Manganese(III) porphyrin supported on polystyrene as a heterogeneous alkene epoxidation and alkane hydroxylation catalyst

Article abstract of DOI:10.1081/SCC-120014040

Carboxymethylated crosslinked polystyrene resin [poly(4-styrylmethylacylchloride) (PSA)] support have been used to covalently attach manganese(III) tetrakis(4-aminophenyl)-porphyrin. This catalyst was found to be efficient for alkene epoxidation and alkane hydroxylation by sodium periodate. This new hydrogenised catalyst is of high stability and reusability.

Full text of DOI:10.1081/SCC-120014040

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MANGANESE(III) PORPHYRIN SUPPORTED ON
POLYSTYRENE AS A HETEROGENEOUS ALKENE
EPOXIDATION AND ALKANE HYDROXYLATION CATALYST
S. Tangestaninejad a , M. H. Habibi a , V. Mirkhani a & M. Moghadam a
a Department of Chemistry , Isfahan University , Isfahan, 81744, Iran
Published online: 16 Aug 2006.
To cite this article: S. Tangestaninejad , M. H. Habibi , V. Mirkhani & M. Moghadam (2002) MANGANESE(III) PORPHYRIN
SUPPORTED ON POLYSTYRENE AS A HETEROGENEOUS ALKENE EPOXIDATION AND ALKANE HYDROXYLATION CATALYST, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:21, 3331-3337, DOI:
10.1081/SCC-120014040
To link to this article: http://dx.doi.org/10.1081/SCC-120014040
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 21, pp. 3331–3337, 2002
MANGANESE(III) PORPHYRIN
SUPPORTED ON POLYSTYRENE
AS A HETEROGENEOUS ALKENE
EPOXIDATION AND ALKANE
HYDROXYLATION CATALYST
*
S. Tangestaninejad, M. H. Habibi,V. Mirkhani,
and M. Moghadam
Department of Chemistry, Isfahan University,
Isfahan 81744, Iran
ABSTRACT
Carboxymethylated crosslinked polystyrene resin [poly(4-
styrylmethylacylchloride) (PSA)] support have been used to
covalently attach manganese(III) tetrakis(4-aminophenyl)-
porphyrin. This catalyst was found to be efficient for alkene
epoxidation and alkane hydroxylation by sodium periodate.
This new hydrogenised catalyst is of high stability and reusability.
The use of synthetic metalloporphyrins as catalysts for hydrocarbons
oxidation has received much attention over the last two decades.[1–3] To
date, however, the utility of these metalloporphyrin catalysts in synthesis
has been limited due to catalyst deactivation through self-destruction and
*Corresponding author. E-mail: stanges@sci.ui.ac.ir
3331
DOI: 10.1081/SCC-120014040
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3332
TANGESTANINEJAD ET AL.
difficulty in recovery of the expensive catalyst. Heterogeneous analogues of
these catalysts not only simplify their use and facilitate product separation,
and prevent intramolecular self-oxidation, but also offer a considerable
economic benefit if the catalyst recycled and reused.[4]
Different methods have been employed to immobilize metallopor-
phyrins on organic or inorganic supports.[5–15] However, attachment of
metalloporphyrins to some of these supports is a reversible process, there-
fore, leaching and loss of their catalytic activities remains a problem. We
now report a novel heterogeneous catalyst for hydrocarbon mono-oxygena-
tion based on chemically modified cross-linked chloromethylated polystyr-
ene. The manganese(III) porphyrin strongly bounds to the support forming
a robust, reusable and active catalyst for oxidation of alkenes and alkanes.
Modified polystyrene support was obtained by cyanation of chloro-
methylated polystyrene in dimethylsulfoxide (DMSO) and hydrolysis to
carboxylic acid by a slight modification of the previously reported method
by Sherrington (Sch. 1).[16] The reaction of this carboxymethylated polysty-
rene with thionyl chloride afforded a solid support, which can be considered
as an insoluble benzoyl chloride. This polymer could readily react with
compounds bearing appropriate functional groups such as amines.
Manganese(III) tetrakis(4-aminophenyl)porphyrin could be covalently
attached to this support in DMF. The polymer-bound porphyrin is insolu-
ble in common organic solvents. The reflectance spectrum clearly indicates a
Soret band at 466 nm and a Q band at 566 nm. IR spectrum of the solid
supported manganese porphyrin shows a ꢀ(CO) at 1670 cmꢀ1. The degree of
manganese porphyrin incorporation into the polymer was determined by
neutron activation analysis (NAA), which shows a value of about 4.5% w/w.
The covalent bonding of the polymer and metalloporphyrin is so strong that
manganese porphyrin is not eluted from the polymer with water and
common organic solvents.
Preliminary investigation on epoxidation of cyclooctene as a typical
substrate in the presence of Mn(TNH2PP)-PSA by sodium periodate revealed
Scheme 1.

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MANGANESE(III) PORPHYRIN
3333
high activity of the catalyst in 2 : 1 CH3CN/H2O mixture. The effect
of different axial ligands upon the rate of epoxidation of cyclooctene was
also investigated. The epoxidation rate decreased in the following order:
imidazole>t-butylpyridine>1-methylimidazole>pyridine. The optimum
condition used for the epoxidation of cyclooctene with this catalyst, employed
the catalyst : oxidant : substrate : imidazole in molar ratio 1 : 100 : 50 : 10.
Mn(TNH2PP)-PSA is an efficient catalyst for epoxidation of different
alkenes and the epoxide yields (Table 1) are comparable to those obtained
using homogeneous catalysts.[17–19] In the case of stilbenes, the trans-stilbene
was converted to trans-epoxide in 55% yield, but cis-stilbene afforded a
75 : 10 mixture of cis- and trans-epoxides. Epoxidation of R-(þ)-limonene
gave a mixture of 1,2- and 8,9-epoxides. The ratio among 1,2- and
8,9-epoxides was found to be 1.25 : 1.
The catalytic hydroxylation of alkanes and arylalkanes with sodium
periodate was performed in the presence of Mn(TNH2PP)-PSA under the
same conditions described for alkene epoxidation (Table 2).
To assess long-term stability and reusability of Mn(TNH2PP)-PSA,
styrene was used as a model substrate, and recycling experiments were carried
out with a single sample of the catalyst. After each experiment, the catalyst
was removed by simple filtration, washed with water and acetonitrile and
reused. The resulted yields and leaching data obtained are listed in Table 3.
We have shown that polystyrene-bound manganese(III) tetrakis(4-
aminophenyl)porphyrin can be used as an effective catalyst for alkene
epoxidation and alkane hydroxylation reactions. The catalyst is robust
toward destructive reactions and can be easily recovered by simple filtration
at the end of the reactions.
EXPERIMENTAL
The porphyrin ligand, 5,10,15,20-tetrakis(4-aminophenyl) porphyrin,
was prepared and metallated according to the literature procedures.[20,21]
Alkenes and alkanes were obtained from Merck or Fluka and were passed
through a column containing active alumina to remove peroxidic impurities.
Modification of Chloromethylated Polystyrene for
Preparation of Poly(4-styrylmethyl)acylchloride
To a solution of DMSO (50 mL), were added chloromethylated
polystyrene (5 g), sodium cyanide (5 g) and refluxed for 4 h. After cooling,
the polymer was filtered, washed with water and acetone and dried at 60ꢁC.

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3334
TANGESTANINEJAD ET AL.
Table 1. Epoxidation of Alkenes with NaIO4 Catalyzed by Mn(TNH2PP)-PSA in
the Presence of Imidazole at Room Temperature
Entry
1
Alkene
Conversion (%)a Epoxide Yield (%)a Reaction Time (h)
91
91
7
2
88
68
7
3
4
100
100
85
70
3
2
5
80
80
7
6
7
65
75
65
75
7
7
8
9
70
55
39(1,2-Epoxide)b
31(8,9-Epoxide)b
7
7
55(trans-Epoxide)b
10
85
75(cis-Epoxide)b
10(trans-Epoxide)b
7
aGLC yield based on starting alkene.
1
bBoth H NMR and GLC data approved the reported yields.

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MANGANESE(III) PORPHYRIN
3335
Table 2. Hydroxylation of Alkanes with NaIO4 Catalyzed by Mn(TNH2PP)-PSA
in Presence of Imidazole at Room Temperature
Entry
1
Alkane
Ketone (%)a
33
Alcohol (%)a
17
Reaction Time (h)
8
2
3
40
35
–
8
8
19
4
5
6
70
35
–
–
–
8
8
8
43
7
8
29
60
–
–
8
8
aGLC yield based on starting alkane.
Table 3. The Result of Mn(TNH2PP)-PSA Catalyst Recovery and
the Manganese Leached in the Epoxidation of Styrene with Sodium
Periodate
Run
Conversion (%)a
Mn Leached (%)b
Time (h)
1
2
3
4
100
95
92
92
1
0.7
0
3
3
3
3
0
aGLC yield based on starting styrene.
bMeasured by atomic absorption spectrometry and based on initial
manganese concentration.

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3336
TANGESTANINEJAD ET AL.
This polymer was heated at 50ꢁC for 4 h in concentrated sulfuric acid
(100 mL) for hydrolysis of the cyanide groups.
The polymer was filtered, washed several times with water and dried.
The polymer was refluxed in thionyl chloride (20 mL) for 8 h. After cooling to
room temperature, the thionyl chloride was removed under reduced pressure
and the resulted carboxymethylated polystyrene was washed with acetone
and dried.
The FT-IR spectra of polymer 2–4 showed characteristic bands due to
CꢂN and C¼O stretching vibrations at 2212, 1765 and 1705 cmꢀ1, respect-
ively. The conversion yield of first step of the reactions shown in Sch. 1,
determined potentiometrically by measuring of the released chloride ion,
was 80–85%. The conversions of the second and third steps, determined
from the IR spectra, were almost complete.
Immobilization of Mn(TNH2PP) on
Poly(4-styrylmethylacylchloride)
To a solution of Mn(TNH2PP) (0.5 g) in DMF (50 mL), were added
poly(4-styrylmethylacylchloride) (5 g) and triethylamine (3 mL). The mixture
was heated at 100ꢁC for 8 h. After cooling to room temperature, the catalyst
was filtered, washed with methanol and acetone and dried.
Typical Procedure for Oxidation Reactions Catalyzed by
Mn(TNH2PP)-PSA
All of the reactions were carried out at room temperature under air in a
25 mL flask equipped with a magnetic stirrer bar. A solution of NaIO4
(2 mmol) in H2O (5 mL) was added to a mixture of alkene or alkane (1 mmol),
Mn(TNH2PP)-PSA (20 mmol) and imidazole (0.2 mmol) in CH3CN (10 mL).
The progress of reaction was monitored by GLC. The reaction mixture was
diluted with CH2Cl2 (20 mL) and filtered. The resin was thoroughly washed
with CH2Cl2 an combined washings and filterates were purified on silica-gel
1
plates or silica-gel column. IR and H NMR spectral data confirmed the
identities of the products.
ACKNOWLEDGMENT
We thank the financial support of this work by the Isfahan University
Research Council.

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MANGANESE(III) PORPHYRIN
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Received in Japan August 7, 2001

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