Dioxetane
Encyclopedia
The chemical substance
1,2-dioxetane (1,2-dioxacyclobutane) is an 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).
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 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.
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.
The luminescence of glowsticks and luminescent bangles and necklaces involves 1,2-dioxetanedione
(C2O4), another dioxetane derivative that decomposes to carbon dioxide.
Other dioxetane derivatives are used in clinical analysis, where the their light emission (which can be measured even at very low levels) allows chemists to detect very low concentrations of body fluid constituents.
Chemistry
Chemistry is the science of matter, especially its chemical reactions, but also its composition, structure and properties. Chemistry is concerned with atoms and their interactions with other atoms, and particularly with the properties of chemical bonds....
1,2-dioxetane (1,2-dioxacyclobutane) is an heterocyclic
Heterocyclic compound
A heterocyclic compound is a cyclic compound which has atoms of at least two different elements as members of its ring. The counterparts of heterocyclic compounds are homocyclic compounds, the rings of which are made of a single element....
organic compound
Organic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...
with formula C2O2H4, containing a ring of two adjacent oxygen atoms and two adjacent carbon atoms. It is therefore an organic peroxide
Peroxide
A peroxide is a compound containing an oxygen–oxygen single bond or the peroxide anion .The O−O group is called the peroxide group or peroxo group. In contrast to oxide ions, the oxygen atoms in the peroxide ion have an oxidation state of −1.The simplest stable peroxide is hydrogen peroxide...
, and can be viewed as a dimer of formaldehyde
Formaldehyde
Formaldehyde is an organic compound with the formula CH2O. It is the simplest aldehyde, hence its systematic name methanal.Formaldehyde is a colorless gas with a characteristic pungent odor. It is an important precursor to many other chemical compounds, especially for polymers...
(COH2).
In the 1960s, biochemists
Biochemistry
Biochemistry, sometimes called biological chemistry, is the study of chemical processes in living organisms, including, but not limited to, living matter. Biochemistry governs all living organisms and living processes...
discovered that some derivatives of 1,2-dioxetane have a fleeting existence as intermediates in the reactions responsible for the bioluminescence
Bioluminescence
Bioluminescence is the production and emission of light by a living organism. Its name is a hybrid word, originating from the Greek bios for "living" and the Latin lumen "light". Bioluminescence is a naturally occurring form of chemiluminescence where energy is released by a chemical reaction in...
in fireflies
Firefly
Lampyridae is a family of insects in the beetle order Coleoptera. They are winged beetles, and commonly called fireflies or lightning bugs for their conspicuous crepuscular use of bioluminescence to attract mates or prey. Fireflies produce a "cold light", with no infrared or ultraviolet frequencies...
, glow-worms and other luminescent creatures. 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
University of Alberta
The University of Alberta is a public research university located in Edmonton, Alberta, Canada. Founded in 1908 by Alexander Cameron Rutherford, the first premier of Alberta and Henry Marshall Tory, its first president, it is widely recognized as one of the best universities in Canada...
in Edmonton
Edmonton
Edmonton is the capital of the Canadian province of Alberta and is the province's second-largest city. Edmonton is located on the North Saskatchewan River and is the centre of the Edmonton Capital Region, which is surrounded by the central region of the province.The city and its census...
: 3,3,4-trimethyl-1,2-dioxetane, prepared as a yellow solution in benzene
Benzene
Benzene is an organic chemical compound. It is composed of 6 carbon atoms in a ring, with 1 hydrogen atom attached to each carbon atom, with the molecular formula C6H6....
. When heated to 333 K, it decomposed smoothly (rather than explosively, as many peroxides do) to acetone
Acetone
Acetone is the organic compound with the formula 2CO, a colorless, mobile, flammable liquid, the simplest example of the ketones.Acetone is miscible with water and serves as an important solvent in its own right, typically as the solvent of choice for cleaning purposes in the laboratory...
and acetaldehyde
Acetaldehyde
Acetaldehyde is an organic chemical compound with the formula CH3CHO or MeCHO. It is one of the most important aldehydes, occurring widely in nature and being produced on a large scale industrially. Acetaldehyde occurs naturally in coffee, bread, and ripe fruit, and is produced by plants as part...
with the emission of pale blue light.
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.
The luminescence of glowsticks and luminescent bangles and necklaces involves 1,2-dioxetanedione
1,2-Dioxetanedione
The chemical compound 1,2-dioxetanedione, or 1,2-dioxacyclobutane-3,4-dione, often called peroxyacid ester, is an unstable oxide of carbon with formula C2O4...
(C2O4), another dioxetane derivative that decomposes to carbon dioxide.
Other dioxetane derivatives are used in clinical analysis, where the their light emission (which can be measured even at very low levels) allows chemists to detect very low concentrations of body fluid constituents.