Dimethyldioxirane

Dimethyldioxirane

File:Dimethyldioxirane Structural Formula V.2.svg
File:DMDO-stick.png
File:DMDO3D.png   Carbon, C   Hydrogen, H   Oxygen, O
Names
IUPAC name 3,3-Dimethyldioxirane
Other names DMDO Monoperoxyacetone, Murray's reagent
Identifiers
CAS Number	74087-85-7 checkY
3D model (JSmol)	Interactive image
ChemSpider	103073 checkY
ECHA InfoCard
E number
PubChem CID	115197
UNII	R5RAT196DJ checkY
CompTox Dashboard (EPA)	{{#property:P3117}}
InChI InChI=1S/C3H6O2/c1-3(2)4-5-3/h1-2H3 checkY Key: FFHWGQQFANVOHV-UHFFFAOYSA-N checkY InChI=1/C3H6O2/c1-3(2)4-5-3/h1-2H3 Key: FFHWGQQFANVOHV-UHFFFAOYAF
SMILES CC1(OO1)C
Properties
Chemical formula	C3H6O2
Molar mass	74.08 g/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). checkY verify (what is checkY☒N ?) Infobox references

Dimethyldioxirane (DMDO) is the organic compound with the formula (CH₃)₂CO₂. It is the dioxirane derived from acetone and can be viewed as the monomer of acetone peroxide. It is a powerful selective oxidizing agent that finds some use in organic synthesis. It is known only in the form of a dilute solution, usually in acetone, and hence the properties of the pure material are largely unknown.

Synthesis

DMDO is not commercially available because of chemical instability. DMDO can be prepared as dilute solutions (~0.1 M) by treatment of acetone with potassium peroxymonosulfate KHSO
₅, usually in the form of Oxone (2KHSO₅·KHSO₄·K₂SO₄).

File:Dimethyldioxirane Synthesis V.2.svg

The preparation of DMDO is rather inefficient (typical yields < 3%) and typically only yields a relatively dilute solution in acetone (only up to approximately 0.1 M). This is tolerable as preparation uses inexpensive substances: acetone, sodium bicarbonate, and oxone. Cold solutions (−10 to −20 °C) of DMDO are stable for days. Decomposition is accelerated by light and by heavy metals. The concentration of DMDO may be assayed immediately prior to its use.

Methyl(trifluoromethyl)dioxirane (H
₃C)(F
₃C)CO
₂ can be similarly prepared from methyl trifluoromethyl ketone. It is a stronger oxidant than DMDO.

Uses

DMDO is most commonly used for the oxidation of alkenes to epoxides. One advantage of using DMDO is that the only byproduct of oxidation is acetone, a fairly innocuous and volatile compound. DMDO oxidations are particularly mild, sometimes allowing oxidations which might not otherwise be possible.

Despite its high reactivity, DMDO displays good selectivity for electron-rich olefins. DMDO will also oxidize several other functional groups. For example, DMDO will oxidize primary amines to nitro compounds and sulfides to sulfoxides. In some cases, DMDO will even oxidize unactivated C-H bonds:

File:Dioxirane oxidations.png

DMDO can also be used to convert nitro compounds to carbonyl compounds (Nef reaction).

File:Nef DMDO.png

See also

• Difluorodioxirane
• Dioxirane
• Shi epoxidation