Ion exchange catalysis in oxidation of organic compounds with KMnO4

Article abstract of DOI:10.1081/SCC-120016369

The oxidation of organic compounds under ion exchange resin (IER) catalysis by KMnO₄ has been studied in CH₂Cl₂ under reflux conditions. Secondary aliphatic and aromatic alcohols are converted to ketones, alkyl arenes and sulfides oxidized to corresponding ketones and sulfones, respectively, and thiols undergo oxidative coupling reactions to give disulfides. The experimental procedure is simple and products are easily isolated in good yields.

Full text of DOI:10.1081/SCC-120016369

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Ion Exchange Catalysis in Oxidation of Organic
Compounds with KMnO
Ahmad Shaabani , Fatemeh Teimouri & Donald G. Lee
4
a
a
b
a
Department of Chemistry, Shahid Beheshti University, Tehran, Iran
Department of Chemistry, University of Regina, Regina, Canada
b
Available online: 17 Aug 2006
To cite this article: Ahmad Shaabani, Fatemeh Teimouri & Donald G. Lee (2003): Ion Exchange Catalysis in Oxidation of
Organic Compounds with KMnO , Synthetic Communications: An International Journal for Rapid Communication of Synthetic
4
Organic Chemistry, 33:6, 1057-1065
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Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 6, pp. 1057–1065, 2003
Ion Exchange Catalysis in Oxidation of Organic
Compounds with KMnO4
1
,
1
2
Ahmad Shaabani, * Fatemeh Teimouri, and Donald G. Lee
1
Department of Chemistry, Shahid Beheshti University,
Tehran, Iran
2
Department of Chemistry, University of Regina,
Regina, Canada
ABSTRACT
The oxidation of organic compounds under ion exchange resin (IER)
catalysis by KMnO has been studied in CH Cl under reflux condi-
4
2
2
tions. Secondary aliphatic and aromatic alcohols are converted to
ketones, alkyl arenes and sulfides oxidized to corresponding ketones
and sulfones, respectively, and thiols undergo oxidative coupling
reactions to give disulfides. The experimental procedure is simple
and products are easily isolated in good yields.
*
Correspondence: Ahmad Shaabani, Department of Chemistry, Shahid
Beheshti University, P.O. Box 19396-4716, Tehran, Iran; E-mail: a-shaabani@
sbu.ac.in.
1
057
DOI: 10.1081/SCC-120016369
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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1
058
Shaabani, Teimouri, and Lee
A wide range of organic synthesis have been accomplished using the
[
1–4]
acidic and basic forms of ion exchange resin as catalyst.
The advan-
tages in using insoluble ion exchange resins in catalysis are that they are
readily available and corrosion problems involving apparatus and plant
are minimal. In addition, it can be easily removed from reaction mixture
and the bulk reaction volume is not contaminated with acid or base or
their related fragments.
Very recently, we reported the oxidation of organic compounds
under solventfree ion exchange resin ca ta lysis by NaBrO atroom te m-
3
[
5]
perature. In continuation of our studies on the application of KMnO
6–11]
4
[
in oxidation of organic compounds,
we wish to report ion exchange
resin catalysis in oxidation of organic compounds by means of KMnO4
as a simple methodology and an efficient oxidant system under heterog-
enous conditions in CH Cl .
2
2
As indicated in Sch. 1, secondary aliphatic and aromatic alcohols are
converted into the corresponding ketones in good yields (Table 1).
Carboxylic acids are obtained in comparable yields from the oxidation
of primary alcohols (Entries 9 and 10).
As can be seen from the Table 2, alkyl arenes are converted into the
corresponding carbonyl compounds in good yields under ion exchange
catalysis by KMnO . The products are identical to those obtained under
4
heterogeneous conditions where the KMnO4 is supported on
[
11]
CuSO .5H O and alumina,
4
however, the reaction times are reduced
2
from a few days to a few hours. As indicated in Sch. 2, the reaction displays
an interesting selectivity for compound containing oxygen as part of a
cyclic side chain. It is interesting that toluene and p-xylene readily oxidized
with this system to corresponding acids (Entries 10 and 11).
Alkyl and aryl sulfides are converted into the corresponding sulfones
in good yields (Table 3). This is a highly useful reaction for the prepara-
tion of sulfones which are important intermediates in the synthesis
Scheme 1.

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IER Oxidation of Organic Compounds
1059
Table 1. Oxidation of alcohols to carbonyl compounds by KMnO /IER in
4
2 2
CH Cl under reflux conditions.
M.p. of
2,4-DNP
( C)
M.p. of
product
( C)
Time Yield
(h)
ꢀ
ꢀ
Entry
1
Reactant
Product
(%)
a
a
4
91
255–257 (258)
249–250 (250)
40–42
b
(
42)
2
3
4.15
4.30
93
94
–
a
145–148 (148)
160–162 (162)
–
a
4
5
4.30
5
93
92
–
–
a
55–58 (58)
a
a
6
7
5
93
92
104–106 (106)
–
–
4.30
115–117 (117)
a
8
9
4.15
4.15
93
95
142–144 (144)
–
–
130–133
b
133)
(
1
0
1
4
5
94
–
–
–
108–110
107–111)
b
(
1
No Reaction
–
a
[18]
From ref.
From ref.
b
[19]
[
12]
of many organic compounds.
The observation that benzyl phenyl
sulfide and dibenzyl sulfide are oxidized to the corresponding sulfones
indicate that the reactions proceed by way of an oxygen transfer mecha-
nism (Sch. 3). If the reactions involved electron transfer instead of oxygen
transfer, substantial amounts of benzaldehyde would have been
[13,14]
formed.

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060
Shaabani, Teimouri, and Lee
Table 2. Oxidation of alkyl arenes to carbonyl compounds by KMnO /IER in
4
2 2
CH Cl under reflux conditions.
Time Yield
(h) (%) 2,4-DNP ( C) product( C)
M.p. of
M.p. of
ꢀ
ꢀ
Entry Reactant
1
Product
a
5.30 91 248–250 (250)
5.45 93 190–191 (191)
–
–
a
2
3
b
7
7
95
–
127 (127)
a
b
4
5
6
93 253–256 (258)
41–42 (42)
b
b
6.30 94
7.30 93
–
–
72–74 (71–74)
172–174 (174)
a
b
7
8
9
7.30 94 280–282 (283)
(81–84) 84
b
8.15 90
–
(47–49) 48
a
5.45 92 198–200 (200)
–
b
1
0
1
3
6
90
93
–
–
120–122 (121)
b
1
Sub. (Sub.)
a
[18]
[19]
From ref.
From ref.
b

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IER Oxidation of Organic Compounds
1061
Scheme 2.
Aromatic and aliphatic thiols are also oxidatively coupled under
these conditions in relatively high yields (Table 4, Sch. 4). The reaction
times are shorter than those reported for the corresponding heteroge-
[15]
neous reactions.
EXPERIMENTAL
All products are known compounds and were identified by compar-
ison of their physical and spectral data with those of authentic samples.
Melting points were determined in open capillaries using an oil-bath and
are uncorrected. IR spectra were as neat films or as KBr pellets on a
1
Shimadzu 470 spectrometer. H NMR spectra were recorded at 90 MHz
on a JEOL EX-90 instrument with CDCl as solventand Me Si as an
3
4
internal standard. Yields reported refer to isolated products or 2,4-dini-
trophenylhydrazone derivatives (2,4-DNP) of the carbonyl com-
[
16,17]
pounds.
the Fisher Scientific Company.
The ion exchange resin, Rexyn 101 H, was obtained from
TYPICAL PROCEDURE
Oxidation of Cyclohexanol with KMnO /IER
4
Cyclohexanol (0.101 g, 1 mmol) was dissolved in CH Cl (30 mL) and
2
2
placed in a round-bottomed flask. Finely grounded KMnO (1 g) and
4
IER (1 g) were added and the mixture was stirred at reflux conditions
for 4.30 h. The product was filtered through sintered glass and residue
washed with CH Cl (20 mL). The solventwas evapora et d ot give a
2
2
product (0.93 mmol, 93%). The melting point of the 2,4-DNP derivative
ꢀ
ꢀ
[18]
was 160–162 C (Lit. 162 C).

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Shaabani, Teimouri, and Lee
Table 3. Oxidation of sulfides to sulfones by KMnO /IER in CH Cl under
4
2
2
reflux conditions.
ꢀ
Entry
1
Reactant
Product
Time (h) Yield (%)
M.p. or B.p. ( C)
a
5
5
6
85
94
89
85–87 (86–86.5)
b
2
3
152–155 (154–155)
b
97–100 (97)
b
b
4
6
90
133–137 (133–137)
128–129 (128–130)
5
6
7
91
87
b
5.30
144–146 (146)
b
7
8
9
5.30
4
88
95
151–155 (155)
c
35–40 (28–45)
b
4
4
88
91
45–46 (45–46)
b
1
0
74–76 (74)
a
[21]
From ref.
b
[19]
[22]
From ref.
From ref.
c
Scheme 3.

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IER Oxidation of Organic Compounds
1063
Table 4. Coupling of thiols by KMnO /IER in CH Cl under reflux conditions.
4
2
2
ꢀ
Entry Reactant
1
Product
Time (h) Yield (%) M.p. or B.p. ( C)
a
2.30
96
71–73 (71–72)
b
2
3
94
127–130 (125–130)
b
3
4
5
2.30
2.15
2.45
94
95
96
91–93 (92.5)
c
113–116 (114–115)
185–188 (186–188)
d
a
[20]
[23]
[24]
[19]
From ref.
b
From ref.
From ref.
c
d
From ref.
Scheme 4.
Oxidation of Indan with KMnO /IER
4
Indan (0.118 g, 1 mmol) was dissolved in CH Cl (30 mL) and placed
2
2
in a round-bottomed flask with a magnetic stirrer. Finely grounded
KMnO (1 g) and IER (1 g) was added and the mixture was stirred at
4
reflux conditions and the extent of reaction monitored by using of TLC.
After 7 h, analysis of the liquid phase by TLC indicated complete
conversion to 1-indanone. The product was filtered through sintered
glass and residue washed with CH Cl (20 mL). The solventwas evapo-
2
2
rated to give a product (0.93 mmol, 93%) which showed only one
ꢀ
TLC spot and 2,4-DNP derivative of indanone melted at 253–256 C
ꢀ
[
18]
(
Lit. 258 C).
Oxidation of Dibenzyl Sulfide with KMnO /IER
4
Dibenzyl sulfide (0.214 g, 1 mmol) dissolved in CH Cl (30 mL),
2
2
was placed in a round-bottomed flask equipped with a magnetic stirrer.

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Finely grounded KMnO (1 g) and IER (1 g) was added and the mixture
4
was stirred at reflux conditions and the extent of reaction monitored
by using of TLC. After 5.30 h, analysis of the liquid phase by TLC
indicated complete conversion to dibenzyl sulfone. The product was
filtered through sintered glass and residue washed with CH Cl
2
2
(
8
(
20 mL). The solventwas evaporaetd ot give a product(0.88 mmol,
8%) which produced only one TLC spotand me let d at151–155
Lit. 155 C).
ꢀ
C
[19]
ꢀ
Oxidation of Benzyl Thiol with KMnO /IER
4
Benzyl thiol (0.124 g, 1 mmol) was dissolved in CH Cl (30 mL) and
2
2
placed in a round-bottomed flask with a magnetic stirrer. Finely
grounded KMnO (1 g) and IER (1 g) added. The mixture was stirred
4
at reflux conditions and the extent of reaction monitored by use of TLC.
After 2.30 h, analysis of the liquid phase by TLC indicated complete
conversion to dibenzyl disulfide. The product was filtered through sin-
tered glass and residue washed with CH Cl (20 mL). The solventwas
2
2
evaporated to give a product (0.96 mmol, 96%) which produced only one
ꢀ
[20]
TLC spotand mel et d at71–73 C (Lit. 71–72 C).
ꢀ
ACKNOWLEDGMENT
Financial support by the Research Council of Shahid Beheshti
University is acknowledged.
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1
2
3
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IER Oxidation of Organic Compounds
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Received in the UK February 18, 2001

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