Eight cyclooctatetraene

Benzene cyclobutadiene and cyclooctatetraene provide clear examples of Huckel s rule Benzene with six tt electrons is a An + 2) system and is predicted to be aromatic by the rule Square cyclobutadiene and planar cyclooctatetraene are An systems with four and eight tt electrons respectively and are antiaromatic... 

Section 11 19 An additional requirement for aromaticity is that the number of rr elec Irons m conjugated planar monocyclic species must be equal to An + 2 where n is an integer This is called Huckel s rule Benzene with six TT electrons satisfies Huckel s rule for n = 1 Square cyclobutadiene (four TT electrons) and planar cyclooctatetraene (eight rr electrons) do not Both are examples of systems with An rr electrons and are antiaromatic... 

The addition of benzonitrile oxide to cyclooctatetraene produced a monoadduct which was induced to undergo valence tautomerism to produce a tricycloisoxazoline (Scheme 104). A similar reaction with tropone gave a minimum of eight adducts from which two monoadducts were isolated (Scheme 104) (70T5113). 

The Hiickel rule predicts aromaticity for the six-7c-electron cation derived from cycloheptatriene by hydride abstraction and antiaromaticity for the planar eight-rc-electron anion that would be formed by deprotonation. The cation is indeed very stable, with a P Cr+ of -1-4.7. ° Salts containing the cation can be isolated as a product of a variety of preparative procedures. On the other hand, the pK of cycloheptatriene has been estimated at 36. ° This value is similar to those of normal 1,4-dienes and does not indicate strong destabilization. Thus, the seven-membered eight-rc-electron anion is probably nonplanar. This would be similar to the situation in the nonplanar eight-rc-electron hydrocarbon, cyclooctatetraene. 

The crystal structure of the potassium salt of 1,3,5,7-tetramethylcyclootatetraene dianion has been determined by X-ray dififaction. ° The eight-membered ring is planar, with aromatic C—C bond lengths of about 1.41 A without significant alternation. The spectroscopic and structural studies lead to the conclusion that the cyclooctatetraene dianion is a stabilized delocalized structure. 

The pattern of orbital energies in Figure 11.13 provides a convincing explanation for why benzene is aromatic while square cyclobutadiene and planar- cyclooctatetraene are not. We start by counting tt electrons cyclobutadiene has four, benzene six, and cyclooctatetraene has eight. These tt electrons are assigned to MOs in accordance with the usual rules—lowest energy orbitals first, a maximum of two electrons per orbital. 

I Cyclooctatetraene has eight it electrons and is not aromatic. The ir electrons are localized into four double bonds rather than delocalized around the ring, and the molecule is tub-shaped rather than planar. 

The presence of a ring-current is characteristic of all Hiickel aromatic molecules and is a good test of aromaticity. For example, benzene, a six-7r-clectron aromatic molecule, absorbs at 7.37 5, but cyclooctatetraene, an eight--iT-electxon nonaromatic molecule, absorbs at 5.78 8. 

The interest in azacyclooctatetraenes is mainly due to their structural similarity to cycloocta-tetraene.1 3 Most synthetic efforts have concentrated on a comparison of the unusual chemical and physical properties of cyclooctatetraene with its aza analogs. Besides studies concerning the aromaticity, the primary focus of much work has concerned the stability of the eight-membered ring and its valence isomerization. 

Cyclooctatetraene (COT) —> Semibullvalene (SB) Photorearrangement. Irradiation of COT yields semibullvalene [97], in spite of the fact that this photochemical reaction is forbidden by orbital conservation mles. The Longuet-Higgins loop for this system actually predicts that this should happen, although the reaction is phase preserving. (Fig. 42). This is another example of type C loop (Fig. 11). Only six of the eight electrons re-pair as COT transforms to SB. The reaction is made possible by the fact that COT valence isomerization, a phase-inverting reaction (four electron-pair Hiickel system), takes place simultaneously. One expects to produce in the reaction a COT isomer, that can be detected solely by proper substitution. 

Similar conformation is believed to exist for cycloheptane. Another eight remembered ring, cyclooctatetraene exists in the tub form as shown. 

On the basis of topological criteria, Balaban predicted in 1965 the aromaticity of compounds with 10-jr-electron systems in eight-membered rings with two heteroatoms (analogous to the cyclooctatetraene dianion).250 Schroth and co-workers were among the first to investigate the systems experimentally, and they synthesized compounds 210—213 (Scheme... 

A planar molecular structure in the solid state was observed for dilithiated dibenzo[a, e]cyclooctatetraene by Rabideau and coworkers. Dilithiated 233 is formed in THF by the reaction of compound 232 with an excess of metallic lithium at room temperature (Scheme 81). In the solid state, two lithium-TMEDA units are capping both sides of the central eight-membered ring plane . 

A good example is cyclooctatetraene (Box 1.11) formally the higher homologue of benzene, it is a An type containing eight p-electrons. This... 

Nonbridged and nonaromatic anulenes such as derivatives of cyclooctatetraene ([8]anulene) (cf. 117 to 121) are chiral owing to the nonplanarity of the eight-mem bered... 

The species (CH)8Mg, or we should say its THF 2.5-solvate, is readily formed from cyclooctatetraene and Mg. The NMR spectrum shows eight equivalent ring atoms and so suggests either the cyclooctatetraene dianion and Mg salt or a putative (and highly fluxional) solvated magnesacyclopentene (or more properly magnesabicyclonon-atriene). However, there is no structural data for the rf open sandwich species and the enthalpy of formation of this simple and sensible half-sandwich, or tight ion pair, cannot even be estimated. 

Eight-membered heterocyclic systems embrace a very broad variety of compounds ranging from cyclic ethers and imines to highly labile analogs of cyclooctatetraene, and the properties and chemical behavior of these compounds of course depend entirely on the extent and location of unsaturation. For this reason, preparative methods and reactions are treated together for each ring system and oxidation level. 

Eight-membered rings with two O, S or N atoms or combinations of these heteroatoms in a 1,2- or 1,4-relationship and three double bonds possess conjugated tt-electron frameworks and can be designated as dihetera[8]annulenes (78AHC(23)55). These 1,2- or 1,4-diheterocins are isoelectronic with the cyclooctatetraene dianion, and if planar represent potentially aromatic IOtt-electron systems. Considerable interest has attached to the degree of aromaticity of these compounds from both theoretical and experimental standpoints. Most theoretical treatments have led to the conclusion that 1,2-diheterocins, because of... 

Cyclooctatetraene has eight 77 electrons and thus does not satisfy the (An + 2) 77 electron requirement of the Hiickel rule. 

Nickel catalysts for the syntheses of cyclic compounds were first successfully utilized by Reppe, who was able to prepare cyclooctatetraene from acetylene (65). This eight-membered ring synthesis, and also the preparation of cyclic products from strained olefins (e.g., bicycloheptene and norbornadiene) and acrylonitrile, have been adequately reviewed elsewhere (7) and will therefore not be considered further. A short account of the cyclization reactions of butadiene using nickel-containing catalysts has appeared previously in this series (/). The discovery of new synthetic possibilities and a deeper understanding of the mechanism of these reactions justify a more extensive treatment. 

ESR cavity produces a signal (nonuplet, ajj = 3,23 G), which indicates eight equivalent protons. When bicyclo [6.1.0] nonatriene (196) was reduced in the ESR cavity the spectra of the cyclononatriene radical anion (197) and of the methyl-cyclooctatetraene radical anion (198 Eq. (251) ) were observed. 

An interesting extension of cyclooctatetraene polymerisation is the polymerisation of trimethylsilyl-substituted cyclooctatetraene to give soluble polyacetylene substituted with one trimethylsilyl group every eight carbon atoms [162], Such materials have been used to construct solar cells [165],... 

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