A Selective Method for Catalytic Cleavage of Oximes to Their Carbonyl Compounds Using 10% H2O2 and [Mn(L22pyfp)Cl](ClO4) as a Catalyst

Full text of DOI:10.1080/00304948.2018.1549904

Organic Preparations and Procedures International
The New Journal for Organic Synthesis
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A Selective Method for Catalytic Cleavage of
Oximes to Their Carbonyl Compounds Using 10%
H O and [Mn(L
)Cl](ClO ) as a Catalyst
22pyfp 4
2
2
Abbas Aminimanesh, Reza Golbedaghi & Leila Hadi
To cite this article: Abbas Aminimanesh, Reza Golbedaghi & Leila Hadi (2019): A Selective
Method for Catalytic Cleavage of Oximes to Their Carbonyl Compounds Using 10% H O and
2
2
[
Mn(L22pyfp)Cl](ClO ) as a Catalyst, Organic Preparations and Procedures International, DOI:
4
10.1080/00304948.2018.1549904
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Organic Preparations and Procedures International, 0:1–6, 2019
2019 Taylor & Francis Group, LLC
#
ISSN: 0030-4948 print / 1945-5453 online
DOI: 10.1080/00304948.2018.1549904
A Selective Method for Catalytic Cleavage of
Oximes to Their Carbonyl Compounds Using 10%
H O and [Mn(L
)Cl](ClO ) as a Catalyst
2
2
22pyfp
4
Abbas Aminimanesh, Reza Golbedaghi, and Leila Hadi
Department of Chemistry, Payame Noor University, P.O. Box 19395-3697,
Tehran, Iran
1–3
In continuance of our systematic study of oxidation methods
we wish to report an
easy and selective method for the conversion of aromatic, aliphatic, and cyclic oximes
4
–7
to their corresponding aldehydes and ketones
by using the new catalyst
8
{
[Mn(L22pyfp)Cl](ClO )} with H O as an oxidant (Scheme 1).
4
2 2
8
For this work, the Mn(II) complex was synthesized by the reported procedure and
the structure of the complex is shown in Figure 1.
convenient reaction of an oxime in refluxing CH CN with
A
3
[
Mn(L22pyfp)Cl](ClO ) and H O produced the corresponding carbonyl compound in
4 2 2
good to excellent yields.
We first checked the catalytic activities of [Mn(L22pyfp)Cl](ClO ) and hydrogen
4
peroxide toward benzaldehyde oxime in CH CN as a test reaction. Benzaldehyde is a
3
suitable target compound, as it is readily over-oxidized to benzoic acid. Thus the forma-
tion of benzoic acid is a direct indication of the selectivity of the protocol. Ethanol,
methanol, chloroform, acetonitrile and hexane were used as solvents (Table 1); our
findings suggested that CH CN was the best of the solvents examined in terms of time
3
and yields.
Different molar ratios of the catalyst, benzaldehyde oxime, and H O were used
2
2
(
(
Table 2). Stirring of a solution of the catalyst (0.2 mmol), benzaldehyde oxime
1 mmol) and H O (7 ml, 10%) in CH CN under reflux resulted in the formation of
2
2
3
benzaldehyde in quantitative yield within 55 min. Without the Mn-complex catalyst,
benzaldehyde was only formed in 20% yield (entry 1) and without H O benzaldehyde
2
2
was not formed at all (entry 2).
The results for deoximation of a variety of structures are summarized in Table 3.
The results represented in Table 3 show that the reaction is useful for a variety of
aromatic, aliphatic and cyclic oximes. Sterically hindered ketoximes (entries 10, 11, 12)
were successfully converted to the corresponding ketones in good yield. Aldoximes are
converted to the corresponding aldehydes efficiently (entries 1, 2, 3, 4). Over-oxidation
of aldehydes to carboxylic acids and production of the by-products was not observed.
Received January 27, 2018; in final form August 15, 2018.
Address correspondence to Abbas Aminimanesh, Department of Chemistry, Payame Noor
University, P.O. Box 19395-3697, Tehran, Iran. E-mail: a_aminima@yahoo.com
1

2
Aminimanesh et al.
4 2 2
Scheme 1. Conversion of oximes to carbonyl compounds by [Mn(L22pyfp)Cl](ClO ) and H O .
Figure 1. X-ray crystal structure of the [Mn(L22pyfp)Cl](ClO ) complex.
4
Table 1
Optimization of Solvent in Oxidation of Benzaldehyde Oxime to Benzaldehyde
a,b
Entry
Solvent
C H
CHCl3
Time (Min)
Yield (%)
1
2
3
4
5
6
7
90
90
90
90
90
10
20
45
50
95
95
0
6
12
CH OH
3
C H OH
2
5
CH CN
3
CH CN
55
100
3
Solvent-Free
a
Yields refer to isolated pure products.
Reaction conditions: oxime (1 mmol), H O (10 ml, 10%), [Mn(L
b
)Cl](ClO ) (0.3 mmol)
22pyfp 4
2
2
under reflux conditions.
An important advantage of [Mn(L22pyfp)Cl](ClO ) is its simple recovery from the
4
reaction mixture and its reusability. These aspects were tested using acetophenone
oxime as a model substrate. The recovery of catalyst was very simple. The carbonyl
products are soluble in CHCl or Et O, while the catalyst is insoluble. The catalyst was
3
2

Catalytic Cleavage of Oximes to Their Carbonyl Compounds
3
Table 2
Optimization of Catalyst and Oxidant for Oxidation of Benzaldehyde Oxime to
Benzaldehyde
a,b
Entry Amount of [Mn(L22pyfp)Cl](ClO ) (mmol) Amount of H O (ml) Yield (%)
4
2 2
1
2
3
4
5
6
7
8
9
1
0
10
0
20
–
0.2
0.05
0.08
0.09
0.1
0.12
0.2
0.3
0.2
10
10
10
10
10
10
10
7
40
55
62
65
70
95
95
95
0
a
Yields refer to isolated pure products.
Reaction conditions: oxime (1 mmol), different amounts of H
b
2
O
2
and catalyst in CH
3
CN
under reflux for 55 min.
separated by simple filtration from the reaction mixture after each experiment. As
shown in Table 4, [Mn(L22pyfp)Cl](ClO ) is reusable, although by the fourth isolation
4
significant loss of activity was noted.
In conclusion, we have shown a simple and convenient method for the effective
conversion of oximes to the corresponding aldehydes or ketones. Formation of by prod-
ucts and over-oxidation of aldehydes to carboxylic acids were not observed. Easy
removal of the catalyst [Mn (L22pyfp)Cl] (ClO ) is another advantage.
4
Experimental Section
Chemicals were purchased from Merck, Fluka and Aldrich Chemical Companies. All
yields refer to the isolated products. All products were known and identified by the
comparison of their m.p., b.p., IR and NMR with those reported for the authentic sam-
9
–15
ples.
The progress of reaction was monitored by TLC (silica gel as stationary phase
1
and n-hexane/acetone 9:1 as solvent). IR and H NMR spectra were recorded using a
Shimadzu Infrared Spectrophotometer FT-IR Model IR Prestige 21 (KBr pellets) and a
1
9
0 MHz Jeol FT-NMR spectrometer, respectively. H NMR chemical shifts were meas-
ured relative to TMS.
General Procedure for Deoximation by [Mn (L22pyfp)Cl] (ClO4)
To a solution of oxime (1 mmol) in acetonitrile (10 ml), [Mn (L22pyfp)Cl] (ClO4)
(
0.2 mmol, 0.112 g) was added; then hydrogen peroxide (7 ml, 10%) was slowly added.
The mixture was then stirred at reflux. The progress of reaction was monitored by TLC
silica gel as stationary phase and n-hexane/acetone 9:1 as solvent). After completion of
(
the reaction (Table 3), the solvent was removed under reduced pressure and then 10 ml
CHCl or THF was added and stirred for 10 min, the mixture was filtered and the solid
3
residue was washed with CHCl or THF (5 ml). Evaporation of the solvent from the
3
residue gave crude products. The pure carbonyl compound was isolated by column

4
Aminimanesh et al.
Table 3
Deoximation of Oximes by [Mn(L22pyfp)Cl](ClO ) and H O
4
2 2
a,b
Entry
Substrate
Product
Time/min Yield (%)
9
1
55
95
10
2
45
95
9
3
4
50
85
90
11
85
9
0
2
5
6
7
60
65
45
90
1
92
1
86
9
8
9
60
85
10
105
80
9
1
0
80
70
(Continued)

Catalytic Cleavage of Oximes to Their Carbonyl Compounds
5
Table 3
(
Continued).
a,b
Entry
Substrate
Product
Time/min Yield (%)
13
1
1
100
73
1
4
9
5
c
1
1
1
1
2
3
4
5
115
60
60
70
1
90
60
120
60
a
Oxime (1 mmol), H O (7 ml, 10%), [Mn(L22pyfp)Cl](ClO ) (0.2 mmol), CH CN (10 ml)
2
2
4
3
under reflux, 45-120 min.
b
Yields refer to the isolated pure products.
c
Product was separated by distillation under reduced pressure and yield determined as 2,4-
dinitrophenyl hydrazone derivative.
Table 4
Reusability of [Mn(L22pyfp)Cl](ClO ) Catalyst in the Oxidation of
4
Acetophenone Oxime
a,b
Run No.
Time (min)
Yield (%)
1
2
3
4
60
60
60
60
90
82
70
65
a
Isolated yield.
Oxime (1 mmol), H
b
2
O
2
4 3
(7 ml, 10%), [Mn(L22pyfp)Cl](ClO ) (0.2 mmol), CH CN (10 ml)
under reflux condition.
chromatography on silica gel (eluent: n-hexane/acetone 9:1) in good to excellent yields
Table 3). The yield of butanone product was determined as its 2,4-dinitrophenyl hydra-
(
zone derivative. We present analytical data of three selected examples (aromatic aldox-
ime, aromatic and aliphatic ketoxime, converted in each case to the parent carbonyl
compound) from Table 3:
ꢀ ꢀ
9
4
-Chlorobenzaldehyde. m.p. 44-46 C, lit. 45-48 C. IR (KBr): 3421, 3087, 2924,
ꢁ
1 1
2
857, 2758, 1698, 1574, 1483, 1385, 1207, 815 cm . H NMR (90 MHz, CDCl ) d
3
(ppm): 7.480-7.716 (dd, 4H), 9.919 (s, 1H).

6
Aminimanesh et al.
0
ꢀ
12
ꢀ
4
-Hydroxyacetophenone. m.p. 108-110 C, lit. 109-111 C. IR (KBr): 3243,
ꢁ
1 1
3
007, 2927, 1674, 1605, 1576, 1511, 1459, 1310, 1250, 1181, 1024, 836 cm . H
NMR (90 MHz, CDCl ) d (ppm): 8.752 (s, 1H), 7.854-6.991 (dd, 4H), 2.578 (s, 3H).
3
15
ꢀ ꢀ
2
-Methylcyclohexanone. b.p. 154-157 C, lit. 162-163 C. IR (KBr): 3402, 2925,
854, 2359, 1715, 1456, 1375 cm . H NMR (90 MHz, CDCl ) d (ppm): 2.854-2.515
ꢁ
1 1
2
3
(m, 4H), 1.979 (m, 3H), 1.602 (m, 2H), 1.108 (s, 3H).
Acknowledgments
We are grateful to the Department of Chemistry of Payame Noor University and
Ministry of Science Research and Technology for the financial support.
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