Regeneration of ketones from oximes in dry media under microwave irradiation

Article abstract of DOI:10.1081/SCC-120003142

Regeneration of ketones from oximes have been achieved using HCOOH/SiO₂ as solid support catalyst in dry media under microwave irradiation with 86～94% yield.

Full text of DOI:10.1081/SCC-120003142

This article was downloaded by: [Stony Brook University]
On: 01 November 2014, At: 07:53
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
REGENERATION OF KETONES FROM OXIMES IN DRY
MEDIA UNDER MICROWAVE IRRADIATION
a
b
c
Jian-Feng Zhou , Shu-Jiang Tu & Jun-Cai Feng
a
Department of Chemistry , Huaiyin Normal College , Huaiyin, 223001, China
Department of Chemistry , Xuzhou Normal University , Xuzhou, 221009, China
Department of Chemistry , Nanjing University , Nanjing, 210093, China
b
c
Published online: 21 Aug 2006.
To cite this article: Jian-Feng Zhou , Shu-Jiang Tu & Jun-Cai Feng (2002) REGENERATION OF KETONES FROM OXIMES IN DRY
MEDIA UNDER MICROWAVE IRRADIATION, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 32:7, 959-962, DOI: 10.1081/SCC-120003142
To link to this article: http://dx.doi.org/10.1081/SCC-120003142
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, 32(7), 959–962 (2002)
REGENERATION OF KETONES FROM
OXIMES IN DRY MEDIA UNDER
MICROWAVE IRRADIATION
1
2
3,
Jian-Feng Zhou, Shu-Jiang Tu, and Jun-Cai Feng *
1
Department of Chemistry,
Huaiyin Normal College, Huaiyin 223001, China
2
Department of Chemistry,
Xuzhou Normal University, Xuzhou 221009, China
3
Department of Chemistry,
Nanjing University, Nanjing 210093, China
ABSTRACT
Regeneration of ketones from oximes have been achieved
using HCOOH/SiO as solid support catalyst in dry media
2
under microwave irradiation with 86 ꢀ 94% yield.
Oximes are extensively employed for characterization and purification
1
of carbonyl compounds as well as in the preparation of amides. Oximes
can be prepared from carbonyl and non-carbonyl compounds (i.e. Barton
2
–3
reaction
etc.); therefore, deoximation of such oximes provides an alter-
native method for the synthesis of carbonyl compounds. In recent years
cleavage of oximes to regenerate the parent carbonyl compounds has
received much attention. Owing to the relative hydrolytic stability of
oximes, a wide variety of deoximation reagents have been developed such
*
Corresponding author.
9
59
Copyright & 2002 by Marcel Dekker, Inc.
www.dekker.com

9
60
ZHOU, TU, AND FENG
4
5
as chromium trioxide-silica gel and Ni(II)-complex catalyst . However,
these methods were performed in liquid phase and require stoichiometric
or excess amounts of organic solvents. In some cases, reaction time is long
6
(
12 ꢀ 94 h) and the yield obtained very low.
Microwave irradiation in organic synthesis is a useful technique.
7
Dry media using microwave heating have attracted much attention.
A number of deoximation methods has been developed in dry media under
8
microwave irradiation, such as silica supported ammonium persulfate, silica
9
10
11,12
supported sodium periodate, pyridinium chloro-chromate and clayfen.
In our laboratory, HCOOH/SiO was used as a solid support catalyst for
synthesis of nitriles in dry media under microwave irradiation.
HCOOH/SiO was also used for synthesis of amides from ketones and
hydroxylamine in dry media under microwave irradiation, but further
investigation revealed that most ketones cannot be converted to amides
under these conditions. We found that the deoximation of ketoximes using
2
1
3
2
1
4
HCOOH/SiO as solid support catalyst in dry media under microwave
2
irradiation was easy. Here we report a new and efficient method to regenerate
ketones from oximes in dry media under microwave irradiation. The reactions
are generally complete in 2–4 min with excellent yield.
The results obtained are shown in Table 1.
EXPERIMENTAL
All reagents were commercially available and used without further
1
purification. HCOOH/SiO2 was prepared from literature procedure.
4
Melting points were determined in open capillaries and uncorrected. IR
spectra were recorded on a Nicolet FT-IR 5DX instrument. The reactions
were carried out under atmospheric pressure with a modified commercial
microwave oven (Sanle WP650D 650 W). All oximes were prepared by the
standard procedures from commercially available ketones.
GENERAL PROCEDURE
Oxime (10 mmol) and HCOOH/SiO (5 g) were thoroughly mixed in a
2
flask (50 ml), connected to refluxing equipment. After irradiation by micro-
wave for 2 ꢀ 4 min (as indicated by TLC), the mixture was cooled to room
temperature, dichloromethane was added, the mixture filtered and the fil-
trate washed with water and dried with anhydrous magnesium sulfate. The
solvent was evaporated to give crude product, which was further purified by
recrystallization or distillation.

REGENERATION OF KETONES
961
Table 1. Regeneration of Ketones from Oximes Using HCO
Under Microwave Irradiation
2
H/SiO
2
in Dry Media
Yield
ꢁ
Reaction
Time (min)
M.P. ( C) or b.p.
ꢁ
a
15
b
Entry
Products
( C) (Lit.)
(%)
1
2
2
2
130/133.33 Pa (130/133.33 Pa)
155/133.33 Pa (155/133.33 Pa)
86
87
3
4
5
6
7
8
9
0
1
2
C H COCH
6
3
4
2
2
3
3
3
4
4
3
66–67/0.88 Pa (67/0.88 Pa)
82–84/1.4 Pa (84–85/1.4 Pa)
79.5–80.5 (80–81)
92
90
94
94
93
92
91
5
3
C
6
5
H COC
2
H
5
4-O
3-O
2
NC
NC
6
H
4
COCH
COCH
3
3
2
6
H
4
80–81 (81)
4-ClC H COCH
3
98–99/1.23 Pa (99/1.23 Pa)
115–117/1.23 Pa (117/1.23 Pa)
107–108 (109)
111–112/1.93 Pa (112.5/1.93 Pa) 91
88/0.45 Pa (88–90/0.53 Pa)
48–49 (48.5–49)
6
4
3-BrC
6
4
H COCH
3
4-HOC
4-CH C H COCH
6
H
COCH
4 3
1
1
1
3
6
4
3
3,4-(CH
3
)
2
C
6
H
3
COCH
3
89
93
6 5 6 5
C H COC H
1
1
a
3
4
3
2
54–55 (56)
94–95 (95)
88
94
C H COCOC H
5
6
5
6
All products were characterized by m.p. (or b.p.), IR spectra.
b
Yields of the isolated products.
Based on these results, HCOOH/SiO can be used as an excellent
2
deoximation reagent for regeneration of ketones from oximes in dry
media under microwave irradiation.
REFERENCES
1
. Bosch, A.I.; Creez, P.; Diez-Barra, E.; Loupy, A.; Lange, F. Synlett
995, 1259.
. Barton, D.H.R.; Beaton, J.M.; Pechell, M.M. J. Am. Chem. Soc. 1961,
3, 4083.
1
2
8
3
4
. Barton, D.H.R.; Beaton, J.M. J. Am. Chem. Soc. 1961, 83, 4083.
. Bendale, P.M.; Khadilkar, B.M. Synth. Commun. 2000, 30, 665. And
reference cited therein.

9
62
ZHOU, TU, AND FENG
5. Blay, G.; Benach, E.; Fernandez, I.; Galletero, S.; Pedro, J.R.; Ruiz, R.
Synthesis 2000, 403.
6. Maloney, J.R.; Lyle, R.E.; Savendra, J.E.; Lyle, G.G. Synthesis
1978, 212.
7. Varma, R.S.; Dahuya, R. Tetrahedron Lett. 1997, 38, 2043.
8. Varma, R.S.; Meshram, H.M. Tetrahedron Lett. 1997, 38, 5427.
9. Varma, R.S.; Dahuya, R.; Sauni, R.K. Tetrahedron Lett. 1997, 38,
8819.
1
1
1
1
0. Chakraborty, V.; Bordoloi, M. J. Chem. Res. (S) 1999, 120.
1. Heravi, M.M.; Ajami, D.; Mojtahedi, M.M. J. Chem. Res. (S) 2000, 126.
2. Heravi, M.M. et al. Monatsh. Chem. 2000, 131, 187.
3. Feng, J.C.; Liu, B.; Dai, L.; Bian, N.S. Synth. Commun. 1998, 28,
3
765.
4. Feng, J.C.; Liu, B.; Dai, L.; Bian, N.S. Chinese Chemical Letters
998, 9, 795; Chem. Abstract 1999, 131, 322209f.
5. Cadogan, J.I.G.; Ley, S.V.; Pattenden, G.; Raphael, R.A.; Rees,
C.W. Dictionary of Organic Compounds, 6th Ed.; Chapman and Hall
1
1
1
(
UK), 1996.
Received in the USA April 5, 2001