Dimethyldioxirane (DMDO) is the

organic compound Some chemical authorities define an organic compound as a chemical compound that contains a carbon–hydrogen or carbon–carbon bond; others consider an organic compound to be any chemical compound that contains carbon. For example, carbon-co ...

with the formula . It is the

dioxirane In chemistry, dioxirane (systematically named dioxacyclopropane, also known as methylene peroxide or peroxymethane) is an organic compound with formula . The molecule consists of a ring with one methylene and two oxygen atoms. It is of interes ...

derived from

acetone Acetone (2-propanone or dimethyl ketone) is an organic compound with the chemical formula, formula . It is the simplest and smallest ketone (). It is a colorless, highly Volatile organic compound, volatile, and flammable liquid with a charact ...

and can be viewed as the

monomer A monomer ( ; ''mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or two- or three-dimensional network in a process called polymerization. Classification Chemis ...

acetone peroxide Acetone peroxide ( also called APEX and mother of Satan) is an organic peroxide and a primary explosive. It is produced by the reaction of acetone and hydrogen peroxide to yield a mixture of linear monomer and cyclic dimer, trimer, and tet ...

. It is a powerful selective oxidizing agent that finds some use in

organic synthesis Organic synthesis is a branch of chemical synthesis concerned with the construction of organic compounds. Organic compounds are molecules consisting of combinations of covalently-linked hydrogen, carbon, oxygen, and nitrogen atoms. Within the gen ...

. 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

with

potassium peroxymonosulfate Potassium peroxymonosulfate is widely used as an oxidizing agent, for example, in pools and spas (usually referred to as monopersulfate or "MPS"). It is the potassium salt (chemistry), salt of peroxymonosulfuric acid. Potassium peroxymonosulfate ...

, usually in the form of

Oxone Potassium peroxymonosulfate is widely used as an oxidizing agent, for example, in pools and spas (usually referred to as monopersulfate or "MPS"). It is the potassium salt of peroxymonosulfuric acid. Potassium peroxymonosulfate per se is rarely e ...

(2KHSO₅·KHSO₄·K₂SO₄). : Dimethyldioxirane Synthesis V

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:

sodium bicarbonate Sodium bicarbonate ( IUPAC name: sodium hydrogencarbonate), commonly known as baking soda or bicarbonate of soda (or simply “bicarb” especially in the UK) is a chemical compound with the formula NaHCO3. It is a salt composed of a sodium cat ...

, and

oxone Potassium peroxymonosulfate is widely used as an oxidizing agent, for example, in pools and spas (usually referred to as monopersulfate or "MPS"). It is the potassium salt of peroxymonosulfuric acid. Potassium peroxymonosulfate per se is rarely e ...

. 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 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

amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...

s to

nitro compound In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups (). The nitro group is one of the most common explosophores (functional group that makes a compound explosive) used globally. The nit ...

s and

sulfide Sulfide (also sulphide in British English) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to large families o ...

s to

sulfoxide In organic chemistry, a sulfoxide, also called a sulphoxide, is an organosulfur compound containing a sulfinyl () functional group attached to two carbon atoms. It is a polar functional group. Sulfoxides are oxidized derivatives of sulfides. E ...

s. In some cases, DMDO will even oxidize unactivated C-H bonds: : DMDO can also be used to convert

s to carbonyl compounds (

Nef reaction In organic chemistry, the Nef reaction is an organic reaction describing the acid hydrolysis of a salt of a primary or secondary nitroalkane () to an aldehyde () or a ketone () and nitrous oxide (). The reaction has been the subject of several ...

).{{cite journal, first1=Waldemar, last1=Adam, first2=Mieczyslaw, last2=Makosza, first3=Chantu R., last3=Saha-Möller, first4=Cong-Gui, last4=Zhao, title=A Mild and Efficient Nef Reaction for the Conversion of Nitro to Carbonyl Group by Dimethyldioxirane (DMD) Oxidation of Nitronate Anions, journal=

Synlett ''Synlett'' is an international scientific journal for accounts and rapid communications of original contributions of fundamental research in synthetic organic chemistry. The impact factor of this journal is 2.419 (2017). ''Nature'' featured a br ...

, year=1998, volume=1998, issue=12, pages=1335–1336, doi=10.1055/s-1998-1947 :

References

Reagents for organic chemistry Organic peroxides Dioxiranes Oxidizing agents

Synthesis

Uses

See also

References