Environmentally friendly solvent-free processes: Novel dual catalyst system in Henry reaction

Organic Process Research and Development

Volumn 7, Issue 3, 2003, Pages 254-258

  Bhattacharya, Apurba ^a   Purohit, Vikram C ^a   Rinaldi, Frank ^b  

^a TEXAS A AND M UNIVERSITY KINGSVILLE   (United States)

^b BRISTOL MYERS SQUIBB   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALDEHYDE DERIVATIVE; ALKANE DERIVATIVE; MINERAL; SOLVENT; SURFACTANT;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; ENVIRONMENT; HENRY REACTION; POLYMERIZATION; SYNTHESIS;

EID: 0037708618     PISSN: 10836160     EISSN: None     Source Type: Journal    
DOI: 10.1021/op020222c     Document Type: Article

References (53)

1. (a) Process Chemistry Collaboration, Education Concentrate. Chem. Eng. News 2001, 79 (July 23), 41.
2. th Southwest Regional Meeting, October 2001; pp 17-20.
3. For related references, see: (a) Cablewski, T.; Faux, F.; Strauss, C. R. J. Org. Chem. 1994, 59, 3408. (b) Raner, K. D.; Strauss, C. R.; Trainor, R. W.; Thorn, J. S. J. Org. Chem. 1995, 60, 2456. (c) Strauss, C. R.; Trainor, R. W. Aust. J. Chem. 1995, 48, 1665.
4. For related references, see: (a) Cablewski, T.; Faux, F.; Strauss, C. R. J. Org. Chem. 1994, 59, 3408. (b) Raner, K. D.; Strauss, C. R.; Trainor, R. W.; Thorn, J. S. J. Org. Chem. 1995, 60, 2456. (c) Strauss, C. R.; Trainor, R. W. Aust. J. Chem. 1995, 48, 1665.
5. For related references, see: (a) Cablewski, T.; Faux, F.; Strauss, C. R. J. Org. Chem. 1994, 59, 3408. (b) Raner, K. D.; Strauss, C. R.; Trainor, R. W.; Thorn, J. S. J. Org. Chem. 1995, 60, 2456. (c) Strauss, C. R.; Trainor, R. W. Aust. J. Chem. 1995, 48, 1665.
6. For related references, see (a) Hall, N. Science 1994, 266, 32. (b) Newman, A. Environ. Sci. Technol. 1994, 28 (11), 463A. (c) Sheldon, R. A. CHEMTECH 1994 (March), 38-47. (d) Amato, I. Science. 1993, 259, 1538. (e) Ilman, D. L. Chem. Eng. News. 1993, (Sept 6), 26. (f) Ember, L. CHEMTECH 1993 (June), 3. (g) Crenson, M. Dallas Morning News 1993 (Sept. 13), 1D. Ember. (h) Pollution Prevention Act, U. S. C.13101-13109, 1990, 42. (i) Browner, C. M. EPA Journal 1993, 3 (19), 6-8.
7. For related references, see (a) Hall, N. Science 1994, 266, 32. (b) Newman, A. Environ. Sci. Technol. 1994, 28 (11), 463A. (c) Sheldon, R. A. CHEMTECH 1994 (March), 38-47. (d) Amato, I. Science. 1993, 259, 1538. (e) Ilman, D. L. Chem. Eng. News. 1993, (Sept 6), 26. (f) Ember, L. CHEMTECH 1993 (June), 3. (g) Crenson, M. Dallas Morning News 1993 (Sept. 13), 1D. Ember. (h) Pollution Prevention Act, U. S. C.13101-13109, 1990, 42. (i) Browner, C. M. EPA Journal 1993, 3 (19), 6-8.
8. For related references, see (a) Hall, N. Science 1994, 266, 32. (b) Newman, A. Environ. Sci. Technol. 1994, 28 (11), 463A. (c) Sheldon, R. A. CHEMTECH 1994 (March), 38-47. (d) Amato, I. Science. 1993, 259, 1538. (e) Ilman, D. L. Chem. Eng. News. 1993, (Sept 6), 26. (f) Ember, L. CHEMTECH 1993 (June), 3. (g) Crenson, M. Dallas Morning News 1993 (Sept. 13), 1D. Ember. (h) Pollution Prevention Act, U. S. C.13101-13109, 1990, 42. (i) Browner, C. M. EPA Journal 1993, 3 (19), 6-8.
9. For related references, see (a) Hall, N. Science 1994, 266, 32. (b) Newman, A. Environ. Sci. Technol. 1994, 28 (11), 463A. (c) Sheldon, R. A. CHEMTECH 1994 (March), 38-47. (d) Amato, I. Science. 1993, 259, 1538. (e) Ilman, D. L. Chem. Eng. News. 1993, (Sept 6), 26. (f) Ember, L. CHEMTECH 1993 (June), 3. (g) Crenson, M. Dallas Morning News 1993 (Sept. 13), 1D. Ember. (h) Pollution Prevention Act, U. S. C.13101-13109, 1990, 42. (i) Browner, C. M. EPA Journal 1993, 3 (19), 6-8.
10. For related references, see (a) Hall, N. Science 1994, 266, 32. (b) Newman, A. Environ. Sci. Technol. 1994, 28 (11), 463A. (c) Sheldon, R. A. CHEMTECH 1994 (March), 38-47. (d) Amato, I. Science. 1993, 259, 1538. (e) Ilman, D. L. Chem. Eng. News. 1993, (Sept 6), 26. (f) Ember, L. CHEMTECH 1993 (June), 3. (g) Crenson, M. Dallas Morning News 1993 (Sept. 13), 1D. Ember. (h) Pollution Prevention Act, U. S. C.13101-13109, 1990, 42. (i) Browner, C. M. EPA Journal 1993, 3 (19), 6-8.
11. For related references, see (a) Hall, N. Science 1994, 266, 32. (b) Newman, A. Environ. Sci. Technol. 1994, 28 (11), 463A. (c) Sheldon, R. A. CHEMTECH 1994 (March), 38-47. (d) Amato, I. Science. 1993, 259, 1538. (e) Ilman, D. L. Chem. Eng. News. 1993, (Sept 6), 26. (f) Ember, L. CHEMTECH 1993 (June), 3. (g) Crenson, M. Dallas Morning News 1993 (Sept. 13), 1D. Ember. (h) Pollution Prevention Act, U. S. C.13101-13109, 1990, 42. (i) Browner, C. M. EPA Journal 1993, 3 (19), 6-8.
12. For related references, see (a) Hall, N. Science 1994, 266, 32. (b) Newman, A. Environ. Sci. Technol. 1994, 28 (11), 463A. (c) Sheldon, R. A. CHEMTECH 1994 (March), 38-47. (d) Amato, I. Science. 1993, 259, 1538. (e) Ilman, D. L. Chem. Eng. News. 1993, (Sept 6), 26. (f) Ember, L. CHEMTECH 1993 (June), 3. (g) Crenson, M. Dallas Morning News 1993 (Sept. 13), 1D. Ember. (h) Pollution Prevention Act, U. S. C.13101-13109, 1990, 42. (i) Browner, C. M. EPA Journal 1993, 3 (19), 6-8.
13. For related references, see (a) Hall, N. Science 1994, 266, 32. (b) Newman, A. Environ. Sci. Technol. 1994, 28 (11), 463A. (c) Sheldon, R. A. CHEMTECH 1994 (March), 38-47. (d) Amato, I. Science. 1993, 259, 1538. (e) Ilman, D. L. Chem. Eng. News. 1993, (Sept 6), 26. (f) Ember, L. CHEMTECH 1993 (June), 3. (g) Crenson, M. Dallas Morning News 1993 (Sept. 13), 1D. Ember. (h) Pollution Prevention Act, U. S. C.13101-13109, 1990, 42. (i) Browner, C. M. EPA Journal 1993, 3 (19), 6-8.
14. Browner, C. M. EPA Journal 1993, 3 (19), 6-8.
15. A. R. Gavaskar. Onsite Solvent Recovery. U.S. EPA/600/R-94/026; Cincinnati, Ohio, Sept 1993.
16. Green Chemistry Theory and Practice; Anastas, P. T., Warner, J. C., Eds.; Oxford University; pp 1-129.
17. (a) Henry, L. Compt. Rend. 1895, 120, 1265. (b) Kamlet, J. U.S. Patent 2,151,517, 1939. (c) Fernandez, R. Application to Sugars. Carbohydr. Res. 1993, 247, 239. (d) Kambe, S.; Yasuda, H. Bull. Chem. Soc. Jpn. 1968, 41 (6), 1444.
18. (b) Kamlet, J. U.S. Patent 2,151,517, 1939.
19. (c) Fernandez, R. Application to Sugars. Carbohydr. Res. 1993, 247, 239.
20. (d) Kambe, S.; Yasuda, H. Bull. Chem. Soc. Jpn. 1968, 41 (6), 1444.
21. (a) Sittig, M. Pharmaceutical Manufacturing Encyclopedia, 2nd ed.; Vol. 1 and 2.
22. (b) Pharmazeutische Wirkstoffe, Synthesen. Patente. Anwendungen Von A. Kleeman und J. Engel.
23. (c) Barrett, A. G. M.; Grabowski G. Chem. Rev. 1986, 86, 751.
24. (d) Brown, A. W. A.; Robinson, D. B. W.; Hurtig, H.; Wenner, B. J. Can. J. Res. 1948, 26D, 177.
25. (e) Bousquet, E. W.; Kirby, J. E.; Searle, N. E. U.S. Patent 2,335,384.
26. (f) Brian, P. W.; Grove, J. F.; Mcgowan, J. C. Nature 1946, 158, 876.
27. (g) McGowan, J. C.: Brian, P. W.; Hemming, H. G. Ann. Appl. Biol. 1948, 35, 25.
28. (h) Varma, R. S.; Dahiya, R.; Kumar. S. Tetrahedron Lett. 1997, 38 (29), 5131 and references cited therein.
29. (a) For base-catalyzed nitroaldol, see: Hoover, F. W.; Hass, H. J. Org. Chem. 1947, 12, 506.
30. (b) Wollenberg, R. H.; Miller, S. I. Tetrahedron Lett. 1978, 3219.
31. (c) Solladie-Cavalo, A.; Khiar, N. Tetrahedron Lett. 1988, 2189.
32. (d) Colvin, E. W.; Beck, A. K.; Seebach, D. Helv. Chim. Acta 1981, 64, 2264.
33. (e) Bonetti, G. A.; DeSavigny, C. B.; Michalski, C.; Rosenthal, R. J. Org. Chem. 1968, 33, 237.
34. (f) Schchter, H.; Gardikes, J.J.; Cantrell, T. S.; Tiers, G. V. D. J. Am. Chem. Soc. 1967, 89, 3005.
35. (g) Seebach, D.; Beck, A. K.; Mukhopadhyay, T.; Thomas, E. Helv. Chim. Acta 1982, 65, 1101.
36. (h) Kisinga, P.; Verkede, G. J. Org. Chem. 1999, 64, 4298.
37. (i) Luzzio, F. Tetrahedron 2001, 57, 915.
38. (a) Dehmlow, E. V.; Dehmlow, S. S. In Phase Transfer Catalysis, Monographs in Modern Chemistry, 11; Ebel, H. F., Ed.; Verlag Chemie: Weinheim, Germany, 1983.
39. (b) Arkhipovich, G. N.; Ugolkova, E. A. Koznaski, K. S. Polym. Bull. 1984, 12, 181.
40. (a) Pittman, C. U.; Evans, G. O. Chem. Technol. 1973, 3, 566.
41. (b) Bailar, J. C. Catal. Rev. 1974, 10 (1).
42. (c) Hanson, D. L.; Katzer, J. R.; Gates, B. C.; Schuit, G. C. A. J. Catal. 1974, 32, 204.
43. Since the reaction occurs in a single liquid phase, the term "dual catalyst" was introduced to differentiate the role of Triton-X from that of a conventional phase transfer catalyst (PTC), where the reaction takes place in the aqueous/organic interface. Triton-X is also differentiated from traditional crown ethers, since crown ethers do not act as a surfactant. In this case, although KOH is the active catalyst, the presence of Triton-X is imperative. Control experiments performed in absence of Triton-X showed decomposition of both nitroalkanes and aldehyde under otherwise identical conditions. For references on a similar dual catalytic effect by Triton-X type suffactants in a chiral PTC system, see: Dolling, U.-H.; Hughes, D. L.; Bhattacharya, A.; Ryan, K. M.; Karady, S.; Weinstock. L. M.; Grenda, V. J.; Grabowski, E. J. J. Efficient Asymmetric Alkylations via Chiral Phase-Transfer Catalysis. In A Novel Dual Catalysis. Catalysis of Organic Reactions; Paul N. Rylander, P. N., Greenfield, H., Augustine, R. L., Eds.; 1988; Vol. 33, pp 65-86.
44. (a) Soladie-Cavalo, A.; Khiar, N. Tetrahedron Lett. 1988, 2189.
45. (b) Susai, H.; Yamada, Y.; Yoichi, M. A.; Suzuki, T.; Shibasaki, M. Tetraheron Lett. 1994, 50 (43), 12313.
46. (c) Sasai, H.; Kim. W.-S.; Suzuki, T.; Shibasaki, M.; Mitsuda, M.; Hasegaowa, J.; Ohasi, T. Tetrahedron Lett. 1994, 35 (33), 6123.
47. (a) Dolling, U.-H.; Hughes, D. L.; Bhattacharya, A.; Ryan, K. M.; Karady, S.; Weinstock, L. M.; Grabowski, E. J. J. Efficient Asymmetric Alkylations via Chiral Phase-Transfer Catalysis: Applications and Mechanism: Starks, C. M., Ed.; In Phase Transfer Catalysis; New Chemistry, Catalysts, and Applications; ACS Symposium Series 326; American Chemical Society: Washington, DC, 1987, Chapter 7, pp 67-81.
48. (b) Bhattachrya, A.; Dolling, U.-H.; Grabowski, E. J. J.; Karady; Ryan, K. M.; Weinstock, L. M. Efficient Catalytic Asymmetric Alkylations. Angew. Chem. 1986, 98, 442.
49. (c) Dolling, U.-H.; Davis, P.; Grabowski, E. J. J. J. Am. Chem. Soc. 1984, 106, 446.
50. Lunts, L. H. C.; Main, B. G.; Tucker, H. In Medicinal Chemistry, The Role of Organic Chemistry in Drug Research; Robert, S. M., Price, B. J., Eds.; Academic Press: New York, 1985; pp 49-92.
51. (a) Rebeck, J. Angew. Chem., Int. Ed. Engl. 1990, 29, 245.
52. (b) March, J. Advanced Organic Chemistry, 4th ed.; John Wiley; pp 82-93 and references therein.
53. We did not perform any extensive safety studies. In general, nitroalkanes have low flammability, but they are often chemically unstable. Since the reactions are conducted in the liquid phase, safety should be less of an issue. Also, these reactions could potentially be conducted in a continuous or semicontinuous mode in a flow reactor where only small amount of substrate comes in contact with the reagent at any given time, instead of a batch mode, to make the process even safer. The following EPA web page is a source of excellent information about the safety of reactive groups including nitro compounds. [http://www.epa.gov/ceppo/cameo/help/chaptera.htm#913100].