This document summarizes key information about dioxirane, the smallest cyclic organic peroxide. Dioxirane has an unstable structure with a long O-O bond length of 1.516Å. It was first detected in situ in 1977 and prepared in the laboratory in 1972. Dioxirane's most common reaction is oxygen atom transfer, such as converting alkenes to epoxides. It has applications as an oxidizing agent in organic synthesis and disinfection.

3. 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

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

5. Physical Properties
Density 1.3±0.1 g/cm3
Boiling Point -83.8±23.0 °C at 760
mmHg
Molar Volume 35.3±3.0 cm3
Molar mass 46.03 g/mol
Index of Refraction 1.361
Properties

6. 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)

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

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

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

10. Preperation of First Dioxirane
 By Talbott and Thompson in 1972
 Prepare Perfluorodimethyldioxirane by F2 oxidation
of the precursor dialkoxides.
(Talbot & Thompson, 1972)

11. 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.

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

13. 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)

14. 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)

15. 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)

16. 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)

17. 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

18. 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.

19. 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.