Dioxirane

preperation and reactions of dioxirane with industrial and biological applications.

1. DIOXIRANE

2. Introduction Heterocyclic compound Smallest cyclic organic Peroxide Contain one carbon and two oxygen atoms Molar mass is 46.03 g/mol. Highly unstable Mostly computational study Dioxirane derivatives are more stable

3. Structure Microwave analysis indicates bond lengths as C-H 1.090 Å C-O 1.388 Å O-O 1.516 Å The O-O bond is very long and the reason for instability of dioxirane .

4. Physical Properties Density 1.3±0.1 g/cm 3 Boiling Point -83.8±23.0 °C at 760 mmHg Molar Volume 35.3±3.0 cm 3 Molar mass 46.03 g/mol Index of Refraction 1.361 Properties

5. Bayer Villiger Reaction First literature reference was made in 1899. Intermediate in the conversion of the cyclic ketone menthone to its corresponding lactone by monoperoxysulfuric acid was a dioxirane menthone (Bayer &Villiger,1899)

6. In-situ detection of Dioxirane Dioxirane has been detected during the low temperature of (-196) degree centigrade in the reaction of ethylene and ozone.

7. In-situ detection of Dioxirane ( Lovas & Suneram , 1977)

8. Preperation of Dimethyldioxirane Ketone react with oxone to form dimethyldioxirane . (Murray etal ., 1988)

9. Preperation of First Dioxirane By Talbott and Thompson in 1972 Prepare Perfluorodimethyldioxirane by F 2 oxidation of the precursor dialkoxides . (Talbot & Thompson, 1972)

10. Perfluoro-dimethyldioxirane They isolated the dioxirane by low temperature gas chromatography. Dioxiorane were pale yellow with max. Wavelength of 306nm. Indication of dioxirane as a Pale Yellow colour is and important aspect for laboratory point of view.

11. Reactions of Dioxirane Most common reaction of dioxirane is 0-atom transfer, particularly to unsaturated materials

12. Reaction with Alkenes Dimethyldioxirane converts alkenes to their corresponding epoxides Reaction is stereospecific 2,5,5-trimethyl-2,3-hexadien was converted to the corresponding spirodioxide in 84% yield in 10 min at room temperature (Crandall & Batal , 1988)

13. Reactions with Nitrogen containing Compounds Solutions of dimethyldioxirane have been used to oxidize primary amine to nitro compounds in a rapid and nearly quantitative fashion hydroxylamine (Murray 1989)

14. Saturated Hydrocarbons Dimethyldioxirane can also oxidize saturated hydrocarbons Reaction with dimethyloxirane is slow and take hours Methyl( trifluoro -methyl) dioxirane give rapid oxidation in few minutes (Murray , 1989)

15. Pharmaceutical Applications Macrocyclic natural product, epothilones is an antitumor agent with antimitotic activity that is more effective than taxol Epithilones synthesis involves dimethyldioxirane oxidation. ( Wessjohann , 1997) Dimethyldioxirane generated in-situ from pyruvate and oxone Act as oxidizing agent for disinfection Effective for distruction of various strains of bacteria, fungi and bacterial endospores (Wong et al., 2003)

16. Industrial applications Act as an oxidizing agent in organic synthesis Use in development of conventional laboratory plants Dimethyldioxirane is suitable for batch process Dimethyloxirane used to convert amines to nitro compounds Dioxirane compounds are useful for bleaching fabrics

17. References Heffner, R. J., & Steltenkamp , R. J. (1996).  U.S. Patent No. 5,525,121 . Washington, DC: U.S. Patent and Trademark Office. Murray, R. W. (1989). Chemistry of dioxiranes . 12. Dioxiranes .  Chemical Reviews ,  89 (5), 1187-1201. Suenram , R. D., & Lovas , F. J. (1978). Dioxirane . Its synthesis, microwave spectrum, structure, and dipole moment.  Journal of the American Chemical Society ,  100 (16), 5117-5122.

18. Reference Wessjohann , L. (1997). Epothilones : Promising Natural Products with Taxol ‐Like Activity.  Angewandte Chemie International Edition in English ,  36 (7), 715-718. Lovas , F. J., & Suenram , R. D. (1977). Identification of dioxirane (H2COO) in ozone-olefin reactions via microwave spectroscopy.  Chemical Physics Letters ,  51 (3), 453-456. Crandall. J. K.: Batal. D. J. J. Ore. Chem. 1988. 53. 1340.