Preparation of cyclic sulfites by transesterification of diols and diisopropyl sulfite

Synthetic Communications

Volumn 27, Issue 4, 1997, Pages 701-707

  King, Steven A ^a   Pipik, Brenda ^a   Conlon, David A ^a   Bhupathy, M ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOSULFUR DERIVATIVE; SULFOXIDE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; IN VITRO STUDY; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS;

EID: 0030943248     PISSN: 00397911     EISSN: None     Source Type: Journal    
DOI: 10.1080/00397919708003344     Document Type: Article

References (17)

1. Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. (Washington, D. C.), 1994, 94, 2483. Lohray, B. B.; Ahuja, J. R. J. Chem. Soc. Chem. Commun. 1991, 95. Lohray, B. B. Synthesis 1992, 11, 1035. Nymann, K.; Svendsen, J. S. Acta Chem. Scand. 1994, 48, 183.
2. Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. (Washington, D. C.), 1994, 94, 2483. Lohray, B. B.; Ahuja, J. R. J. Chem. Soc. Chem. Commun. 1991, 95. Lohray, B. B. Synthesis 1992, 11, 1035. Nymann, K.; Svendsen, J. S. Acta Chem. Scand. 1994, 48, 183.
3. Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. (Washington, D. C.), 1994, 94, 2483. Lohray, B. B.; Ahuja, J. R. J. Chem. Soc. Chem. Commun. 1991, 95. Lohray, B. B. Synthesis 1992, 11, 1035. Nymann, K.; Svendsen, J. S. Acta Chem. Scand. 1994, 48, 183.
4. Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. (Washington, D. C.), 1994, 94, 2483. Lohray, B. B.; Ahuja, J. R. J. Chem. Soc. Chem. Commun. 1991, 95. Lohray, B. B. Synthesis 1992, 11, 1035. Nymann, K.; Svendsen, J. S. Acta Chem. Scand. 1994, 48, 183.
5. Labelle, M.; Belley, M.; Gareau, Y.; Gauthier, J. Y.; Guay, D.; Gordon, R.; Grossman, S. G.; Jones, T. R.; Leblanc, Y.; McAuliffe, M.; McFarlane, C.; Masson, P.; Metters, K. M.; Ouimet, N.; Patrick, D. H.; Piechuta, H.; Rochette, C.; Sawyer, N.; Xiang, Y. B.; Pickett, C. B.; Ford-Hutchinson, A. W.; Zamboni, R. J.; Young, R. N. Bioorg. Med Chem. Lett. 1995, 5, 283.
6. Schreiner, P. R.; Schleyer, P. v. R.; Hill, R. K. J. Org. Chem. 1993, 58, 2822.
7. Bristow, P. A.; Tillett, J. G. Tetrahedron Lett. 1967, 901. Tillett, J. G. Chem. Rev. 1976, 76, 747.
8. Bristow, P. A.; Tillett, J. G. Tetrahedron Lett. 1967, 901. Tillett, J. G. Chem. Rev. 1976, 76, 747.
9. Bristow, P.A.; Tillet, J.G. J. Chem. Soc. (C) 1968, 684. Di-t-butyl sulfite cannot be easily prepared due to the spontaneous decomposition of the intermediate, t-butyl chlorosulfite.
10. Diisopropyl Sulfite: Toluene (500 mL) and isopropanol (240 g, 306 mL, 4.00 mol) were combined under nitrogen in a 2 L flask equipped with a dropping funnel. Thionyl chloride (119 g, 73 mL, 1.00 mol) was added from the dropping funnel over 30 min maintaining the reaction temperature at 15-25 °C. Some HCl evolution is noted as the reaction proceeds. When the addition was complete, the reaction mixture is put under vacuum to remove HCl. The pressure is slowly lowered. When gas evolution ceases the mixture is concentrated to remove toluene and excess isopropanol. The yield is 157 g (95%). Triethylamine (1 mL) is added to remove residual HCl and the incipient precipitate is filtered away.
11. 13C-NMR: 64.1, 28.3.
12. 3, 62 MHz) δ (ppm): 118.6, 67.3, 22.5, 19.3, 9.8.
13. Literature yields for cyclic sulfite formation using thionyl chloride. a) Itoh, O.; Kohmura, Y.; Ichikawa, Y.; Umezu, M.; Okita, T.; Ichikawa, K. Bull. Chem. Soc. 1980, 53, 146. b) Szmant, H. H.; Emerson, W. J. Am. Chem. Soc. 1956, 78, 454. c) Hanselmann, P. European Patent 0 491 323 A2. d) Wiggins, L. F.; Beard, C. C.; James, J.W. U.K. Patent 944,406. e) Lohray, B. B. Synthesis 1992, 11, 1035.
14. Literature yields for cyclic sulfite formation using thionyl chloride. a) Itoh, O.; Kohmura, Y.; Ichikawa, Y.; Umezu, M.; Okita, T.; Ichikawa, K. Bull. Chem. Soc. 1980, 53, 146. b) Szmant, H. H.; Emerson, W. J. Am. Chem. Soc. 1956, 78, 454. c) Hanselmann, P. European Patent 0 491 323 A2. d) Wiggins, L. F.; Beard, C. C.; James, J.W. U.K. Patent 944,406. e) Lohray, B. B. Synthesis 1992, 11, 1035.
15. Literature yields for cyclic sulfite formation using thionyl chloride. a) Itoh, O.; Kohmura, Y.; Ichikawa, Y.; Umezu, M.; Okita, T.; Ichikawa, K. Bull. Chem. Soc. 1980, 53, 146. b) Szmant, H. H.; Emerson, W. J. Am. Chem. Soc. 1956, 78, 454. c) Hanselmann, P. European Patent 0 491 323 A2. d) Wiggins, L. F.; Beard, C. C.; James, J.W. U.K. Patent 944,406. e) Lohray, B. B. Synthesis 1992, 11, 1035.
16. Literature yields for cyclic sulfite formation using thionyl chloride. a) Itoh, O.; Kohmura, Y.; Ichikawa, Y.; Umezu, M.; Okita, T.; Ichikawa, K. Bull. Chem. Soc. 1980, 53, 146. b) Szmant, H. H.; Emerson, W. J. Am. Chem. Soc. 1956, 78, 454. c) Hanselmann, P. European Patent 0 491 323 A2. d) Wiggins, L. F.; Beard, C. C.; James, J.W. U.K. Patent 944,406. e) Lohray, B. B. Synthesis 1992, 11, 1035.
17. Literature yields for cyclic sulfite formation using thionyl chloride. a) Itoh, O.; Kohmura, Y.; Ichikawa, Y.; Umezu, M.; Okita, T.; Ichikawa, K. Bull. Chem. Soc. 1980, 53, 146. b) Szmant, H. H.; Emerson, W. J. Am. Chem. Soc. 1956, 78, 454. c) Hanselmann, P. European Patent 0 491 323 A2. d) Wiggins, L. F.; Beard, C. C.; James, J.W. U.K. Patent 944,406. e) Lohray, B. B. Synthesis 1992, 11, 1035.