1648
S. Lai, D. G. Lee
PAPER
Table 2 Effect of Solid Supports on the Yields of 4-Methoxyben-
zaldehyde Obtained from the Oxidation of trans-Anethole and trans-
4-Methoxycinnnamic Acid
min and then filtered through Celite. The residue was washed with
CH2Cl2 (3 10 mL). The filtrate and washings were combined,
dried (MgSO4) and concentrated to give 4-methylbenzaldehyde
(117 mg, 97%) as a colorless oil.
IR (film): = 3032, 2732, 1702, 1690, 1605, 1577 cm–1.
1H NMR (CDCl3, 200 MHz): = 9.96 (1 H, s), 7.78 (2 H, d, J = 7.8
Hz), 7.33 (2 H, d, J = 7.8 Hz), 2.43 (3 H, s).
Solid Supporta
Yield
(%)b
Yield
(%)c
Amberlite 1200 (H)
Amberlite 36
92
90
60
14
88
5
94
92
97
92
95
0
13C NMR (CDCl3, 50 MHz): = 191.9, 145.5, 134.1, 129.7, 129.6,
21.8.
Amberlite IR-120d
Amberlite IR-120 (sodium form)
Amberlyst 15
Acknowledgement
The authors are pleased to acknowledge financial support from the
Natural Sciences and Engineering Research Council of Canada.
Rexyn RG 50 (H)
Rexyn 101 (H)
93
9
95
90
91
0
References
Al2O3 (acidic, Brockmann 1)d
(1) Lee, D. G.; Chen, T. In Comprehensive Organic Synthesis,
Vol. 7; Trost, B. M., Ed.; Pergamon: Oxford, 1991, 541–
591.
(2) Berglund, R. A. In Encyclopedia of Reagents for Organic
Synthesis, Vol. 6; Paquette, L. A., Ed.; Wiley: New York,
1995, 3837–3843.
(3) Martin, V. S.; Palazon, J. M.; Rodriguez, C. M. In
Encyclopedia of Reagents for Organic Synthesis, Vol. 6;
Paguette, L. A., Ed.; Wiley: New York, 1995, 4415–4422.
(4) March, J. Advanced Organic Chemistry; Wiley: New York,
1992, 1181.
(5) Arndt, D. Manganese Compounds as Oxidizing Agents in
Organic Chemistry; Open Court: LaSalle IL, 1981, 241–
246.
d
SiO2
34
2
CuSO4 5H2O
Molecular sieves 5 Å
Molecular sieves 5 Åd
Florisild
4
0
7
89
90
36
a Solid supports were obtained from Aldrich or Fisher.
b trans-Anethole (1 mmol) was oxidized by KMnO4 (3 mmol) and sol-
id support (1.6 g) in CH2Cl2 (5 mL) for 80 min.
c trans-4-Methoxycinnamic acid (1 mmol) was oxidized by KMnO4
(3 mmol) and solid support (1.6 g) in CH2Cl2 (5 mL) for 30 min.
d H2O (0.4 mL) was added.
(6) Noureldin, N. A.; Lee, D. G. J. Org. Chem. 1982, 47, 2790.
(7) (a) Noureldin, N. A.; Zhao, D.; Lee, D. G. J. Org. Chem.
1997, 62, 8767. (b) Zhao, D.; Lee, D. G. Synthesis 1994,
915.
(8) Noureldin, N. A.; McConnell, W. B.; Lee, D. G. Can. J.
Chem. 1984, 62, 2113.
(9) Noureldin, N. A.; Caldwell, M.; Hendry, J.; Lee, D. G.
Synthesis 1998, 1587.
(10) (a) Harris, C. E.; Chrisman, W.; Bickford, S. A.; Lee, L. Y.;
Torreblanca, A. E.; Singaram, B. Tetrahedron Lett. 1997,
38, 981. (b) Sreekumar, R.; Padmakumar, R. Tetrahedron
Lett. 1997, 38, 5143.
(11) (a) Joshi, P. L.; Hazra, B. G. J. Chem. Res. (S) 2000, 38.
(b) Parish, E. J.; Li, S. J. Chem. Res. (S) 1996, 288.
(c) Salvador, J. A. R.; Sa e Melo, M. L.; Campos Neves, A.
S. Tetrahedron Lett. 1996, 37, 687. (d) Das, J.;
Chandrasekaran, S. Tetrahedron 1994, 50, 11709. (e) Lee,
D. G.; Chen, T.; Wang, Z. J. Org. Chem. 1993, 58, 2918.
(f) Baskaran, S.; Islam, I.; Vankar, P. S.; Chandrasekaran, S.
J. Chem. Soc., Chem. Commun. 1992, 626. (g) Baskaran,
S.; Islam, I.; Vankar, P. S.; Chandrasekaran, S. J. Chem.
Soc., Chem. Commun. 1990, 1670. (h) Syamala, M. S.; Das,
J.; Baskaran, S.; Chandrasekaran, S. J. Org. Chem. 1992, 57,
1928. (i) Baskaran, S.; Das, J.; Chandrasekaran, S. J. Org.
Chem. 1989, 54, 5182.
were all obtained commercially and used without further purifica-
tion. The products, all previously prepared compounds, were iden-
tified spectroscopically (1H NMR, 13C NMR and IR) by comparison
with literature data.
Oxidation of Styrenes and Cinnamic Acid Derivatives by
KMnO4 under Heterogeneous Conditions; Typical Procedures
Condition c; p-Anisaldehyde: To a solution of anethole (0.148 g, 1.0
mmol) in CH2Cl2 (35 mL) was added KMnO4/alumina reagent (4.65
g). The heterogeneous mixture was stirred at r.t. until TLC analysis
indicated that the reaction was complete (4 h). The contents of the
flask were filtered through Celite and washed with CH2Cl2 (3 15
mL). The product was separated by evaporation of the solvent to
give p-anisaldehyde (0.128 g, 94%).
IR (film): = 3009, 2739, 1684, 1604, 1578, 1511, 1461 cm–1.
1H NMR (CDCl3, 200 MHz): = 9.90 (1 H, s), 7.85 (2 H, d, J = 8.7
Hz), 7.01 (2 H, d, J = 8.7 Hz), 3.89 (3 H, s).
13C NMR (CDCl3, 50 MHz): = 190.6, 164.4, 131.7, 129.7, 114.1,
55.3.
(12) Lee, D. G.; Noureldin, N. A. J. Am. Chem. Soc. 1983, 105,
3188.
(13) (a) Prabhakaran, P. W.; Venkatachalam, S.; Ninan, K. N.
European Polymer J. 1999, 35, 1743. (b) Abraham, S.;
Rajan, P. K.; Sreekumar, K. Polymer J. 1997, 29, 12.
Condition b; 4-Methylbenzaldehyde: Amberlite 1R-120 (Mallinck-
rodt, 0.8 g) and H2O (0.4 mL) were ground in a mortar for 3 min to
give a wet powder and added to 4-methylcinnamic acid (162 mg,
1.0 mmol) dissolved in CH2Cl2 (5 mL) followed by finely ground
KMnO4 (490 mg, 3.00 mmol). This mixture was stirred at r.t. for 20
Synthesis 2001, No. 11, 1645–1648 ISSN 0039-7881 © Thieme Stuttgart · New York