Phase transfer catalyzed oxidation of alcohols with sodium hypochlorite

Tetrahedron Letters

Volumn 39, Issue 40, 1998, Pages 7263-7266

  Mirafzal, Gholam A ^a   Lozeva, Albena M ^a  

^a DRAKE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; HYPOCHLORITE SODIUM;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; GAS CHROMATOGRAPHY; MASS SPECTROMETRY; ORGANIC CHEMISTRY; OXIDATION;

EID: 0032191496     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)01584-6     Document Type: Article

References (15)

1. 1. Collins, J. C.; Hes, W. W.; Franck, F. J. Tetrahedron Lett. 1968, 3363.; Corey, E. J.; Suggs, J. W. Tetrahedron Lett, 1975, 2647.; Corey, E. J; Schmidt, G. Tetrahedron Lett. 1979, 399.; Cheng, Y. S.; Liu, W. L.; Chen, S. Synthesis, 1980, 223.; Czernecki, S.; Georgoulis, C.; Stevens, C. L.; Vijayakumaran, K. Tetrahedron Lett. 1985, 1699.; Pletcher, D; Tait, S. J. D. J. Chem. Soc. Perkin Trans II, 1979, 788; Landini, D.; Montanari, F.; Rolla, F. Synthesis 1979, 134.; Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Texbook of Practical Organic Chemistry. 5th Ed. 1989, P. 668.; Taylor, R. J. K.; Wei, X. Tetrahedron Lett. 1998, 39, 3815.
2. 1. Collins, J. C.; Hes, W. W.; Franck, F. J. Tetrahedron Lett. 1968, 3363.; Corey, E. J.; Suggs, J. W. Tetrahedron Lett, 1975, 2647.; Corey, E. J; Schmidt, G. Tetrahedron Lett. 1979, 399.; Cheng, Y. S.; Liu, W. L.; Chen, S. Synthesis, 1980, 223.; Czernecki, S.; Georgoulis, C.; Stevens, C. L.; Vijayakumaran, K. Tetrahedron Lett. 1985, 1699.; Pletcher, D; Tait, S. J. D. J. Chem. Soc. Perkin Trans II, 1979, 788; Landini, D.; Montanari, F.; Rolla, F. Synthesis 1979, 134.; Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Texbook of Practical Organic Chemistry. 5th Ed. 1989, P. 668.; Taylor, R. J. K.; Wei, X. Tetrahedron Lett. 1998, 39, 3815.
3. 1. Collins, J. C.; Hes, W. W.; Franck, F. J. Tetrahedron Lett. 1968, 3363.; Corey, E. J.; Suggs, J. W. Tetrahedron Lett, 1975, 2647.; Corey, E. J; Schmidt, G. Tetrahedron Lett. 1979, 399.; Cheng, Y. S.; Liu, W. L.; Chen, S. Synthesis, 1980, 223.; Czernecki, S.; Georgoulis, C.; Stevens, C. L.; Vijayakumaran, K. Tetrahedron Lett. 1985, 1699.; Pletcher, D; Tait, S. J. D. J. Chem. Soc. Perkin Trans II, 1979, 788; Landini, D.; Montanari, F.; Rolla, F. Synthesis 1979, 134.; Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Texbook of Practical Organic Chemistry. 5th Ed. 1989, P. 668.; Taylor, R. J. K.; Wei, X. Tetrahedron Lett. 1998, 39, 3815.
4. 1. Collins, J. C.; Hes, W. W.; Franck, F. J. Tetrahedron Lett. 1968, 3363.; Corey, E. J.; Suggs, J. W. Tetrahedron Lett, 1975, 2647.; Corey, E. J; Schmidt, G. Tetrahedron Lett. 1979, 399.; Cheng, Y. S.; Liu, W. L.; Chen, S. Synthesis, 1980, 223.; Czernecki, S.; Georgoulis, C.; Stevens, C. L.; Vijayakumaran, K. Tetrahedron Lett. 1985, 1699.; Pletcher, D; Tait, S. J. D. J. Chem. Soc. Perkin Trans II, 1979, 788; Landini, D.; Montanari, F.; Rolla, F. Synthesis 1979, 134.; Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Texbook of Practical Organic Chemistry. 5th Ed. 1989, P. 668.; Taylor, R. J. K.; Wei, X. Tetrahedron Lett. 1998, 39, 3815.
5. 1. Collins, J. C.; Hes, W. W.; Franck, F. J. Tetrahedron Lett. 1968, 3363.; Corey, E. J.; Suggs, J. W. Tetrahedron Lett, 1975, 2647.; Corey, E. J; Schmidt, G. Tetrahedron Lett. 1979, 399.; Cheng, Y. S.; Liu, W. L.; Chen, S. Synthesis, 1980, 223.; Czernecki, S.; Georgoulis, C.; Stevens, C. L.; Vijayakumaran, K. Tetrahedron Lett. 1985, 1699.; Pletcher, D; Tait, S. J. D. J. Chem. Soc. Perkin Trans II, 1979, 788; Landini, D.; Montanari, F.; Rolla, F. Synthesis 1979, 134.; Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Texbook of Practical Organic Chemistry. 5th Ed. 1989, P. 668.; Taylor, R. J. K.; Wei, X. Tetrahedron Lett. 1998, 39, 3815.
6. 1. Collins, J. C.; Hes, W. W.; Franck, F. J. Tetrahedron Lett. 1968, 3363.; Corey, E. J.; Suggs, J. W. Tetrahedron Lett, 1975, 2647.; Corey, E. J; Schmidt, G. Tetrahedron Lett. 1979, 399.; Cheng, Y. S.; Liu, W. L.; Chen, S. Synthesis, 1980, 223.; Czernecki, S.; Georgoulis, C.; Stevens, C. L.; Vijayakumaran, K. Tetrahedron Lett. 1985, 1699.; Pletcher, D; Tait, S. J. D. J. Chem. Soc. Perkin Trans II, 1979, 788; Landini, D.; Montanari, F.; Rolla, F. Synthesis 1979, 134.; Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Texbook of Practical Organic Chemistry. 5th Ed. 1989, P. 668.; Taylor, R. J. K.; Wei, X. Tetrahedron Lett. 1998, 39, 3815.
7. 1. Collins, J. C.; Hes, W. W.; Franck, F. J. Tetrahedron Lett. 1968, 3363.; Corey, E. J.; Suggs, J. W. Tetrahedron Lett, 1975, 2647.; Corey, E. J; Schmidt, G. Tetrahedron Lett. 1979, 399.; Cheng, Y. S.; Liu, W. L.; Chen, S. Synthesis, 1980, 223.; Czernecki, S.; Georgoulis, C.; Stevens, C. L.; Vijayakumaran, K. Tetrahedron Lett. 1985, 1699.; Pletcher, D; Tait, S. J. D. J. Chem. Soc. Perkin Trans II, 1979, 788; Landini, D.; Montanari, F.; Rolla, F. Synthesis 1979, 134.; Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Texbook of Practical Organic Chemistry. 5th Ed. 1989, P. 668.; Taylor, R. J. K.; Wei, X. Tetrahedron Lett. 1998, 39, 3815.
8. 1. Collins, J. C.; Hes, W. W.; Franck, F. J. Tetrahedron Lett. 1968, 3363.; Corey, E. J.; Suggs, J. W. Tetrahedron Lett, 1975, 2647.; Corey, E. J; Schmidt, G. Tetrahedron Lett. 1979, 399.; Cheng, Y. S.; Liu, W. L.; Chen, S. Synthesis, 1980, 223.; Czernecki, S.; Georgoulis, C.; Stevens, C. L.; Vijayakumaran, K. Tetrahedron Lett. 1985, 1699.; Pletcher, D; Tait, S. J. D. J. Chem. Soc. Perkin Trans II, 1979, 788; Landini, D.; Montanari, F.; Rolla, F. Synthesis 1979, 134.; Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Texbook of Practical Organic Chemistry. 5th Ed. 1989, P. 668.; Taylor, R. J. K.; Wei, X. Tetrahedron Lett. 1998, 39, 3815.
9. 1. Collins, J. C.; Hes, W. W.; Franck, F. J. Tetrahedron Lett. 1968, 3363.; Corey, E. J.; Suggs, J. W. Tetrahedron Lett, 1975, 2647.; Corey, E. J; Schmidt, G. Tetrahedron Lett. 1979, 399.; Cheng, Y. S.; Liu, W. L.; Chen, S. Synthesis, 1980, 223.; Czernecki, S.; Georgoulis, C.; Stevens, C. L.; Vijayakumaran, K. Tetrahedron Lett. 1985, 1699.; Pletcher, D; Tait, S. J. D. J. Chem. Soc. Perkin Trans II, 1979, 788; Landini, D.; Montanari, F.; Rolla, F. Synthesis 1979, 134.; Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Texbook of Practical Organic Chemistry. 5th Ed. 1989, P. 668.; Taylor, R. J. K.; Wei, X. Tetrahedron Lett. 1998, 39, 3815.
10. 2. Stevens, R.V.; Chapman, K.T.; Stubbs, C. A.; Tam, W. W.; Albizatie, K. F. Tetrahedron Lett. 1982, 23, 4647. This article reported successful oxidation of secondary alcohols using sodium hypochlorite in acetic acid. However, the method is not effective for oxidation of primary alcohols and alcohols containing double bonds. It is reported that oxidation of primary alcohols leads to dimeric esters under the acidic condition described. For instance, oxidation of 1-decanol leads to decyl decanoate as the major product. Also oxidation of alcohols containing double bonds is reported to produce chlorine-containing products. Reactions times are long, they typically require 2-4 hours for completion. In addition, reagents used are potentially dangerous. Glacial acetic acid is corrosive and causes burns; the vapor is extremely irritating to mucous membranes and the upper respiratory tract, and a sodium hypochlorite solution in glacial acetic acid emits chlorine gas, which is a respiratory and eye irritant. We believe our method of phase transfer catalyzed oxidation of alcohol in ethyl acetate is superior over this both in terms of its application and safety consideration.
11. 3. This paper was presented in the Division of Chemical Education at the 213th ACS National Meeting in San Francisco, California, April 13-17, 1997 (Abstract # 100).
12. 4. In the absence of phase transfer catalyst, little or no reaction is evident and the alcohol is recovered unchanged.
13. 5. Other commercial bleaches work as effectively when used fresh. For precise work, samples may be titrated according to the procedure of Kolthoff, I. M.; Belcher, R. Volumetric Analysis, Interscience: New York, 1957, P. 262.
14. 6. Materials and Methods: 1-Octanol, 2-phenylethanol, 2-octanol, cholesterol, benzyl alcohol, 9-fluorenol, benzhydrol, tetrabutylammonium bromide, ethyl acetate, dichloromethane were all purchased from Aldrich Chemical Company and were used as such without further purification. Thin layer chromatography (TLC) was performed on Eastman Kodak TLC plates (coated film, #13179) with a fluorescence indicator. Commercial Clorox Fresh Scent Bleach (5.25% Sodium hypochlorite) was used. Fourier-transform infrared (FT-IR) were performed neat or as solutions in dichloromethane on a Nicolet 510P Spectrometer. The low resolution mass spectra (LRMS) were obtained on a Hewlett-Packard 5970 GC-MS spectrometer equipped with an HP-1 Cross-linked Methyl Silicone Gum (12 m × 0.2 mm × 0.33 mm film thickness) capillary column. The initial column temperature of 60°C (1 min) then 10°/min increments up to 250° (5min) were used for all the analysis except cholesterol where the initial column temperature of 150°C (1 min) then 10°/min increments up to 250°C (15 min) were used.
15. -1. Microscale oxidation reactions using 0.556 mmol of the appropriate alcohol, 1.5 mL of ethyl acetate, 1.5 mL of bleach, and 0.030 g (0.093 mmol) of tetrabutylammonium bromide produced a similar yield of products but in a shorter period of time, about 20 minutes.