Ceric(IV) ammonium nitrate mediated transesterification and esterification

Article abstract of DOI:10.1081/SCC-120004264

The transesterification of carboxylic esters and the esterification of carboxylic acids are effected under mild conditions in the presence of ceric(IV) ammonium nitrate (CAN).

Full text of DOI:10.1081/SCC-120004264

This article was downloaded by: [Duke University Libraries]
On: 03 May 2012, At: 00:30
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
CERIC(IV) AMMONIUM NITRATE MEDIATED
TRANSESTERIFICATION AND ESTERIFICATION
Bogdan Štefane a , Marijan Kočevar a & Slovenko Polanc a
a Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5,
Ljubljana, SI-1000, Slovenia
Available online: 16 Aug 2006
To cite this article: Bogdan Štefane, Marijan Kočevar & Slovenko Polanc (2002): CERIC(IV) AMMONIUM NITRATE MEDIATED
TRANSESTERIFICATION AND ESTERIFICATION, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 32:11, 1703-1707
To link to this article: http://dx.doi.org/10.1081/SCC-120004264
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to
anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae, and drug doses should
be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims,
proceedings, demand, or costs or damages whatsoever or howsoever caused arising directly or indirectly in
connection with or arising out of the use of this material.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
SYNTHETIC COMMUNICATIONS, 32(11), 1703–1707 (2002)
CERIC(IV) AMMONIUM NITRATE
MEDIATED TRANSESTERIFICATION
AND ESTERIFICATION
*
Bogdan Stefane, Marijan Kocevar, and
Slovenko Polanc
Faculty of Chemistry and Chemical Technology,
University of Ljubljana, Askerceva 5,
SI-1000 Ljubljana, Slovenia
ABSTRACT
The transesterification of carboxylic esters and the esterifica-
tion of carboxylic acids are effected under mild conditions in
the presence of ceric(IV) ammonium nitrate (CAN).
Transesterification and esterification represent powerful methods to
synthesise a variety of organic esters.[1] Typically, the reactions are catalysed
by strong acids or bases[1,2] and enzymes.[3] There are reports on using
titanium(IV) alkoxides,[4] tetraalkyldistannoxanes,[5] aluminium oxide,[6]
[7]
ZrO2 or binary Mo-ZrO2 oxide, and ferric perchlorate adsorbed on
silica gel[8] as catalysts for transesterification and esterification.
As a part of our continuous efforts concerning reactions of hydrazides
and their derivatives,[9] we have recently reported on the application of
ceric(IV) ammonium nitrate as a reagent for the conversion of hydrazides
to esters.[10] We would like to report herein the first application of ceric(IV)
*Corresponding author.
1703
Copyright & 2002 by Marcel Dekker, Inc.
www.dekker.com

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
1704
STEFANE, KOCEVAR, AND POLANC
Scheme 1.
ammonium nitrate for transesterification and esterification reactions
(Scheme 1).
Initially, transesterification of ethyl hypurate was studied (Table 1,
Entries 1 and 2). In order to achieve a high conversion of the starting
ester in reasonable time, two equivalents of CAN were required. Similar
transformations with different starting esters and alcohols were carried
out. In all cases, the reaction led to a single product and after evaporation,
followed by extraction with dichloromethane, we isolated esters in pure
form and high yields.
Having demonstrated that CAN served efficiently in the transesterifi-
cation reactions, we decided to investigate the use of CAN for esterification
reactions. As it is evident from Table 2, CAN can also be applied for
esterification of carboxylic acids.
Although the precise mechanism of transesterification of carboxylic
esters and esterification of carboxylic acids with CAN remains unclear, the
reaction might be explained by the initial coordination of carboxylic oxy-
gens by Ce(IV), which is followed by nucleofilic attack by alcohol, deriving
carboxylic esters.
The method cannot be applied to substrates containing thiol and sul-
phide groups or to 1,3-ketoesters due to oxidation of substrates.
Furthermore, mandelic acid undergoes decarboxylation and oxidation lead-
ing quantitatively to benzaldehyde (Table 2, Entry 10).
In conclusion, the fact that metals often behave as the equivalents of
hydrogen has long been recognized by chemists. As Davies said:[11]
‘‘Anything hydrogen can do, a metal can do better.’’ Cerium (IV) ammonium
nitrate is introduced herein for this purpose. The described approach seems to
be a method of choice for a simple preparation of various esters employing
mild reaction conditions and giving high yields of the desired products.
EXPERIMENTAL
In a typical experiment, CAN (2 mmol) was added at room temperature
to a suspension of carboxylic acid or to a solution of ester 1 (1 mmol) in the
appropriate alcohol 2 (5–8 ml). The reaction mixture was stirred at r.t. for the
time indicated in Tables 1 and 2, evaporated to dryness, treated with water

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
CERIC(IV) AMMONIUM NITRATE
1705

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
1706
STEFANE, KOCEVAR, AND POLANC
Table 2. Esterifications Mediated by CAN
Reaction Time Yield
(%)b
Entry
Starting Material
Producta
(h)
1
2
3
4
5
6
7
8
9
10
PhCONHCH2CO2H
PhCONHCH2CO2Me
36
40
97
90
88
95
86
73
99
92
81
99
4-PyCONHCH2CO2H 4-PyCONHCH2CO2Me
4-NO2C6H4CO2H 4-NO2C6H4CO2Me
4-Cl, 3-NO2C6H3CO2H 4-Cl, 3-NO2C6H3CO2Me
4-ClC6H4CH2CO2H
4-PyCO2H
PhCH¼CHCO2H
PhCONHCH2CO2H
PhCONHCH2CO2H
PhCH(OH)CO2H
408
336
360
240
240
360
192
4-ClC6H4CH2CO2Me
4-PyCO2Me
PhCH¼CHCO2Me
PhCONHCH2CO2Et
PhCONHCH2CO2Bui
PhCHO
0.5
11
53
97
aAll products are identical with those available from commercial sources and those
from the literature.
bYields of isolated products are given.
(10 cm3) and product extracted with dichloromethane (6 ꢁ 15 cm3). The
organic phase was dried over anhydrous sodium sulfate and evaporated to
yield the corresponding ester 3. Selected examples are listed in Tables 1 and 2.
ACKNOWLEDGMENTS
The authors thank Dr. Bogdan Kralj and Dr. Dusan Zigon (Mass
Spectrometry Center, Jozef Stefan Institute, Ljubljana, Slovenia) for mass
measurements. The Ministry of Education, Science and Sport of Slovenia
(PO-0503-0103) and the Slovenian Science Foundation are gratefully
acknowledged for the financial support.
REFERENCES
1. (a) Mulzer, J. In Comprehensive Organic Synthesis, Trost, B.M., Ed.;
Pergamon Press, 1991; Vol. 6, p. 339; (b) Sandler, S.R.; Caro, W. Organic
Functional Group Preparation; Academic Press Inc., 1983; p. 397;

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
CERIC(IV) AMMONIUM NITRATE
1707
(c) Otera, J. Chem. Rev. 1993, 1449. (d) For a comprehensive list of
transesterification and esterification methods, see, Larock, R. C.
Comprehensive Organic Transformations, 2nd Ed.; Wiley, 1999;
p. 1863, 1932 and 1969.
2. Taber, D.F.; Amedio, J.C.; Patel, Y.K. J. Org. Chem. 1985, 50, 3618.
3. Santaniello, E.; Ferraboschi, P.; Grisenti, P. Enzyme Microb. Technol.
1993, 15, 367.
4. (a) Seebach, D.; Hunglerbuehler, E.; Naef, R.; Shnurrenberger, P.;
Weidman, B.; Zueger, M. Synthesis 1992, 138; (b) Haslam, J.H. US
Patent 2, 822, 348, 1958; (c) Pellegatta, C.J.; Casosoux, P.-L. Catal.
Lett. 1997, 43, 139; (d) Krasik, P. Tetrahedron Lett. 1998, 39, 4223.
5. Otera, J.; Dan-Oh, N.; Nozaki, H. J. Org. Chem. 1991, 56, 5307.
6. Postner, G.H.; Oda, M. Tetrahedron Lett. 1981, 22, 5003.
7. Manohar, B.V.; Reddy, R.; Reddy, B.M. Synth. Commun. 1998, 28,
3183.
8. Parmar, A.; Kaur, J.; Goyal, R.; Kumar, B.; Kumar, H. Synth.
Commun. 1998, 28, 2821.
9. (a) Kocevar, M.; Susin, P.; Polanc, S. Synthesis 1993, 773; (b) Kocevar,
M.; Mihorko, P.; Polanc, S. Synlett 1995, 241; (c) Kocevar, M.;
Mihorko, P.; Polanc, S. J. Org. Chem. 1995, 60, 1466; (d) Kosmrlj,
J.; Kocevar, M.; Polanc, S. Synlett 1996, 652; (e) Stefane, B.; Kocevar,
M.; Polanc, S. J. Org. Chem. 1997, 62, 7156; (f ) Kosmrlj, J.; Kocevar,
M.; Polanc, S. J. Chem. Soc., Perkin. Trans. I 1998, 3917; (g) Lenarsic,
R.; Kocevar, M.; Polanc, S. J. Org. Chem. 1999, 64, 2558; (h) Kafka,
S.; Trebse, P.; Polanc, S.; Kocevar, M. Synlett 2000, 254.
10. Stefane B.; Kocevar, M.; Polanc, S. Tetrahedron Lett. 1999, 40, 4429.
11. Davies, A.G. J. Chem. Soc. Perkin Trans. I 2000, 1997.
Received in the Netherlands May 30, 2001

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.