Battye, P. J.; Ihsan, E. M.; Moodie, R. B. J. Chem.
Soc., Perkin Trans. 2 1980, 741–748; (c) Chryistiuk, E.;
Williams, A. J. Am. Chem. Soc. 1987, 109, 3040–3046.
9. Castro, E. A.; Ureta, C. J. Org. Chem. 1989, 54, 2153–2159.
10. Bell, R. P. The Proton in Chemistry; Methuen: London, 1959;
p 159.
11. Gresser, M. J.; Jencks, W. P. J. Am. Chem. Soc. 1977, 99, 6963–
6970.
12. (a) Castro, E. A.; Gil, F. J. J. Am. Chem. Soc. 1977, 99,
7611–7612; (b) Castro, E. A.; Freudenberg, M. J. Org. Chem.
For the reaction with piperidine, compound 8a was identified
as one of the products. This was achieved by comparison of
the UV–vis spectrum at the end of the reaction with that of an
authentic sample at the same experimental conditions.
Acknowledgment
M.A. thanks CONICYTof Chile (AT-24050119) and M.G. is
grateful to DIPUC of our University for doctoral fellow-
ships.
´
1980, 45, 906–910; (c) Castro, E. A.; Iban˜ez, F.; Lagos, S.;
Schick, M.; Santos, J. G. J. Org. Chem. 1992, 57, 2691–2694;
(d) Castro, E. A.; Cubillos, M.; Aliaga, M.; Evangelisti, S.;
Santos, J. G. J. Org. Chem. 2004, 69, 2411–2416.
13. Castro, E. A. Chem. Rev. 1999, 99, 3505–3524 and references
therein.
14. Satterthwait, A. C.; Jencks, W. P. J. Am. Chem. Soc. 1974, 96,
7018–7031.
15. Castro, E. A.; Cubillos, M.; Santos, J. G.; Tellez, J. J. Org.
Chem. 1997, 62, 2512–2517.
References and notes
1. Kevill, D. N. The Chemistry of the Functional Groups: The
Chemistry of Acyl Halides; Patai, S., Ed.; Wiley: New York,
NY, 1972; Chapter 12.
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184–188; Butler, A. R.; Robertson, I. H.; Bacaloglu, R. J. Chem.
Soc., Perkin Trans. 2 1974, 1733–1736; La, S.; Lee, I. J. Korean
Chem. Soc. 1980, 24, 288–294; Kevill, D. N.; Kyong, J. B.;
Weitl, F. L. J. Org. Chem. 1990, 55, 4304–4311; Koo, I. S.;
16. Pearson, R. G. J. Chem. Educ. 1968, 45, 581; Pearson, R. G.
J. Org. Chem. 1989, 54, 1423–1430.