W.-B. Pan et al. / Tetrahedron Letters 44 (2003) 331–334
333
10. Wakasugi, K.; Nakamura, A.; Tanabe, Y. Tetrahedron
Lett. 2001, 42, 7427.
11. See e.g.: (a) Zacharie, B.; Connolly, T. P.; Penney, C. L.
J. Org. Chem. 1995, 60, 7072; (b) Vedejs, E.; Daugulis, O.
J. Org. Chem. 1996, 61, 5702; (c) Wright, S. W.; Hage-
man, D. L.; McClure, L. D. Tetrahedron Lett. 1997, 38,
7345; (d) Thierry, J.; Yue, C.; Potier, P. Tetrahedron Lett.
1998, 39, 1557.
Scheme 2.
12. Nair, V.; Mathew, J.; Prabhakaran Chem. Soc. Rev. 1997,
127.
13. Trahanovsky, W. S.; Robbins, M. D. J. Am. Chem. Soc.
1971, 93, 5256.
14. Lumieux, R. V.; Ratchiffe, R. M. Can. J. Chem. 1979, 57,
1244.
reaction took place much faster requiring only 2 min.
In the event, no esterification occurred, instead result-
ing in the formation of 4-methoxybenzaldehyde 9 and
1-methoxy-4-nitrobenzene 10 in 20 and 68% yields,
respectively (Scheme 2).24,25
15. Nair, V.; Nair, L. G. Tetrahedron Lett. 1998, 39, 4585.
16. Nair, V.; George, T. G.; Nair, L. G.; Panicker, S. B.
Tetrahedron Lett. 1999, 40, 1195.
17. Nair, V.; George, T. G. Tetrahedron Lett. 2000, 41, 3199.
18. Nair, V.; Nair, L. G.; George, T. G.; Augustine, A.
Tetrahedron 2000, 56, 7607.
In conclusion, we have explored a facile and efficient
route for the esterification reaction between aliphatic
and aromatic carboxylic acids and simple primary or
secondary alcohols, (which also act as solvents) using
cerium(IV) ammonium nitrate. This method did not
necessitate the use of a dehydrating reagent and/or the
azeotropic removal of water. Evidently, the present
procedure appears attractive for its operational simplic-
ity, and generally high yields of products.
19. Iacobellis, N. S.; De Vay, J. E. Physiol. Plant. Pathol.
1987, 30, 421.
20. Spectral data of: compound 4c (colorless liquid): 1H
NMR (CDCl3, 200 MHz) l 7.43–7.35 (m, 2H), 7.21–7.12
(m, 2H), 3.68 (s, 3H), 3.57 (s, 2H); 13C NMR (CDCl3, 50
MHz) l 171.0, 135.9, 132.1, 130.0, 129.8, 127.8, 122.3,
51.9, 40.4; EI–MS m/z 230 ((M+1)+, 11), 228 ((M−1)+,
11), 171 (55), 169 (55), 105 (55), 89 (100). 4d (colorless
liquid): 1H NMR (CDCl3, 200 MHz) l 7.47 (d, 2H,
J=8.6 Hz), 7.19 (d, 2H, J=8.6 Hz), 3.72 (s, 3H), 3.63 (s,
2H); 13C NMR (CDCl3, 50 MHz) l 171.5, 132.5, 131.2,
130.7, 120.6, 51.7, 39.9; EI-MS m/z 230 ((M+1)+, 58), 228
((M−1)+, 58), 171 (91), 169 (100), 89 (38). 4e (colorless
liquid): 1H NMR (CDCl3, 200 MHz) l 7.34–7.16 (m,
4H), 3.76 (s, 2H), 3.67 (s, 3H); 13C NMR (CDCl3, 50
MHz) l 170.6, 134.2, 132.1, 131.2, 129.2, 128.4, 126.6,
51.7, 38.6; EI-MS m/z 186 ((M+2)+, 3), 184 (M+, 7), 149
(74), 125 (100). 4f (colorless liquid): 1H NMR (CDCl3,
200 MHz) l 7.27 (s, 1H), 7.23–7.11 (m, 3H), 3.66 (s, 3H),
3.57 (s, 2H); 13C NMR (CDCl3, 50 MHz) l 171.0, 135.7,
134.0, 129.5, 129.2, 127.3, 127.1, 51.8, 40.3; EI-MS m/z
186 ((M+2)+, 5), 184 (M+, 15), 127 (31), 125 (100), 105
Acknowledgements
We thank the National Science Council of the Republic
of China for financial support of this program.
References
1. (a) Beaz, G. In Comprehensive Organic Synthesis; Trost,
B. M.; Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 6,
p. 323; (b) Franklin A. S. J. Chem. Soc., Perkin Trans. 1
1998, 2451 and 1999, 3537; (c) Otera, J. Chem. Rev. 1993,
93, 1449; (d) Greene, T. W.; Wuts, P. G. In Protective
Groups in Organic Synthesis; 3rd ed.; Wiley-Interscience:
New York, 1999; p. 372.
2. (a) Ziegler, F. E.; Berger, G. D. Synth. Commun. 1979, 9,
539; (b) Hassner, A.; Alexanian, V. Tetrahedron Lett.
1978, 19, 4475.
3. (a) Mukaiyama, T. Angew. Chem., Int. Ed. Engl. 1979,
18, 707; (b) Saigo, K.; Usui, M.; Kikuchi, K.; Shimada,
E.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1977, 50, 1863.
4. Inanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.;
Yamaguchi, M. Bull. Chem. Soc. Jpn. 1977, 52, 1989.
5. (a) Ohta, S.; Shimabayashi, A.; Aono, M.; Okamoto, M.
Synthesis 1982, 833; (b) Staab, H. A. Angew. Chem., Int.
Ed. Engl. 1962, 1, 351.
1
(28), 89 (57). 4g (colorless liquid): H NMR (CDCl3, 200
MHz) l 7.26 (dd, 2H, J=8.6 Hz), 7.17 (dd, 2H, J=8.6
Hz), 3.65 (s, 3H), 3.56 (s, 2H); 13C NMR (CDCl3, 50
MHz) l 171.0, 132.7, 132.3, 130.4, 128.4, 51.7, 40.1;
EI-MS m/z 186 ((M+2)+, 8), 184 (M+, 16), 127 (28), 125
(100), 89 (44). 4h (colorless liquid): 1H NMR (CDCl3, 200
MHz) l 7.31–7.17 (m, 2H), 6.97–6.86 (m, 2H), 3.82 (s,
3H), 3.69 (s, 3H), 3.65 (s, 2H); 13C NMR (CDCl3, 50
MHz) l 172.1, 157.4, 130.7, 128.4, 122.9, 120.4, 110.4,
55.3, 51.7, 35.6; EI-MS m/z 180 (M+, 24), 121 (65), 91
(100). 4i (colorless liquid): 1H NMR (CDCl3, 200 MHz) l
7.24 (t, 1H, J=8.4 Hz), 6.85 (s, 1H), 6.89–6.79 (m, 2H),
3.79 (s, 3H), 3.69 (s, 3H), 3.61 (s, 2H); 13C NMR (CDCl3,
50 MHz) l 171.6, 159.6, 135.2, 129.3, 121.4, 114.7, 112.4,
54.9, 51.7, 40.9; EI-MS m/z 180 (M+, 37), 121 (100), 91
(36), 77 (38).
6. Meseguer, J. D.; Coll, A. L. P.; Lizarbe, J. R. F.; Bilbao,
A. Z. Synthesis 1980, 547.
7. (a) Denis, J. N.; Greene, A. E. J. Am. Chem. Soc. 1988,
110, 5917; (b) Kim, S.; Lee, J. I.; Ko, Y. K. Tetrahedron
Lett. 1984, 25, 4943.
21. Beckwith, A. L. J.; Gerba, S. Aust. J. Chem. 1992, 45,
289.
8. Saitoh, K.; Shiina, I.; Mukaiyama, T. Chem. Lett. 1998,
679.
22. Salerno, C. P.; Magde, D.; Patron, A. P. J. Org. Chem.
2000, 65, 3971.
9. Wakasugi, K.; Misaki, T.; Yamada, K.; Tanabe, Y.
Tetrahedron Lett. 2000, 41, 5249.