J. Chem. Sci. Vol. 127, No. 3, March 2015, pp. 493–497. ꢀc Indian Academy of Sciences.
DOI 10.1007/s12039-015-0801-6
K [Fe(CN) ].3H O supported on silica gel: An efficient and selective
3
6
2
reagent for the cleavage of oximes to their corresponding carbonyl
compounds in aqueous medium
∗
ABBAS AMINI MANESH and BEHZAD SHIRMARDI SHAGHASEMI
Department of Chemistry, Payame Noor University, 19395-4697 Tehran, I. R. of IRAN
e-mail: a_aminima@yahoo.com
MS received 5 June 2014; revised 27 August 2014; accepted 29 August 2014
Abstract. K3[Fe(CN)6].3H2O supported on silica gel, a new oxidant, for efficient, simple and selective cleav-
age of ketoximes and aldoximes to their corresponding carbonyl compounds in aqueous medium is described.
Further oxidation of aldehydes to carboxylic acid and formation of by-products were not observed. α − β
unsaturated oxime was deoximated smoothly without oxidation of the double bond.
Keywords. K3[Fe(CN)6].3H2O, Silica gel; oxime; aldehyde; ketone.
1
. Introduction
K [Fe(CN) ].3H O supported on SiO as a new oxidant
3 6 2 2
(
scheme 1).
Oximes can be prepared from carbonyl and non-
carbonyl compounds, and compounds having active
methylene groups.1 These solid compounds are used
for isolation, purification and characterization of the
parent carbonyl compounds. Carbonyl groups can be
protected by oximation, and in turn, these oximes
,2
2
. Experimental
3
2
.1 General methods and materials
can serve as an intermediate for the preparation of In this study, all of the oximes were prepared as reported
4
25
nitriles of amides via the Beckmann rearrangement elsewhere, except benzaldehyde oxime, which pur-
5
1
or to activate the carbonyl group. Thus, there has chases from Merck (Darmstadt, Germany). IR and H
been an increasing interest in the development of NMR spectra were recorded using a Shimadzu Infrared
methods for the conversion of oximes into their cor- Spectrophotometer FT-IR Model IR Prestige 21 (KBr
responding carbonyl compounds and a number of pellets) and a 90 MHz Jeol FT-NMR spectrometer,
methods and compounds such as 1,3-Dibromo-5,5- respectively. H NMR chemical shifts were measured
dimethylhydantoin, microwave, CeO –ZrO , Potas- relative to TMS. Silica-supported K [Fe(CN) ].3H O
1
6
7
8
2
2
3 6 2
9
sium bromide and Ammonium heptamolybdate, Sil- (oxidant B) was prepared by impregnating 2.0 g of sil-
ica Sulfuric acid,10 Bi(OTf) ·4H O, Ionic liquid,
11
12
ica with aqueous solutions of K
[Fe(CN) ].3H O (1 g
O). The mixture was stirred overnight at
3
2
3
6 2
13
poly[4-vinyl-N, N-dichlorobenzenesulfonamide], me- in 30 mL H
2
14
15
talloporphyrins, 1,3-Dichloro-5,5-dimethylhydantoin,
reflux temperature, followed by drying using a rotary
-Nitro-4,5-dichloropyridazin-3(2H)-one, N-bromo- evaporator at 110 C which gives yellow powders.
16
◦
2
17
N-benzoyl-4-toluenesulfonamide, Tetra-n-alkylammo-
nium bromates have been explored.
18
In a nutshell, the regeneration of carbonyl com- 2.2 General Procedure for Deoximation
pounds from oximes can be achieved using a variety
of methods, including oxidative, reductive, and pho- To a solution of oxime (1 mmol) in ethanol (10 mL),
tochemical techniques.19 In continuation of our sys- 0.1 g oxidant B (0.393 mmol) was added. Then H
O
2
20–24
tematic study and research on oxidation methods,
(1 mL) was added to the solution. The resulting mix-
we report a new, simple and selective method for the ture was stirred at reflux conditions and the progress
conversion of aliphatic, aromatic and cyclic oximes of the reaction monitored by thin layer chromatography
to their corresponding aldehydes and ketones by (hexane-acetone, 8:2 v/v). After completion of the reac-
tion, the oxidant was removed by filtration and washed
∗
For correspondence
with 2 × 5 mL ethanol. The solvent was removed from
493