Regeneration of carbonyl compounds by oxidative cleavage of carbon-nitrogen double bonds with molecular oxygen in the presence of copper(I) chloride/kieselghur as catalyst

Article abstract of DOI:10.1081/SCC-100000213

Kieselghur-supported copper(I) chloride was found to be an efficient and convenient catalyst for the oxidative cleavage of oximes, phenylhydrazones, and p-nitrophenylhydrazones to the corresponding carbonyl compounds with molecular oxygen.

Full text of DOI:10.1081/SCC-100000213

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REGENERATION OF CARBONYL COMPOUNDS BY
OXIDATIVE CLEAVAGE OF CARBON-NITROGEN DOUBLE
BONDS WITH MOLECULAR OXYGEN IN THE PRESENCE
OF COPPER(I) CHLORIDE/KIESELGHUR AS CATALYST
Mohammed M. Hashemi a & Yousef A. Beni a
a Department of Chemistry , Sharif University of Technology , P.O. Box 11365-9516,
Tehran, Iran
Published online: 16 Aug 2006.
To cite this article: Mohammed M. Hashemi & Yousef A. Beni (2001) REGENERATION OF CARBONYL COMPOUNDS BY
OXIDATIVE CLEAVAGE OF CARBON-NITROGEN DOUBLE BONDS WITH MOLECULAR OXYGEN IN THE PRESENCE OF COPPER(I)
CHLORIDE/KIESELGHUR AS CATALYST, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 31:2, 295-299, DOI: 10.1081/SCC-100000213
To link to this article: http://dx.doi.org/10.1081/SCC-100000213
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SYNTHETIC COMMUNICATIONS, 31(2), 295–299 (2001)
REGENERATION OF CARBONYL
COMPOUNDS BY OXIDATIVE
CLEAVAGE OF CARBON-NITROGEN
DOUBLE BONDS WITH MOLECULAR
OXYGEN IN THE PRESENCE OF
COPPER(I) CHLORIDE/KIESELGHUR
AS CATALYST
Mohammed M. Hashemi∗ and Yousef A. Beni
Department of Chemistry, Sharif University of Technology,
P.O. Box 11365-9516 Tehran, Iran
ABSTRACT
Kieselghur-supported copper(I) chloride was found to be
an efficient and convenient catalyst for the oxidative cleavage of
oximes, phenylhydrazones, and p-nitrophenylhydrazones to the
corresponding carbonyl compounds with molecular oxygen.
Oximes, phenylhydrazones, and p-nitrophenylhydrazones have been em-
ployed as ketone or aldehyde functional group equivalents in organic synthesis
(1–3). The regeneration of carbonyl compounds from their derivatives provides an
attractive method for the synthesis of aldehydes and ketones.
Many methods have been developed for the oxidative cleavage of oximes,
phenylhydrazone, and p-nitrophenylhydrazones to the corresponding carbonyl
∗ To whom correspondence should be addressed.
295
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
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HASHEMI AND BENI
compounds (4–29), but some of them have limitations for oximes, and some,
in spite of generality, have the drawback of using expensive oxidants, tedious
work-up, low chemical yields, strong oxidative conditions (4–29), or side product
formation.
During the course of our systematic study on catalytic oxidation of organic
compounds with molecular oxygen, we have recently developed a heterogeneous
catalytic method based on copper(I) chloride adsorbed on Kieselghur that is an ef-
ficient and convenient catalyst for the oxidation of alkyl halides and alkyl tosylates
to the carbonyl compounds using molecular oxygen (30).
We report here a new and very convenient procedure for the oxidative cleav-
ageofcarbon-nitrogendoublebondsusingmolecularoxygenandCuCl/Kieselghur.
This catalyst is stable, reusable, and easily prepared by the addition of weighed
amounts of Kieselghur to an aqueous solution of CuCl, followed by evaporation of
solvent to dryness. The oxidative cleavage of carbon-nitrogen double bonds is car-
ried out in DCM as solvent and work-up is simply by extraction and separation of
the catalyst by filtration. After removal of the solvent and purification of products
by chromatography, carbonyl compounds are obtained in high yields (Table 1).
This catalyst is reusable and the reusability of the catalyst after 4 succes-
sive oxidations of benzaldehyde oxime to benzaldehyde is shown in Table 2. The
catalyst was recovered quantitatively after each experiment.
EXPERIMENTAL
Chemicals were purchased from Merck, Aldrich, and Riedel de Haen AG
chemical companies and were used without further purification. IR spectra were
1
recorded (KBr) on a FT-IR Unicam Mattson 1000 Spectrophotometer. H-NMR
spectra were recorded on a Brucker AC-80 (80 MHz) spectrometer in CDCl3
and chemical shifts are indicated in δ ppm. All products are known compounds
and they were identified by their m.p.s, or b.p.s, IR and 1H-NMR, spectroscopic
properties. All yields refer to pure isolated products. Oximes, phenylhydrazones,
and p-nitrophenylhydrazones were prepared by usual procedure.
Preparation of CuCl/Kieselghur Reagent
To a water solution of CuCl (10 mg in 100 mL of water) Kieselghur (50 g)
was added and the mixture stirred for 30 min. Water was evaporated in vacuo and

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297
Table 1. Oxidative Cleavage of Carbon-Nitrogen Double Bonds Using Molecular Oxygen
and CuCl/Kieselghur
Entry
Substratea
Time (min)
Producta
benzaldehyde
acetophenone
4-methylacetophenone
cyclohexanone
Yield (%)b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
benzaldoxime
20
25
30
25
30
30
30
30
20
25
25
30
30
25
30
30
30
96
97
96
90
85
92
88
91
98
89
97
95
94
98
90
92
86
acetophenone oxime
4-methylacetophenone oxime
cyclohexanone oxime
anthrone oxime
cinnamaldoxime
2-thiophenaldoxime
anthrone
cinnamaldehyde
2-thiophenaldehyde
4-nitrobenzaldehyde
4-methybenzaldehyde
heptanal
4-nitrobenzaldoxime
4-methylbenzaldoxime
heptanal oxime
benzophenone-PHc
benzophenone
4-pyridine carbaldehyde-PHc
4-methylbenzaldyde-PHc
benzaldehyde-PHc
4-pyridinecarbaldehyde
4-methybenzaldyde
benzaldyde
4-methybenzaldyde
acetophenone
4-methylbenzaldyde-4-NPHd
acetophenone-4-NPHd
4-chlorobenzaldehyde-4-NPHd
4-chlorobenzaldyde
aAll compounds were fully characterized by their mps, IR and 1H-NMR spectra.
bYields refer to pure isolated products.
c,dPH represents 4-nitrophenylhydrazone and 4-NPH represents 4-nitrophenylhydrazone.
the residue dried in an oven at 110◦C for 5 h to give 59 g of CuCl/Kieselghur
reagent.
Regeneration of Carbonyl Compounds
To a stirring solution of benzaldehyde oxime (2 mmol) in DCM (25 mL) was
added CuCl/Kieselghur reagent (5 g). The reaction mixture was stirred at room
Table 2. Reusability of Catalysta
Experimental Trial
Starting Material
Product
Yield (%)
1st
benzaldehyde oxime
benzaldehyde oxime
benzaldehyde oxime
benzaldehyde oxime
benzaldehyde
benzaldehyde
benzaldehyde
benzaldehyde
98
95
93
91
2nd
3rd
4th
aAll reactions are carried out under similar conditions as Table 1.

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HASHEMI AND BENI
temperature, during which time oxygen was bubbled at a rate of 10 mL min−1
.
ProgressofthereactionwasmonitoredbyTLC(hexaneethylacetate5:1). Whenthe
reaction was completed, the reaction mixture was filtered through a sintered glass
funnel. The residue was washed thoroughly with the solvent (25 mL). Removal of
the solvent followed by column chromatography on silica gel (hexane ethylacetate
5:1) gave the pure product.
In conclusion, mild reaction conditions, high yields, ease of work-up, plus
stability and reusability of catalyst are the most significant aspects of this method.
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Received in the UK November 24, 1999

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