Y.-J. Ye et al. / Journal of Molecular Catalysis A: Chemical 331 (2010) 29–34
33
4. Conclusion
On the basis of synthesis of styrene–hydroxyethyl methacry-
late copolymer microspheres with functionalized hydroxyl
a
and Mn(III) porphyrin with a functionalized carboxyl, we have
prepared a new type of copolymer microspheres immobilized por-
phyrinatomanganese(III), P(St-co-HEMA)MnP, by a condensation
reaction between a carboxyl in porphyrin ring and a hydroxyl
in copolymer microsphere surface. The copolymer microspheres
have smooth surface and spherical morphology with ca. 4 m
diameter. The catalysis of P(St-co-HEMA)MnP to epoxide cyclo-
hexene in the presence of molecular oxygen and isobutylaldehyde
have been investigated in the presence of molecular oxygen and
isobutylaldehyde. It is found that P(St-co-HEMA)MnP has high
catalytic activity, to be comparable to that of non-supported
MnCMPTTP, and retains its high catalytic activity after being reused
four times. It seems that P(St-co-HEMA)MnP is a mild, reusable
and highly efficient heterogeneous catalyst for the epoxidation of
cyclohexene.
Fig. 4. Changes of the yield of epoxycyclyohexane with catalytic time in the epoxida-
tion of cyclohexene catalyzed by P(St-co-HEMA)MnP. Reaction conditions: catalysts
(0.013 g P(St-co-HEMA)MnP, containing 0.06 mol porphyrinatomanganese(III)),
substrate (2 mmol), isobutylaldehyde (6 mmol), acetone (10 ml), 1 atm of oxygen,
rt.
Acknowledgments
We are grateful to the supports of Guangzhou Municipality Sci-
ence & Technology Bureau of China, the National Natural Science
Foundation of China and National Key Foundation Research Devel-
opment Project (973) Item of China (No. 2007 CB815306).
epoxycyclohexane is almost unchanged with a further increase in
the reaction time. The results suggest that 4 h may be the optimum
reaction time in this experiment system.
are summarized in Table 2. Controlled experiment using P(St-co-
HEMA) as catalyst was carried out and only 12% cyclohexene could
be converted, indicating that the metalloporphyrin is crucial for the
epoxidation. From Table 2, we can find that the yield of cyclohexene
epoxide catalyzed by P(St-co-HEMA)MnP is 93.3% and TON of P(St-
co-HEMA)MnP is 24,049 in the presence of molecular oxygen and
isobutylaldehyde after 4 h. It is obvious that P(St-co-HEMA)MnP
is a highly efficient heterogeneous catalyst for the epoxidation of
cyclohexene and its catalytic activity is comparable to that of non-
supported MnCMPTTP.
It is notable that P(St-co-HEMA)MnP can be completely recov-
ered and effectively reused. After the epoxidation of cyclohexene,
P(St-co-HEMA)MnP was recycled by simple filtration and subse-
quent washing of the solid remnants with acetone. A fresh solution
of substrate was then introduced to the catalytic material, and
the catalyzed reaction was restarted. As shown in Table 2, P(St-
co-HEMA)MnP retains its high yield of cyclohexene epoxide and
high turnover numbers after being reused four times. All reac-
tion solutions analyzed after catalytic reactions did not show the
characteristic Soret band of MnCMPTTP, which demonstrated that
no MnCMPTTP was leaching into the reaction solution. Thus, our
results reveal the stable catalytic capability of this catalyst as well
as the success of this new synthetic route.
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Catalysts
Run
Conv. (%)
Yield (%)
TONc
P(St-co-HEMA)MnPa
1
2
3
4
99.6
99.0
96.0
90.4
93.3
93.0
90.7
83.6
24,049
23,968
23,379
21,545
MnCMPTTPb
P(St-co-HEMA)
1
1
99.1
12.0
95.0
10.0
24,356
a
13 mg P(St-co-HEMA)MnP (containing 0.06 mol MnCMPTTP).
0.06 mol MnCMPTTP.
Turnover number = product (mol)/catalyst (mol).
b
c
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