DEVELOPMENTS IN THE PREPARATION OF DIMETHYLDIOXIRANE DMD/DMDO

Abstract

The synthesis of dimethyldioxirane DMD/DMDO is as complicated as its storage. It should be used within a week after its synthesis. Developments were gained in the synthetic procedure of DMD/DMDO in two steps and enough yield was obtained at moderate temperature compared to literature procedures -78 oC . The dry ice before trap was replaced with a condenser containing chilled methanol which also resulted the condensation of DMD/DMDO back from the vacuum trap. Diethyl formylphosphonate 6 was synthesized by the oxidation of diazomethylphosphonate 5 with DMD/DMDO at different temperatures starting from -78 ºC to 0 ºC

Keywords

• Dimethyldioxirane,ethyl formyphosphonate,oxone

References

1. 1. Hamilton, R., et al., The Reaction of Dimethyl Dioxirane with Diazomethylphosphonates - the First Synthesis of a Formylphosphonate Hydrate. Journal of the Chemical SocietyChemical Communications, 1994(1): p. 37-38.
2. 2. Hamilton, R., et al., Reactions of diazomethylphosphonate: The first synthesis of a formylphosphonate hydrate. Phosphorus Sulfur and Silicon and the Related Elements, 1996. 109(1-4): p. 441-444.
3. 3. Kolodiazhnyi, O.I., Asymmetric synthesis of hydroxyphosphonates. TetrahedronAsymmetry, 2005. 16(20): p. 3295-3340.
4. 4. Dellaria, J.F., et al., New Inhibitors of Renin That Contain Novel Phosphostatine Leu-Val Replacements. Journal of Medicinal Chemistry, 1990. 33(2): p. 534-542.
5. 5. Tao, M., et al., Novel peptidyl phosphorus derivatives as inhibitors of human calpain I. Journal of Medicinal Chemistry, 1998. 41(20): p. 3912-3916.
6. 6. Stowasser, B., et al., New Hybrid Transition-State Analog Inhibitors of Hiv Protease with Peripheral C2-Symmetry. Tetrahedron Letters, 1992. 33(44): p. 6625-6628.
7. 7. Snoeck, R., et al., Antivaccinia Activities of Acyclic Nucleoside Phosphonate Derivatives in Epithelial Cells and Organotypic Cultures. Antimicrobial Agents and Chemotherapy, 2002. 46: p. 3356-3361.
8. 8. Peters, M.L., M. Leonard, and A.A. Licata, Role of alendronate and risedronate in preventing and treating osteoporosis. Cleveland Clinic Journal of Medicine, 2001. 68(11): p. 945-951.

9. 9. Leder, B.Z. and H.M. Kronenberg, Gastroenterologists and choosing the right bisphosphonate. Gastroenterology, 2000. 119(3): p. 866-869.
10. 10. Samanta, S. and C.G. Zhao, Organocatalytic enantioselective synthesis of alpha-hydroxy phosphonates. Journal of the American Chemical Society, 2006. 128(23): p. 7442-7443.
11. 11. Dodda, R. and C.G. Zhao, Organocatalytic highly enantioselective synthesis of secondary alpha-hydroxyphosphonates. Organic Letters, 2006. 8(21): p. 4911-4914.
12. 12. Dodda, R. and C.G. Zhao, Silver(I) triflate-catalyzed direct synthesis of N-PMP protected alpha-aminopropargylphosphonates from terminal alkynes. Organic Letters, 2007. 9(1): p. 165-167.
13. 13. Dodda, R. and C.G. Zhao, Enantioselective synthesis of alphaaminopropargylphosphonates. Tetrahedron Letters, 2007. 48(25): p. 4339-4342.
14. 14. Murray, R.W. and M. Singh, Organic Syntheses, Coll., 1998. 9: p. 5.