A novel and efficient oxidation of 1,2-amino alcohols to dialkylamides

Synlett

Volumn , Issue 12, 2002, Pages 2092-2094

  García Valverde, María ^a   Pedrosa, Rafael ^b   Vicente, Martina ^b  

^a UNIVERSITY OF BURGOS   (Spain)

^b UNIVERSITY OF VALLADOLID   (Spain)

Author keywords

1,2 amino alcohols; Oxidations; Potassium hydroxide; Radical reactions; amino ketones

Indexed keywords

AMIDE; AMINOALCOHOL; KETONE DERIVATIVE; POTASSIUM HYDROXIDE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; OXIDATION;

EID: 0036458156     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2002-35602     Document Type: Article

References (39)

1. Camps, P.; Muñoz-Torrero, D.; Muñoz-Torrero, V. Tetrahedron Lett. 1995, 36, 1917.
2. (a) Burton, R. D.; Bartberger, M. D.; Zhang, Y.; Eyler, J. R.; Schanze, K. S. J. Am. Chem. Soc. 1996, 118, 5655.
3. (b) Chen, L. H.; Farahat, M. S.; Gaillard, E. R.; Farid, S.; Whitten, D. G. J. Photochem. Photobiol. A: Chem. 1996, 95, 21.
4. (c) Kellett, M. A.; Whitten, D. G. Res. Chem. Intermed. 1995, 21, 587.
5. (d) Gan, H.; Kellett, M. A.; Leon, J. W.; Kloeppner, L.; Leinhos, U.; Gould, I. R.; Farid, S.; Whitten, D. G. J. Photochem. Photobiol. A: Chem. 1994, 82, 211.
6. Yuste, F.; Origel, A. E.; Breña, L. J. Synthesis 1983, 109.
7. (a) Benhaliliba, H.; Derdour, A.; Bazureau, J.-P.; Texier-Boullet, F.; Hamelin, J. Tetrahedron Lett. 1998, 39, 541.
8. (b) Harris, C. E.; Lee, L. Y.; Dorr, H.; Singaram, B. Tetrahedron Lett. 1995, 36, 2921; and references therein.
9. Lopez, L.; Troisi, L. Tetrahedron Lett. 1992, 48, 7321.
10. García-Valverde, M.; Pedrosa, R.; Vicente, M.; García-Granda, S.; Gutiérrez-Rodríguez, A. Tetrahedron 1996, 52, 10761.
11. García-Valverde, M.; Nieto, J.; Pedrosa, R.; Vicente, M. Tetrahedron 1999, 55, 2755.
12. For oxidations under air in strongly basic solutions, see: (a) Elkik, E. Bull. Soc. Chim. Fr. 1959, 933. (b) Russell, G. A.; Bemis, A. G. J. Am. Chem. Soc. 1966, 88, 5491. (c) Gersmann, H. R.; Bickel, A. F. J. Chem. Soc. B 1971, 2230. (d) Neumann, R.; Sasson, Y. J. Org. Chem. 1984, 49, 1282.
13. For oxidations under air in strongly basic solutions, see: (a) Elkik, E. Bull. Soc. Chim. Fr. 1959, 933. (b) Russell, G. A.; Bemis, A. G. J. Am. Chem. Soc. 1966, 88, 5491. (c) Gersmann, H. R.; Bickel, A. F. J. Chem. Soc. B 1971, 2230. (d) Neumann, R.; Sasson, Y. J. Org. Chem. 1984, 49, 1282.
14. For oxidations under air in strongly basic solutions, see: (a) Elkik, E. Bull. Soc. Chim. Fr. 1959, 933. (b) Russell, G. A.; Bemis, A. G. J. Am. Chem. Soc. 1966, 88, 5491. (c) Gersmann, H. R.; Bickel, A. F. J. Chem. Soc. B 1971, 2230. (d) Neumann, R.; Sasson, Y. J. Org. Chem. 1984, 49, 1282.
15. For oxidations under air in strongly basic solutions, see: (a) Elkik, E. Bull. Soc. Chim. Fr. 1959, 933. (b) Russell, G. A.; Bemis, A. G. J. Am. Chem. Soc. 1966, 88, 5491. (c) Gersmann, H. R.; Bickel, A. F. J. Chem. Soc. B 1971, 2230. (d) Neumann, R.; Sasson, Y. J. Org. Chem. 1984, 49, 1282.
16. Typical experimental procedure: The amino alcohol (1a-k) (0.1 g) was added to a stirred suspension of KOH (1.0 g) in diethyl ether (20 mL). The stirring was continued for the proper time (Table 1) at room temperature. The solid was filtered off and washed with ether. The solvent was removed to yield the amide. The solid was dissolved in water and the solution acidified with HCl and extracted with ether. The organic layer was dried and the solvent was removed to yield the corresponding carboxylic acid.
17. The starting amino alcohols were purchased from the usual suppliers (1e: 1-dimethylamino-2-propanol, 1f: N-methylephedrine, 1j: 2-dimethylamino-2-methyl-1-propanol, 1k: 1-methyl-2-piperidinemethanol) or synthesized by literature procedures: (a) 1a (2-dimethylamino-1-propanol): Rosnati, V. Gazz. Chim. Ital. 1950, 80, 663. (b) 1b (2-Dibenzylamino-1-propanol) and 1i (2-Dibenzylamino-2-methyl-1-propanol): Kerwin, J. F.; Ullyot, G. E.; Fuson, R. C.; Zirkle, C. L. J. Am. Chem. Soc. 1947, 69, 2961. (c) 1c (2-Dimethylamino-1-butanol): Halverstadt, I. F.; Hardie, W. R.; Willians, A. R. J. Am. Chem. Soc. 1959, 81, 3618. (d) 1d (2-Dimethylamino-2-phenylethanol): Miyano, S.; Lu, L. D.-L.; Viti, S. M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 4350. (e) 1g (2-Dibenzylamino-1-phenyl-1-propanol): Schwan, T. J.; Lougheed, G. S.; Burrous, S. E. J. Heterocyclic Chem. 1974, 11, 807. (f) 1h (2-Butylamino-1-phenyl-1-propanol): Soai, K.; Yokoyama, S.; Hayasaka, T. J. Org. Chem. 1991, 56, 4264.
18. The starting amino alcohols were purchased from the usual suppliers (1e: 1-dimethylamino-2-propanol, 1f: N-methylephedrine, 1j: 2-dimethylamino-2-methyl-1-propanol, 1k: 1-methyl-2-piperidinemethanol) or synthesized by literature procedures: (a) 1a (2-dimethylamino-1-propanol): Rosnati, V. Gazz. Chim. Ital. 1950, 80, 663. (b) 1b (2-Dibenzylamino-1-propanol) and 1i (2-Dibenzylamino-2-methyl-1-propanol): Kerwin, J. F.; Ullyot, G. E.; Fuson, R. C.; Zirkle, C. L. J. Am. Chem. Soc. 1947, 69, 2961. (c) 1c (2-Dimethylamino-1-butanol): Halverstadt, I. F.; Hardie, W. R.; Willians, A. R. J. Am. Chem. Soc. 1959, 81, 3618. (d) 1d (2-Dimethylamino-2-phenylethanol): Miyano, S.; Lu, L. D.-L.; Viti, S. M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 4350. (e) 1g (2-Dibenzylamino-1-phenyl-1-propanol): Schwan, T. J.; Lougheed, G. S.; Burrous, S. E. J. Heterocyclic Chem. 1974, 11, 807. (f) 1h (2-Butylamino-1-phenyl-1-propanol): Soai, K.; Yokoyama, S.; Hayasaka, T. J. Org. Chem. 1991, 56, 4264.
19. The starting amino alcohols were purchased from the usual suppliers (1e: 1-dimethylamino-2-propanol, 1f: N-methylephedrine, 1j: 2-dimethylamino-2-methyl-1-propanol, 1k: 1-methyl-2-piperidinemethanol) or synthesized by literature procedures: (a) 1a (2-dimethylamino-1-propanol): Rosnati, V. Gazz. Chim. Ital. 1950, 80, 663. (b) 1b (2-Dibenzylamino-1-propanol) and 1i (2-Dibenzylamino-2-methyl-1-propanol): Kerwin, J. F.; Ullyot, G. E.; Fuson, R. C.; Zirkle, C. L. J. Am. Chem. Soc. 1947, 69, 2961. (c) 1c (2-Dimethylamino-1-butanol): Halverstadt, I. F.; Hardie, W. R.; Willians, A. R. J. Am. Chem. Soc. 1959, 81, 3618. (d) 1d (2-Dimethylamino-2-phenylethanol): Miyano, S.; Lu, L. D.-L.; Viti, S. M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 4350. (e) 1g (2-Dibenzylamino-1-phenyl-1-propanol): Schwan, T. J.; Lougheed, G. S.; Burrous, S. E. J. Heterocyclic Chem. 1974, 11, 807. (f) 1h (2-Butylamino-1-phenyl-1-propanol): Soai, K.; Yokoyama, S.; Hayasaka, T. J. Org. Chem. 1991, 56, 4264.
20. The starting amino alcohols were purchased from the usual suppliers (1e: 1-dimethylamino-2-propanol, 1f: N-methylephedrine, 1j: 2-dimethylamino-2-methyl-1-propanol, 1k: 1-methyl-2-piperidinemethanol) or synthesized by literature procedures: (a) 1a (2-dimethylamino-1-propanol): Rosnati, V. Gazz. Chim. Ital. 1950, 80, 663. (b) 1b (2-Dibenzylamino-1-propanol) and 1i (2-Dibenzylamino-2-methyl-1-propanol): Kerwin, J. F.; Ullyot, G. E.; Fuson, R. C.; Zirkle, C. L. J. Am. Chem. Soc. 1947, 69, 2961. (c) 1c (2-Dimethylamino-1-butanol): Halverstadt, I. F.; Hardie, W. R.; Willians, A. R. J. Am. Chem. Soc. 1959, 81, 3618. (d) 1d (2-Dimethylamino-2-phenylethanol): Miyano, S.; Lu, L. D.-L.; Viti, S. M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 4350. (e) 1g (2-Dibenzylamino-1-phenyl-1-propanol): Schwan, T. J.; Lougheed, G. S.; Burrous, S. E. J. Heterocyclic Chem. 1974, 11, 807. (f) 1h (2-Butylamino-1-phenyl-1-propanol): Soai, K.; Yokoyama, S.; Hayasaka, T. J. Org. Chem. 1991, 56, 4264.
21. The starting amino alcohols were purchased from the usual suppliers (1e: 1-dimethylamino-2-propanol, 1f: N-methylephedrine, 1j: 2-dimethylamino-2-methyl-1-propanol, 1k: 1-methyl-2-piperidinemethanol) or synthesized by literature procedures: (a) 1a (2-dimethylamino-1-propanol): Rosnati, V. Gazz. Chim. Ital. 1950, 80, 663. (b) 1b (2-Dibenzylamino-1-propanol) and 1i (2-Dibenzylamino-2-methyl-1-propanol): Kerwin, J. F.; Ullyot, G. E.; Fuson, R. C.; Zirkle, C. L. J. Am. Chem. Soc. 1947, 69, 2961. (c) 1c (2-Dimethylamino-1-butanol): Halverstadt, I. F.; Hardie, W. R.; Willians, A. R. J. Am. Chem. Soc. 1959, 81, 3618. (d) 1d (2-Dimethylamino-2-phenylethanol): Miyano, S.; Lu, L. D.-L.; Viti, S. M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 4350. (e) 1g (2-Dibenzylamino-1-phenyl-1-propanol): Schwan, T. J.; Lougheed, G. S.; Burrous, S. E. J. Heterocyclic Chem. 1974, 11, 807. (f) 1h (2-Butylamino-1-phenyl-1-propanol): Soai, K.; Yokoyama, S.; Hayasaka, T. J. Org. Chem. 1991, 56, 4264.
22. The starting amino alcohols were purchased from the usual suppliers (1e: 1-dimethylamino-2-propanol, 1f: N-methylephedrine, 1j: 2-dimethylamino-2-methyl-1-propanol, 1k: 1-methyl-2-piperidinemethanol) or synthesized by literature procedures: (a) 1a (2-dimethylamino-1-propanol): Rosnati, V. Gazz. Chim. Ital. 1950, 80, 663. (b) 1b (2-Dibenzylamino-1-propanol) and 1i (2-Dibenzylamino-2-methyl-1-propanol): Kerwin, J. F.; Ullyot, G. E.; Fuson, R. C.; Zirkle, C. L. J. Am. Chem. Soc. 1947, 69, 2961. (c) 1c (2-Dimethylamino-1-butanol): Halverstadt, I. F.; Hardie, W. R.; Willians, A. R. J. Am. Chem. Soc. 1959, 81, 3618. (d) 1d (2-Dimethylamino-2-phenylethanol): Miyano, S.; Lu, L. D.-L.; Viti, S. M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 4350. (e) 1g (2-Dibenzylamino-1-phenyl-1-propanol): Schwan, T. J.; Lougheed, G. S.; Burrous, S. E. J. Heterocyclic Chem. 1974, 11, 807. (f) 1h (2-Butylamino-1-phenyl-1-propanol): Soai, K.; Yokoyama, S.; Hayasaka, T. J. Org. Chem. 1991, 56, 4264.
23. The resulting amides 2a, 2f (dimethylacetamide); 2b, 2g (dibenzylacetamide); 2h (dibutylacetamide); 2c (dimethylpropanamide); 2d (dimethylbenzamide); 2e (dimethylformamide); 2k (1-methyl-2-piperidone) are commercial products or described in literature; 21 (1-acetylpyrrol-idine): Al-Sehemi, A. G.; Atkinson, R. S.; Fawcett, J. J. Chem. Soc., Perkin Trans 1 2002, 257.
24. (a) Huber, J. E. Tetrahedron Lett. 1968, 3271.
25. (b) Foote, C. S.; Dzakpasu, A. A.; Lin, J. W.-P. Tetrahedron Lett. 1975, 1247.
26. (c) Wasserman, H. H.; Terao, S. Tetrahedron Lett. 1975, 1735.
27. (a) The starting amino ketones were purchased from the usual suppliers (4e: 1-dimethylamino-2-propanone); synthesized by literature procedures. 4f (2-dimethylamino1-phenyl-1-propanone): Welle, F.; Verevkin, S. P.; Keller, M.; Beckhaus, H.-D.; Ruechardt, C. Chem. Ber. 1994, 127, 697.
28. (b) 41 (α-Phenyl-α-pyrrolidinoacetophenone): Heinzelman, R. V.: Aspergren, B. D. J. Am. Chem. Soc. 1953, 75, 3409; or synthesized by known methods.
29. 27NO: C, 78.11; H, 10.41; N, 5.36. Found: C, 78.22; H, 10.63; N, 5.27.
30. (a) Turaeva, D. A.; Kurbatov, Y. V. Russ. J. Org. Chem. 1999, 1092.
31. (b) Turaeva, D. A.; Kurbatov, Y. V.; Kurbatova, A. S. Russ. J. Org. Chem. 1995, 739.
32. The EPR studies were made on the reaction mixtures without filtration. Moreover, the evolution of the EPR spectra taken at different reaction times showed the presence of mixtures of radicals as intermediates in these reactions.
33. (a) Neelakantan, L. J. Org. Chem. 1971, 36, 2256.
34. (b) Alcaide, B.; López-Mardomingo, C.; Pérez-Ossorio, R.; Plumet, J. J. Heterocyclic Chem. 1982, 19, 45.
35. (c) Wu, M. J.; Pridgen, L. N. Synlett 1990, 636.
36. (d) Aylward, J. B. Quart. Rev. 1971, 25, 407.
37. (e) Royer, J.; Hüsson, H. P. J. Org. Chem. 1985, 50, 636.
38. 2: C, 78.15; H, 6.89; N, 4.56. Found: C, 77.77; H, 7.08; N, 4.35.
39. 17NO: C. 76.81; H, 8.43; N, 6.89. Found: C, 76.70; H, 8.62; N, 6.76.