Dimethyldioxirane

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Dimethyldioxirane
DMDO.png DMDO-stick.png
DMDO3D.png
Identifiers
CAS number 74087-85-7 YesY
PubChem 115197
ChemSpider 103073 YesY
Jmol-3D images Image 1
Properties
Molecular formula C3H6O2
Molar mass 74.08 g/mol
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Dimethyldioxirane (DMDO), also referred to as Murray's reagent, is a dioxirane derived from acetone. It is the most commonly used dioxirane in organic synthesis, and can be considered[citation needed] as a monomer of acetone peroxide.

Synthesis[edit]

DMDO is not commercially available because of its instability. DMDO can be prepared by the reaction of acetone with oxone, where the potassium peroxymonosulfate is the active ingredient:[1]

Preparation of DMDO.png

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). However, this is of no consequence, since DMDO is prepared from extremely cheap starting materials: acetone, sodium bicarbonate, and potassium peroxymonosulfate (commercially known as "oxone"). The solution can be stored at low temperatures and assayed immediately prior to use to determine its actual concentration.

Uses[edit]

The most common use for DMDO is the oxidation of alkenes to epoxides. One particular 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. In fact, DMDO is considered the reagent of choice for epoxidation,[dubious ][citation needed] and in nearly all circumstances is as good as or better than peroxyacids such as meta-chloroperoxybenzoic acid (mCPBA).[citation needed]

Despite its high reactivity, DMDO displays good selectivity for olefins. Typically, electron deficient olefins are oxidized more slowly than electron rich ones. 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:

Dioxirane oxidations.png

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

Nef DMDO.png

References[edit]

  1. ^ Robert W. Murray and Megh Singh (1988), "Synthesis of epoxides using dimethyldioxirane]: trans-stilbene oxide", Org. Synth. ; Coll. Vol. 9: 288 
  • Dimethyldioxirane. Crandall, J.K.; Curci, R.; D'Accolti, L.; Fusco, C. Encyclopedia of Reagents for Organic Synthesis (2005). doi:10.1002/047084289X.rd329