1,2-Dioxetane

Names
Preferred IUPAC name 1,2-Dioxetane
Systematic IUPAC name 1,2-Dioxacyclobutane
Other names Ethylene peroxide Peroxyethane
Identifiers
CAS Number	6788-84-7 Y
3D model (JSmol)	Interactive image Interactive image
ChemSpider	108850 Y
PubChem CID	122029
UNII	142GQA523X Y
CompTox Dashboard (EPA)	DTXSID20218105
InChI InChI=1S/C2H4O2/c1-2-4-3-1/h1-2H2 Y Key: BVTJGGGYKAMDBN-UHFFFAOYSA-N Y InChI=1/C2H4O2/c1-2-4-3-1/h1-2H2 Key: BVTJGGGYKAMDBN-UHFFFAOYAG
SMILES C1OOC1 O1OCC1
Properties
Chemical formula	C2H4O2
Molar mass	60.052 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N verify (what is YN ?) Infobox references

The chemical substance 1,2-dioxetane (systematically named 1,2-dioxacyclobutane, also known as ethylene peroxide or peroxyethane) is a heterocyclic, organic compound with formula C₂O₂H₄, containing a ring of two adjacent oxygen atoms and two adjacent carbon atoms. It is therefore an organic peroxide, and can be viewed as a dimer of formaldehyde (COH₂).

Luminescence

In the 1960s, biochemists discovered that some derivatives of 1,2-dioxetane have a fleeting existence as intermediates in the reactions responsible for the bioluminescence in fireflies, glow-worms and other luminescent creatures. The luminescence of glowsticks and luminescent bangles and necklaces involves 1,2-dioxetanedione (C₂O₄), another dioxetane derivative that decomposes to carbon dioxide.^[1] Other dioxetane derivatives are used in clinical analysis, where their light emission (which can be measured even at very low levels) allows chemists to detect very low concentrations of body fluid constituents.^[2]

Derivatives

The hypothesis could not be proved because these four-membered cyclic peroxides are quite unstable. Then in 1968 the first example of a stable dioxetane derivative was made at the University of Alberta in Edmonton: 3,3,4-trimethyl-1,2-dioxetane, prepared as a yellow solution in benzene. When heated to 333 K, it decomposed smoothly (rather than explosively, as many peroxides do) to acetone and acetaldehyde with the emission of pale blue light.^[3]

The second example of a dioxetane derivative was made shortly after: the symmetrical compound 3,3,4,4-tetramethyl-1,2-dioxetane, obtained as pale yellow crystals that sublimed even when kept in the refrigerator. Benzene solutions of this compound also decomposed smoothly with the emission of blue light. By adding compounds that normally fluoresce in UV light the colour of the emitted light could be altered.^[4]

Carbon monoxide

The dioxetane intermediate is capable of generating carbon monoxide and has been explored as a carbon monoxide pro-drug.

• Peroxidation of heme at the alpha-methine bridge generates carbon monoxide and forms biliverdin as a non-enzymatic alternative pathway to heme oxygenase^[5]
• Lipid peroxidation^[6]

Peroxidation of the reactive enol of alpha keto acids, such as the tautomer of phenylpyruvic acid at the benzylic carbon, can form a fluorescing 1,2-dioxetane to generate benzaldehyde and oxalic acid.^[6] Alternatively, a peroxylactone can form (alpha-keto-beta-peroxylactone) which also forms benzaldehyde but liberates carbon dioxide and carbon monoxide.^[7]