Table 1 Continued
Alcohola
Estera
Yieldb (%)
m/zb
mpb/¡C
98
93
90
92
95
266
280
294
308
È
È
È
È
È
1022
11e
10aÈe
11aÈe
382, 384c
98
93
90
92
95
118
146
174
202
È
È
È
È
È
350, 352c
a The reactant carboxylic acids and alcohols, along with the product esters, are deÐned on Scheme 1. b Yields of the pure isolated esters, their
molecular ions [M]` and the melting point of all solid esters are given in the order NaÈe within each group corresponding to the reaction of
alcohol N with the 5 carboxylic acids AÈE. c The e esters show two molecular ion peaks due to the 35Cl and 37Cl isotopes. d No reaction was
observed with 6@ or with 9. e The diester was formed in all cases.
8
9
S. L. Beaukage and K. K. Ogilvie, T etrahedron L ett., 1977, 1691.
N. Ono, T. Yamada, T. Saito, K. Tanaka and A. Kaji, Bull. Chem.
Soc. Jpn, 1978, 51, 2401.
General procedure for the esteriÐcation of alcohols and
carboxylic acids catalysed by ceric ammonium nitrate
10 V. Bocchi, G. Casanti, A. Dossena and R. Marchelli, Synthesis,
1979, 957.
11 J. B. Hendrickson and S. M. Schwartzman, T etrahedron L ett.,
A mixture of an alcohol (1.5 mmol) and a carboxylic acid (1.5
mmol) was allowed to heat at a temperature of 55È60 ¡C in
the presence of ceric ammonium nitrate (0.10 mmol) for a
period of 30È60 min. The reaction was followed by TLC.
Chloroform was added if necessary to dissolve the acid or
alcohol used in the reaction. To work up the reaction the
mixture was poured into cold water (100 ml) and extracted
with petroleum ether (2 ] 100 ml). The organic extract, after
drying over anhydrous sodium sulfate, was evaporated under
reduced pressure to obtain the product ester, which was
further puriÐed by preparative TLC. Since the reactions with
all the substrates were carried out on a small scale with a
minimum amount of CAN, the catalyst could not be recycled
and went into the aqueous phase during work-up.
1975, 277.
12 E. Vedegs, N. S. Bennett, L. M. Conn, S. T. Diver, M. Gingrass,
S. Lin, P. A. Oliver and M. J. Peterson, J. Org. Chem., 1993, 58,
7286.
13 K. Ishihara, M. Kubota, H. Kurihara and H. Yamamota, J. Am.
Chem. Soc., 1995, 117, 4413; K. Ishihara, M. Kubota, H. Kuri-
hara and H. Yamamota, J. Am. Chem. Soc., 1995, 117, 6639.
14 K. Ishihara, M. Kubota, H. Kurihara and H. Yamamota, J. Org.
Chem., 1996, 61, 4560.
15 (a) A. G. M. Barret and D. C. Braddock, Chem. Commun., 1997,
351; (b) T. Hanamoto, Y. Sugimoto, Y. Yakoyama and J.
Inanaga, J. Org. Chem., 1996, 61, 4491.
16 P. A. Porocopiou, S. P. D. Baugh, S. S. Flack and G. G. A. Inglis,
J. Org. Chem., 1998, 63, 2342.
17 P. K. Chowdhury, M. J. Bordoloi, N. C. Barua, P. K. Goswami,
H. P. Sarmah, R. P. Sharma, A. P. Barua, R. K. Mathur and A.
C. Ghosh, US Pat. 5,808,117, 1998; Indian Pat. 1645/DEL, 1994.
18 (a) P. Borah, M. Ahmed and P. K. Chowdhury, J. Chem, Res. (S),
1998, 238; (b) P. Borah, M. Ahmed and P. K. Chowdhury, J.
Chem. Res. (M), 1998, 1173; (c) P. Borah and P. W. Chowdhury,
J. Chem. Res. (S), 1996, 502.
Acknowledgements
The authors thank the Director, RRL Jorhat, for providing
facilities necessary for this work. One of us (P.G.) thanks
CSIR, New Delhi, for a Senior Research Fellowship. The
Quality Control Management Centre of this laboratory is also
gratefully acknowledged for IR, NMR and mass spectral data.
19 P. K. Chowdhury, A. Prelle, D. Schomburg, M. Thielmann and
E. Winterfeldt, L iebigs Ann. Chem., 1987, 1095.
20 A. K. Singhal, P. K. Chowdhury, R. P. Sharma, J. N. Barua and
W. Herz, Phytochemistry, 1982, 21, 462.
References
21 P. K. Chowdhury, N. C. Barua, R. P. Sharma, G. Thyagarajan
and W. Herz, J. Org. Chem., 1980, 45, 535.
1
P. J. Kocienski, in Protecting Groups, ed. D. Enders, R. Noyori
and B. M. Trost, Thieme, Stuttgart, 1994, pp. 119È154.
(a) T. W. Greene, in Protecting Groups in Organic Synthesis, ed.
J. F. W. McOmie, Wiley, New York, 1981, pp. 50È66; (b) E.
Haslam, Protecting Groups in Organic Chemistry, ed. J. F. W.
McOmie, Plenum, London, 1973, p. 183.
22 V. S. Shukla, N. C. Barua, P. K. Chowdhury, R. P. Sharma, M. J.
Bordoloi and U. Rychlewska, T etrahedron, 1986, 42, 1157.
23 J. R. Hewe, K.-L. Chen and S. Anathan, J. Chem. Soc., Chem.
Commun., 1994, 1425.
2
24 M. V. R. Reddy, B. Malhotra and Y. D. Vanker, T etrahedron
L ett., 1995, 36, 4861.
3
4
5
E. Haslam, T etrahedron, 1980, 36, 2409 and references cited
25 A. Ates, A. Gautier, B. Leroy, J. M. Plancher, Y. Quensel and E.
Marko, T etrahedron L ett., 1999, 44, 1299.
therein.
R. Nakao, K. Oka and T. Fukumoto, Bull. Chem. Soc. Jpn., 1981,
54, 1267.
T. Mukaiyama, M. Usui, E. Shimada and K. Saigo, Chem. L ett.,
1975, 1045.
26 V. Nair, L. G. Nair, L. Balagopal and R. Rajan, Indian J. Chem.,
Sect. B, 1999, 38, 1234.
27 (a) L. B. Young and W. Trahanovsky, J. Am. Chem. Soc., 1969,
91, 5060; (b) W. Trahanovsky, P. J. Flash and L. M. Smith, J.
Am. Chem. Soc., 1969, 91, 5068.
6
7
A. Hassner and V. Alexandrian, T etrahedron L ett., 1978, 4475.
(a) A. Hassner, V. Alexandrian and L. Krepski, T etrahedron,
1978, 34, 2069; (b) G. HoÑe and W. Steiglich, T etrahedron L ett.,
1970, 4727.
New J. Chem., 2000, 24, 955È957
957