A facile procedure for the conversion of oximes to ketones and aldehydes by the use of jones reagent adsorbed on kieselguhr reagent

Article abstract of DOI:10.1080/15533174.2011.609861

An efficient oxidation of oximes to their corresponding ketones and aldehydes with Jones reagent supported on kieselguhr under heterogeneous conditions at room temperature in the yield between 84 and 93% is described. The present procedure is an extension of application of Jones reagent supported on kieselguhr.

Full text of DOI:10.1080/15533174.2011.609861

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:282–284, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.609861
A Facile Procedure for the Conversion of Oximes to Ketones
and Aldehydes by the Use of Jones Reagent Adsorbed
on Kieselguhr Reagent
1
,2
1
1
2
1
Ji-Dong Lou, Fang Lin, Xiu Lian Lu, Qiang Wang, and Xiao-Nan Zou
1
College of Life Sciences, China Jiliang University, Hangzhou, Zhejiang, P. R. China
Sirnaomics, Inc., Gaithersburg, Maryland, USA
2
cially owing to their selectivity and inherent toxicity. Jones
An efficient oxidation of oximes to their corresponding ketones reagent is one of the best known chromium (VI) reagents for
and aldehydes with Jones reagent supported on kieselguhr under the oxidations of secondary alcohols to ketones, but it fails to
heterogeneous conditions at room temperature in the yield between
produce satisfactory results for oxidation of primary alcohols,
8
4 and 93% is described. The present procedure is an extension of
including benzyl alcohols to the corresponding aldehydes. This
problem in the oxidation reaction arises due to the fact that
aldehydes react with water and alcohols under acidic aqueous
media employed in the Jones oxidation procedure, producing
hydrates and hemiacetals, which are then oxidized to carboxylic
acids and esters, respectively.[ In addition, Jones reagent
has not been widely used in organic synthesis because they
have the potential health hazards from handling this reagent,
the problems in disposal of the toxic chromium compounds,
the by-product produced in the oxidation, and the difficulty
in product isolation. However, it seems that these disadvan-
tages might be overcome by the way of using supported reagent
technique.[
application of Jones reagent supported on kieselguhr.
Keywords carbonyl compounds, Jones reagent, kieselguhr, oxida-
tion, oximes
12]
INTRODUCTION
Oxime derivatives of carbonyl compounds are highly crys-
talline and are widely used for the characterization and purifica-
tion of carbonyl compounds. Therefore, the regeneration of car-
bonyl compounds under mild conditions is important and of con-
siderable interest, and extensive investigations on the cleavage
of these derivatives to the parent carbonyl compounds have been
13,14]
investigated.[
1,2]
So far, several such procedures for this transfor-
It is well known that many organic reactions have been de-
vised in which the reagents are deposited on various inorganic
solid supports. These novel reagents have advantages over the
conventional homogeneous solution techniques, for instance,
ease of setup and of work-up, mild experimental conditions,
and gain in yield and/or selectivity.
mation have been reported, for example, hydrolytic, oxidative,
[
3–11]
and reductive reactions,
and sometimes the deoximation
process can be undertaken in both homogeneous and heteroge-
neous conditions. Even though some of the known methods or
reagents are carried out under mild reaction conditions, most of
them require drastic conditions, high temperature, long reaction
times, or unreadily available reagents, and have tedious work-
up procedures. Therefore, the development of mild and efficient
methods for the selective cleavage of derivatives containing a
EXPERIMENTAL
carbon-nitrogen double bond such as oximes to afford carbonyl Oxidative Cleavage of Benzophenone Oxime to
compounds continues to be a significant aspect of organic chem- Benzophenone, Typical Procedure
To a vigorously stirred kieselguhr (1 g) Jones reagent[12]
istry.
Until now, hexavalent chromium derivatives have been used (0.24 mL, 2 mmol) is added slowly. CH2Cl2 (26 mL) is added
for the selective oxidative cleavage of regeneration of carbonyl to the obtained mixture. A solution of benzophenone oxime
compounds from oximes. The utility of chromium (VI) reagents (197 mg, 1 mmol) in CH2Cl2 (2 mL) is then added slowly to
in the deoximation transformation has some limitations espe- the previous stirred heterogeneous mixture at room temperature
for 1.5 h. The progress of the reaction is monitored by TLC
using hexane-ethyl acetate (8:2) as eluent. The solid is filtered
and washed with CH2Cl2 (3 × 5 mL). The combined filtrates
Received 26 July 2011; accepted 29 July 2011.
are evaporated to give crude product, which is then purified by
Address correspondence to Ji-Dong Lou, College of Life Sciences,
preparative TLC with hexane:ethyl acetate (7:3) to afford 163
mg (90%) benzophenone.
China Jiliang University, Hangzhou, Zhejiang 310018, China. E-mail:
lou@cjlu.edu.cn
282

CONVERSION OF OXIMES TO KETONES AND ALDEHYDES
283
RESULTS AND DISCUSSION
OH
N
Jones reagent - Kieselguhr
CH Cl RT
O
Previously, we have reported an efficient method for the se-
lective oxidation of alcohols to their corresponding carbonyl
compounds by using Jones reagent supported on kieselguhr.[
In continuation of this study, we are interested in extending the
applicability of this reagent system to the oxidation of other
functional groups. Therefore, we now report here in using Jones
reagent supported on kieselguhr for the oxidative cleavage of
oxime derivatives (1) to the corresponding aldehydes and ke-
tones (2) under heterogeneous conditions at room temperature
R1
R2
R1
R2
2
2,
14]
(1)
(2)
SCH. 1.
Under our experiments, a 1 to 2 molar ratio of the substrate to
Jones reagent supported on kieselguhr is employed. The mixture
of oximes and oxidant is stirred in dichloromethane at room tem-
(Scheme 1).
TABLE 1
Oxidative cleavage of oximes to their corresponding carbonyl compounds with Jones reagent supported on kieselguhr under
heterogeneous conditions
∗
∗∗
Entry
1
Oxime
OH
Time (h)
Product
Yield (%)
N
O
1.5
90
93
OH
N
O
2
1.5
Cl
Cl
Cl
Cl
OH
N
O
3
4
5
1.5
1.5
1.5
92
92
85
OH
N
O
OH
N
N
O
OH
N
O
6
7
2
2
86
90
OH
CHO
N
OH
CHO
8
9
2
90
OCH
3
OCH
3
N
OH
CHO
2
2
86
84
CHO
N
1
0
OH
∗
∗∗
All products were identified by comparison of their physical and spectral data with those of authentic samples. Yield of isolated pure
product.

284
J.-D. LOU ET AL.
perature and all oxidation are completed within 2 h. The progress
of the reaction is monitored with TLC, and the corresponding
aldehydes and ketones are obtained in good yields by purifica-
tion with preparative TLC. The main advantages of the present
oxidation are that the insoluble solid support, kieselguhr, pro-
vides a particular reaction environment capable of enhancing
the reaction selectivity and reactivity, and the present proce-
dure is an extension of application of this reagent as well. The
oxidized products are all known compounds and identified by
spectroscopic comparison with authentic samples. Our results
are listed in Table 1.
4. Salehi, P.; Khodaei, M.M.; Goodarzi, M. A mild and selective deoxima-
tion method using γ -picolinium chlorochromate (γ -PCC). Synth. Commun.
2
002, 32, 1259–1263.
5
. Narender, M.; Reddy, M.S.; Krishnaveni, N.S.; Surendra, K.; Nageswar,
Y.V.D.; Rao, K.R. Deprotection of oximes using iodosobenzene in the
presence of β-cyclodextrin in water. Synth Commun. 2006, 36, 1463–
1470.
6
. Zhang, G.S.; Yang, D.H.; Chen, M.F.; Cai, K. Oxidative deoximation to their
parent carbonyl compounds with ammonium chlorochromate adsorbed on
alumina. Synth Commun. 1998, 28, 2221–2225.
7
. Heravi, M.M.; Hydarzadeh, F.; Farhangi, Y.; Ghassemzadeh, M. Regenera-
tion of carbonyl compounds from oximes by chromium trioxide supported
onto HZSM-5 zeolite under microwave irradiation in solvent-free condi-
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8
. Jain, N.; Kumar, A.; Chauhan, S.M.S. Metalloporphyrin and heteropoly
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models of nitric oxide synthase. Tetrahedron Lett. 2005, 46, 2599–
CONCLUSION
Efficient oxidative cleavage of oximes to their corresponding
carbonyl compounds with Jones reagent supported on kiesel-
guhr under heterogeneous conditions at room temperature in
the yield between 84 and 93% is described. The present proce-
2
602.
9
. Corey, E.J.; Hopkins, P.B.; Kim, S.; Yoo, S.; Nambiar, K.P.; Falck, J.R.
Total synthesis of erythromycins. 5. Total synthesis of erythronolide A. J
Am Chem Soc. 1979, 101, 7131–7134.
dure is an extension of application of Jones reagent supported 10. Curran, D.P.; Brill, F.; Rakiewicz, D.M. A mild reductive conversion of
oximes to ketones. J Org Chem. 1984, 49, 1654–1656.
1. Balicki, R.; Kaczmarek, L. Mild reductive deoximation with TiCl4/NaI
reagent system. Synth Commun. 1991, 21, 1777–1782.
on kieselguhr.
1
12. Cainelli, G.; Cardillo, G. Chromium Oxidations in Organic Chemistry;
Springer-Verlag: Berlin, 1984.
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