SYNTHESIS OF 1,3-BENZODIOXOLES
93
filtered and the resultant solids were dried and activated at 400◦C
for 2 h in an electric furnace to obtain a catalyst.
TABLE 2
Effect of catalyst on Ketalization of cyclohexanone with
catechol
Synthesis of 1,3-benzodioxoles
Entry
Catalyst
MCM-41a
Sulfated MCM-41
Cu(II)-sulfated MCM-41
Ni(II)-MCM-41
Fe(III)-MCM-41
Co(II)-MCM-41
Montmorillonite K-10
HY-Zeolite
Time(h)
Yield %
A mixture of carbonyl compound (10 mmol), catechol
(10 mmol), 10 mL of toluene/benzene, and the catalyst
(10 mol%) were mixed in a two-necked round bottom flask
equipped with thermometer, and a Dean-Stark apparatus was
used to remove the water continuously from the reaction mix-
ture. The mixture was refluxed with stirring for the specified
periods. TLC was used to monitor the progress of the reac-
tion. After completion of the reaction, the reaction mixture was
filtered, washed with H2O (10 mL) and dried over (Na2SO4).
Removal of the solvent followed by recrystallization from di-
ethyl ether gave the desired product. The spectral data (1H NMR
and IR) of the compounds were in agreement with that reported
in literature.[15]
1
2
3
4
5
6
7
8
6.0
5.0
1.0
4.0
1.0
5.0
2.7
6.0
–
12
98
20
90
15
9315
8118
aThe reactions are carried out with untreated MCM-41.
activity for the reaction with the conversion over 98% within
1 h, while the similar catalysts with Ni(II) and Co(II) were not
so efficient with the conversion below 20% even after 4 h. Even
though the Fe(III)-MCM-41 gave a preferable result with the
conversion around 90%, it is having difficulties of catalyst in-
stability and product separation. No reaction was observed over
ZSM-5, SiO2, and Al2O3; HX was found to be slightly active,
whereas NaX was also inactive.
REFERENCES
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In conclusion, we have developed a highly convenient
method for the synthesis of 1,3-benzodioxoles using Cu(II)-
sulfated MCM-41 as catalyst. The yields of the products pro-
duced are very high compared to earlier methods with a shorter
reaction time. The great advantage of the present method is that
the catalyst is easily prepared and can easily be recovered and
reused.
12. Nishida, Y.; Abe, M.; Ohrui, H.; Meguro, H. Tetrahedron: Asymmetry 1993,
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Preparation of Metal-impregnated Sulfated MCM-41
The sulfated MCM-41 catalyst was prepared and charac-
terized by the procedure reported in literature.[17] The metal
impregnated sulfated MCM-41 were prepared by slowly adding
the MCM-41 (1.0 g) to dilute solutions of Cu(NO3)2 (1 M,
12.5 mL), Fe(NO3)3 (1 M, 12.5 mL), Co(NO3)2(1 M, 12.5 mL)
and Ni(NO3)2(1 M, 12.5 mL), respectively, in acetone and stir-
ring for a period of 24 h. After impregnation, suspensions were
14. Jin, T.S.; Zhang, S.L.; Wang, X.F. J. Chem. Res. 2001, 7, 289.
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227; (b) Ficht, S.; Roglin, L.; Ziehe, M.; Breyer, D. Synlett. 2004, 14, 2525;
(c) Xuezheng, L.; Shan, G.; Wenjuan, W. Wenping, C.; Jianguo, Y. Chin. J.
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17. Parida, K.M.; Rath, D. J. Mol. Catal. A: Chem. 2006, 258, 381.
18. Xuezheng, L.; Shan, G.; Jianguo, Y.; Caihua, L.; Xinyu, Y.; Mingyuan, H.
Front. Chem. China 2007, 2, 31.