Cyclododecahexaene or 2nnulene () is a member of the series of

annulene Annulenes are monocyclic hydrocarbons that contain the maximum number of non-cumulated or conjugated double bonds (' mancude'). They have the general formula C''n''H''n'' (when ''n'' is an even number) or C''n''H''n''+1 (when ''n'' is an odd num ...

s with some interest in

organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...

with regard to the study of

aromaticity In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugation alone. The e ...

. Cyclododecahexaene is non-aromatic due to the lack of planarity of the structure. On the other hand the di

anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...

with 14 electrons is a aromatic by Hückel's rules and more stable. According to

in silico In biology and other experimental sciences, an ''in silico'' experiment is one performed on a computer or via computer simulation software. The phrase is pseudo-Latin for 'in silicon' (correct ), referring to silicon in computer chips. It was c ...

experiments the tri-

trans isomer Trans- is a Latin prefix meaning "across", "beyond", or "on the other side of". Used alone, trans may refer to: Sociology * Trans, a sociological term which may refer to: ** Transgender, people who identify themselves with a gender that dif ...

is expected to be the most stable, followed by the 1,7-ditrans and the all cis-isomers (+1 kcal/mol) and by the 1,5-ditrans isomer (+5 kcal/mol). The first 2nnulene with sym-tri-trans configuration was synthesized in 1970 from a tricyclic precursor by

photolysis Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by absorption of light or photons. It is defined as the interaction of one or more photons wi ...

at low temperatures. On heating the compound rearranges to a

bicyclic A bicyclic molecule () is a molecule that features two joined rings. Bicyclic structures occur widely, for example in many biologically important molecules like α-thujene and camphor. A bicyclic compound can be carbocyclic (all of the ring ...

.4.0isomer. Reducing the compound at low temperatures allowed analysis of the dianion by

proton NMR Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or 1H NMR) is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the stru ...

with the inner protons resonating at −4.5 ppm relative to TMS, evidence of an

aromatic In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...

diamagnetic ring current An aromatic ring current is an effect observed in aromatic molecules such as benzene and naphthalene. If a magnetic field is directed perpendicular to the plane of the aromatic system, a ring current is induced in the delocalized π electrons o ...

. :

In one study the 1,7-ditrans isomer is generated at low temperatures in

THF Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water-miscible organic liquid with low viscosity. It is ma ...

dehydrohalogenation In chemistry, dehydrohalogenation is an elimination reaction which removes a hydrogen halide from a substrate (chemistry), substrate. The reaction is usually associated with the synthesis of alkenes, but it has wider applications. Dehydrohalogen ...

of a hexabromocyclododecane with potassium ''tert''-butoxide. Reduction of this compound at low temperature with

caesium Caesium (IUPAC spelling; also spelled cesium in American English) is a chemical element; it has Symbol (chemistry), symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of , which makes it one of only f ...

metal leads first to the

radical anion In organic chemistry, a radical anion is a free radical species that carries a negative charge. Radical anions are encountered in organic chemistry as reduced derivatives of polycyclic aromatic compounds, e.g. sodium naphthenide. An example of a ...

and then to the dianion. The

chemical shift In nuclear magnetic resonance (NMR) spectroscopy, the chemical shift is the resonant frequency of an atomic nucleus relative to a standard in a magnetic field. Often the position and number of chemical shifts are diagnostic of the structure of ...

for the internal protons in this compound is with +0.2 ppm much more modest than in the tri-trans isomer. : Heating the radical ion solution to

room temperature Room temperature, colloquially, denotes the range of air temperatures most people find comfortable indoors while dressed in typical clothing. Comfortable temperatures can be extended beyond this range depending on humidity, air circulation, and ...

leads to loss of one equivalent of hydrogen and formation of the

heptalene Heptalene is a polycyclic hydrocarbon with chemical formula , composed of two fused cycloheptatriene rings. It is an unstable, non-planar compound which is non-aromatic. The dianion, however, satisfies Hückel's rule In organic chemistry, Hü ...

radical anion.

References

{{Annulenes Annulenes Antiaromatic compounds Twelve-membered rings