A mild and environmentally benign procedure for the oxidative cleavage of oximes with potassium permanganate supported on kieselguhr

Article abstract of DOI:10.1080/15533174.2012.680148

A facile, mild, and relative environmentally friendly procedure for the regeneration of aldehydes and ketones from their oximes with potassium permanganate supported on kieselguhr reagent at room temperature under heterogeneous conditions in the yield between 82-96% is described.

Full text of DOI:10.1080/15533174.2012.680148

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A Mild and Environmentally Benign Procedure for
the Oxidative Cleavage of Oximes with Potassium
Permanganate Supported on Kieselguhr
Ji-Dong Lou a b , Fang Lin a , Lihong Huang a & Xiao-Nan Zou a
a College of Life Sciences , China Jiliang University , Hangzhou , Zhejiang , 310018 , China
b Sirnaomics, Inc., 401 Professional Drive , Gaithersburg , MD , 20879 , USA
Accepted author version posted online: 14 May 2012.Published online: 06 Aug 2012.
To cite this article: Ji-Dong Lou , Fang Lin , Lihong Huang & Xiao-Nan Zou (2012) A Mild and Environmentally Benign
Procedure for the Oxidative Cleavage of Oximes with Potassium Permanganate Supported on Kieselguhr, Synthesis and
Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:7, 1027-1029, DOI: 10.1080/15533174.2012.680148
To link to this article: http://dx.doi.org/10.1080/15533174.2012.680148
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:1027–1029, 2012
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.680148
A Mild and Environmentally Benign Procedure
for the Oxidative Cleavage of Oximes with Potassium
Permanganate Supported on Kieselguhr
Ji-Dong Lou,1,2 Fang Lin,1 Lihong Huang,1 and Xiao-Nan Zou1
1College of Life Sciences, China Jiliang University, Hangzhou, Zhejiang 310018, China
2Sirnaomics, Inc., 401 Professional Drive, Gaithersburg, MD 20879, USA
siderable interest in the development of mild techniques for the
conversion of oximes into their corresponding carbonyl com-
pounds.
A facile, mild, and relative environmentally friendly procedure
for the regeneration of aldehydes and ketones from their oximes
with potassium permanganate supported on kieselguhr reagent
at room temperature under heterogeneous conditions in the yield
between 82–96% is described.
RESULTS AND DISCUSSION
It is well known that the use of solid supports has be-
come popular due to their characteristic properties such as
enhanced selectivity and reactivity, straightforward work-up
procedure, milder reaction conditions and associated ease of
manipulation.[7] Potassium permanganate, a relative environ-
mentally friendly and inexpensive reagent, is one of the im-
portant oxidants employed in the deoximation. Adsorption
of potassium permanganate on the surface of solid supports
changes the selectivity and reactivity in various reactions. To
the best of our knowledge, several supported potassium per-
manganate reagents have been reported in the oxidative cleav-
age of oximes to their parent carbonyl compounds, for instance,
potassium permanganate-manganese(II) sulfate,[8] potassium
permanganate-manganese dioxide,[8] potassium permanganate-
wet silica gel,[9] potassium permanganate-montmorillonite K-
10,[10] potassium permanganate-alumina,[11,12] and potassium
permanganate-zeolite.[13] Two of them are carried out under
heterogeneous conditions[12,13] and the rest are performed under
solvent-free conditions,[8–11] all of which have achieved good
results.
We previously reported that potassium permanganate
supported on kieselguhr is a good reagent for the oxidation
of alcohols to aldehydes and ketones under heterogeneous
conditions[14] and solvent-free conditions,[15] respectively. In
continuation of our ongoing program to develop environmen-
tally benign methods, we now report that this reagent can be
successfully employed in the oxidative cleavage of oximes
(1) to the corresponding aldehydes and ketones (2) in high
yields at room temperature under heterogeneous conditions
(Scheme 1).
Keywords: carbonyl compounds, kieselguhr, oxidation, oximes,
potassium permanganate
INTRODUCTION
Oximes of the aldehydes and ketones serve a number of
useful purposes in organic synthesis. Aldehydes and ketones
protected as oximes can later be removed to expose the original
carbonyl functional group in the synthesis of complex organic
molecules. Unstable carbonyl compounds are often converted
to crystalline oximes for purification and characterization.[1,2]
Since oximes can be prepared from non-carbonyl compounds,
their deoximation provides an alternative pathway to the alde-
hydes and ketones.
For the deoximation, three major procedures have been em-
ployed, such as hydrolytic, reductive, and oxidative reactions,
and the deoximation process can be undertaken in both homo-
geneous and heterogeneous conditions.[3–5] The most important
procedure for this transformation are the oxidative cleavage of
oximes and the oxidation methods used are mainly concentrated
on chromium reagents, potassium permanganate, manganese
triacetate, N-bromosuccinimide, dinitrogen tetroxide, sodium
periodate, and tert-butylhydroperoxide.[6] However, although
some of the reported methods are carried out under mild re-
action conditions, most of them require drastic conditions, for
instance, high temperature, long reaction times, toxic reagents,
and tedious work-up procedures. Therefore, there has been con-
In the present procedure, the mixture of oximes and potas-
sium permanganate supported on kieselguhr reagent is stirred
in dichloromethane at room temperature, and a 1 to 2 molar
ratio of the substrate to the oxidant is employed. The progress
Received 17 September 2011; accepted 4 January 2012.
Address correspondence to Ji-Dong Lou, College of Life Sciences,
China Jiliang University, Hangzhou, Zhejiang 310018, China. E-mail:
lou@cjlu.edu.cn
1027

1028
J.-D. LOU ET AL.
OH
R2
of the reaction is monitored with TLC, and the corresponding
KMnO4 - Kieselguhr
CH2Cl2, RT
O
N
aldehydes and ketones is purified by preparative TLC in good
yields. The oxidized products are all known compounds and
identified by spectroscopic comparison with authentic samples.
Our results are listed in the Table 1.
R1
R2
R1
(1)
(2)
SCH. 1.
TABLE 1
Oxidative cleavage of oximes to their corresponding carbonyl compounds with potassium permanganate supported on kieselguhr
reagent.
Entry
Oxime
Time (min)
Producta
Yieldb (%)
OH
N
N
O
1
20
92
OH
O
2
3
20
20
90
92
Cl
Cl
Cl
Cl
OH
N
O
O
OH
OH
N
N
4
20
96
O
5
6
20
20
86
82
OH
N
N
O
CHO
OH
7
20
86
N
OH
CHO
8
9
20
20
84
82
OCH3
N
OCH3
CHO
OH
aAll products were identified by comparison of their physical and spectral data with those of authentic samples.
bIsolated yields.

OXIDATIVE CLEAVAGE OF OXIMES
1029
Comparing with the deoximation using supported potassium
permanganate reagents under heterogeneous conditions previ-
ously reported, the present reagent has some advantages, such as
for most products shorter reaction times and higher yields. The
current method avoids the use of toxic reagents like chrominum
compounds and therefore it may be carried out on a large
scale.
2. Cheronis, N.D.; Entrikin, J.B. Identification of Organic Compounds, Inter-
science: New York, 1963.
3. Corsaro, A.; Chiacchio, U.; Pistara, V. Regeneration of Carbonyl Com-
pounds from the Corresponding Oximes, Synthesis 2001, 1903–1931.
4. Corsaro, A.; Chiacchio, M.A.; Pistara, V. Regeneration of Carbonyl Com-
pounds from the Corresponding Oximes: An Update Until to 2008, Curr.
Org. Chem. 2009, 13, 482–501
5. Sahu, S.; Sahu, S.; Patel, S.; Dash, S.; Mishra, B.K. Deoximation of
keto- and aldoximes to carbonyl compounds, Indian J. Chem. 2008, 47B,
259–271.
6. Zhou, X.; Yuan, Q.; Ji, H. Highly efficient aerobic oxidation of oximes
to carbonyl compounds catalyzed by metalloporphyrins in the presence of
benzaldehyde, Tetrahedron Lett. 2010, 51, 613–617.
7. Smith, K. (Ed.), Solid Supports and Catalysts in Organic Synthesis, Prentice
Hall, New York, 1992.
8. Shaabani, A.; Naderi, S.; Rahmati, A.; Badri, Z.; Darvishi, M.; Lee, D.G.
Cleavage of oximes, semicarbazones, and phenylhydrazones with supported
potassium permanganate, Synthesis 2005, 3023–3025.
9. Hajipour, A.R.; Ruoho, A.E. Wet silica-supported permanganate: A mild
and inexpensive reagent for highly enantiomeric purity conversion of alpha-
sulfinyl oximes and alpha-sulfinyl hydrazones to alpha-keto sulfoxides,
J. Iranian Chem. Soc. 2004, 1, 159–162.
10. Mohammadpoor-Baltork, I.; Khodaei, M.M.; Hajipour, A.R.; Aslani, E.A.
Facile, Mild, and Environmentally Benign Procedure for the Cleavage of
Carbon–Nitrogen Double Bonds Using KMnO4 in the Presence of Mont-
morillonite K-10 Under Solvent-Free Conditions, Monatsh. Chem. 2003,
134, 539–543.
EXPERIMENTAL
Oxidative cleavage of benzophenone oxime to benzophe-
none: Typical Procedure
The potassium permanganate-kieselguhr reagent[14]
(1500 mg) is placed in a flask together with dichloromethane
(30 mL) and the mixture is magnetically stirred. A solution of
benzophenone oxime (197 mg, 1 mmol) in dichloromethane
(5 mL) is added, and after 30 min at RT the solid is filtered
and washed with dichloromethane (3 × 5 mL). The combined
filtrates are evaporated to give crude product, which is pu-
rified by preparative TLC with hexane:ethyl acetate (7:3) to
afford 167 mg (92%) benzophenone.
11. Imanzadeh, G.H.; Hajipour, A.R.; Mallakpour, S.E. Solid state cleavage of
oximes with potassium permanganate supported on alumina, Synth. Com-
mun. 2003, 33, 735–740.
12. Chrisman, W.; Blankinship, M.J.; Taylor, B.; Harris, C.E. Selective de-
oximation using alumina supported potassium permanganate, Tetrahedron
Lett. 2001, 42, 4775–4777.
13. Jadhav, V.K.; Wadgaonkar, P.P.; Joshi, P.L.; Salunkhe, M.M. Oxidation of
oximes to ketones with zeolite supported permanganate, Synth. Commun.
1999, 29, 1989–1995.
14. Lou, J.; Lou, W. Oxidation of alcohols to carbonyl compounds with a new
potassium permanganate adsorbed on kieselguhr Reagent, Synth. Commun.
1997, 27, 3697–3699.
CONCLUSION
In conclusion, a facile and mild procedure for the regenera-
tion of aldehydes and ketones from their oximes is described.
The method offers several advantages including short reaction
times and high yields of the products, cleaner reactions, and
a non-toxic and inexpensive reagent which makes the reaction
process convenient, and it is more economic and environmen-
tally benign.
REFERENCES
15. Lou, J.; Wang, M.; Zhu, L.; Fang, Z. Solvent free oxidation of alcohols
catalyzed by KMnO4 adsorbed on kieselguhr, Catal. Commun. 2003, 4,
647–649.
1. Greene, T.W.; Wuts, P.G.M. Protective Groups in Organic Synthesis, 3rd
ed.; Wiley: New York, 1999.