Solvent free Beckmann rearrangement of ketoximes by anhydrous ferric chloride

Article abstract of DOI:10.1081/SCC-100104423

Beckmann rearrangement of ketoximes is achieved efficiently by anhydrous FeCl₃ in the absence of solvent. Unsymmetrical oximes are selectively produced one of the two possible products in good yields. Similar reactions are not occurred in the presence of solvent.

Full text of DOI:10.1081/SCC-100104423

This article was downloaded by: [University of Wyoming Libraries]
On: 06 October 2013, At: 00:04
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
SOLVENT FREE BECKMANN REARRANGEMENT OF
KETOXIMES BY ANHYDROUS FERRIC CHLORIDE
M. M. Khodaei a , F. A. Meybodi b , N. Rezai b & P. Salehi c
a Department of Chemistry, Razi University, Kermanshah, Iran
b Department of Phytochemistry, Medicinal Plants Research Institute, Shahid Beheshti
University, Tehran, Iran
c Department of Phytochemistry, Medicinal Plants Research Institute, Shahid Beheshti
University, Tehran, Iran
Published online: 09 Nov 2006.
To cite this article: M. M. Khodaei , F. A. Meybodi , N. Rezai & P. Salehi (2001) SOLVENT FREE BECKMANN REARRANGEMENT
OF KETOXIMES BY ANHYDROUS FERRIC CHLORIDE, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 31:13, 2047-2050, DOI: 10.1081/SCC-100104423
To link to this article: http://dx.doi.org/10.1081/SCC-100104423
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of
the Content. Any opinions and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied
upon and should be independently verified with primary sources of information. Taylor and Francis shall
not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other
liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or
arising out of the use of the Content.
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. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

SYNTHETIC COMMUNICATIONS, 31(13), 2047–2050 (2001)
SOLVENT FREE BECKMANN
REARRANGEMENT OF KETOXIMES BY
ANHYDROUS FERRIC CHLORIDE
M. M. Khodaei,1,* F. A. Meybodi, N. Rezai,
and P. Salehi2,*
1Department of Chemistry, Razi University, Kermanshah, Iran
2Department of Phytochemistry, Medicinal Plants Research
Institute, Shahid Beheshti University, Tehran, Iran
ABSTRACT
Beckmann rearrangement of ketoximes is achieved
efficiently by anhydrous FeCl3 in the absence of solvent.
Unsymmetrical oximes are selectively produced one of the
two possible products in good yields. Similar reactions are
not occurred in the presence of solvent.
Recently considerable attention has been paid to solvent free reac-
tions.1,2 These reactions are not only of interest from an ecological point of
view, but in many cases also offer considerable synthetic advantages in terms
of yield, selectivity and simplicity of the reaction procedure. One of the areas
of central attention in this field includes reaction between solids.3,4
Many reagents have been used in the Beckmann rearrangement of
ketoximes in solution.5–16 However most of them are strong Bronsted
acids and cause serious problems on starting materials and products.
*Corresponding authors.
2047
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

ORDER
REPRINTS
2048
KHODAEI ET AL.
Scheme.
Table 1. Beckmann Rearrangement of Ketoximes into Amides by FeCl3 Under
Neat Conditions

ORDER
REPRINTS
BECKMANN REARRANGEMENT OF KETOXIMES
2049
In this communication we present a convenient and efficient method
for isomerization of ketoximes into the corresponding amides by the cheap
and commercially available FeCl3 in the absence of solvent (Scheme). The
results are summarized in the Table.
In an easy procedure the starting materials were mixed together in
a mortar and heated in an oven for the appropriate period of time without
any further agitation. Symmetrical oximes were converted to the corre-
sponding amides in good to excellent yields (Table, entries 1–5). In the
case of unsymmetrical oximes the reaction was stereoselective and one
of the two possible amides produced mainly (Table, entries 6–8).
We also tried to conduct similar reactions in the presence of a number
of solvents, but in most cases a great amount of oxime remained intact and
a few percent of different products were obtained.
In conclusion the present procedure not only has the chemical,
economical and environmental advantages of solvent free reactions but
also constitute a method for high yield Beckmann rearrangement of symme-
trical and unsymmetrical ketoximes.
EXPERIMENTAL
All of the products are known compounds and were identified by
1
comparison of their spectral data (IR, H NMR) and physical properties
with those of authentic samples. Reaction monitoring was accomplished by
thin layer chromatography on silica gel Polygram SIL G/UV 254 sheets.
Yields refer to isolated products.
General Procedure for Conversion of Oximes into Amides
The oxime (10 mmol) and FeCl3 (30–40 mmol) were mixed in a mortar.
The reaction mixture was allowed to stand at 80–90ꢀC for 1.5–3 h. The
progress of reaction was followed by dissolving a sample in acetone and
monitoring on silica gel plates (SIL G/UV 254 Plates). Water (15 ml)
was added and the whole extracted with chloroform (3 Â 20 ml). Drying
and evaporation of the solvent gave the products in 81–95% yields which
recrystallized from n-heptane.

ORDER
REPRINTS
2050
KHODAEI ET AL.
ACKNOWLEDGMENT
We are grateful to Razi University Research Council for financial
support of this work.
REFERENCES
1. Metzger, J.D. Angew. Chem. Int. Ed. 1998, 37, 2975.
2. Tanaka, K. and Toda, F. Chem. Rev. 2000, 100, 1025.
3. Toda, F. Acc. Chem. Res. 1995, 28, 480.
4. Salehi, P.; Farrokhi, A. and Gholizadeh, M. Synth. Commun.
2000, in press.
5. Tivan, E. J. Chem. Soc. 1965, 3881.
6. Morson, R.S. and Broline, B.M. Can. J. Chem. 1973, 51, 942.
7. Costa, A.; Mestres, R. and Riego, Y.M. Synth. Commun. 1982,
12, 1063.
8. Bulta, R.N. and O’Donoghue, D.A. J. Chem. Res. (s) 1983, 18.
9. Eaton, P.E.; Coulson, G.R. and Lea, J.T. J. Org. Chem. 1973, 38, 4071.
10. Broun, R.F.; Van Gulick, N.M. and Schmid, G.H. J. Am. Chem. Soc.
1955, 77, 1094.
11. Ghiaci, M. and Imanzadeh, G.H. Synth. Commun. 1998, 28, 2275.
12. Yashima, T.; Horie, S.; Saito, S. and Hara, N. Nippon Kagaku Kaishi
1977, 1, 77.
13. Costa, A.; Deya, P.M.; Sinisterra, J.V. and Marinas, J.M. Can.
J. Chem. 1980, 58, 1266.
14. Sato, S.; Hasebe, S.; Sakurai, H.; Urabe, K. and Izvmi, Y. Appl. Catal.
1987, 29, 107.
15. Reddy, J.S.; Ravishankar, R.; Sivasanker, S. and Ratnasamy, P. Catal.
Lett. 1993, 17, 139.
16. Alvarez, C.; Cano, A.C.; Rivera, V. and Marquez, C. Synth. Commun.
1987, 17, 279.
Received in the Netherlands September 13, 2000

Request Permission or Order Reprints Instantly!
Interested in copying and sharing this article? In most cases, U.S. Copyright
Law requires that you get permission from the article’s rightsholder before
using copyrighted content.
All information and materials found in this article, including but not limited
to text, trademarks, patents, logos, graphics and images (the "Materials"), are
the copyrighted works and other forms of intellectual property of Marcel
Dekker, Inc., or its licensors. All rights not expressly granted are reserved.
Get permission to lawfully reproduce and distribute the Materials or order
reprints quickly and painlessly. Simply click on the "Request
Permission/Reprints Here" link below and follow the instructions. Visit the
U.S. Copyright Office for information on Fair Use limitations of U.S.
copyright law. Please refer to The Association of American Publishers’
(AAP) website for guidelines on Fair Use in the Classroom.
The Materials are for your personal use only and cannot be reformatted,
reposted, resold or distributed by electronic means or otherwise without
permission from Marcel Dekker, Inc. Marcel Dekker, Inc. grants you the
limited right to display the Materials only on your personal computer or
personal wireless device, and to copy and download single copies of such
Materials provided that any copyright, trademark or other notice appearing
on such Materials is also retained by, displayed, copied or downloaded as
part of the Materials and is not removed or obscured, and provided you do
not edit, modify, alter or enhance the Materials. Please refer to our Website
User Agreement for more details.
Order now!
Reprints of this article can also be ordered at
http://www.dekker.com/servlet/product/DOI/101081SCC100104423