Huckel rule aromaticity

We saw in Chapter 12 that aromaticity reveals itself in various ways Qualitatively aro matic compounds are more stable and less reactive than alkenes Quantitatively their heats of hydrogenation are smaller than expected Theory especially Huckels rule furnishes a structural basis for aromaticity Now lets examine some novel fea tures of their NMR spectra... 

Annulene, [22]annulene, and [24]annulene have all been reported. The NMR spectrum of [22]annulene is consistent with regarding the molecule as aromatic, whereas those of the [20] and [24] analogs are not. In each case, there is some uncertainty as to the preferred conformation in solution, and the NMR spectra are temperature-dependent. Although the properties of these molecules have not been studied as completely as those of the smaller systems, they are consistent with the predictions of the Huckel rule. 

The Huckel rule is strictly applicable only to monocyclic compounds, but the genera] concept of aromaticity can be extended beyond simple monocyclic compounds to include polycyclic aromatic compounds. Naphthalene, with two... 

Bond angle/bond length relationships do not readily account for the bond localization noted for starphenylene (116) and triphenylene (124). A cursory examination of the structures reveals that in these cases the annelated cycles can have an aromatic character of their own. In staiphenylene the cycle would contain four electrons and be antiaromatic, whereas in triphenylene the cycle would have six electrons and be aromatic. From the simple Huckel rule, the antiaromatic cycle should be disfavored. In such a case, structural stabilization can be accomplished by greater contribution from the resonance form that has single-bond character at the endo-honA. The reverse is expected for the aromatic cycle. This model is simple, predictive, and accurate ... 

Q Which of the following heterocycles conform to the Huckel rule (4h +2) for aromaticity (i) furan (ii) l//-azepine (iii) pyrylium perchlorate [chlorate(VIl)] ... 

Anions of small heterocyclics are little known. They seem to be involved in some elimination reactions of oxetan-2-ones (80JA3620). Anions of large heterocycles often resemble their acyclic counterparts. However, anion formation can adjust the number of electrons in suitable systems so as to make a system conform to the Huckel rule, and render it aromatic if flat geometry can be attained. Examples are found in Chapter 5.20. Anion formation in selected large heterocycles can also initiate transannular reactions (see also Section 5.02.7 below). 

Like porphyrins, heteroporphyrins are aromatic and confirm the [4n+2] it-elecfron Huckel rule (00MI3). Replacing N with O, S, Se, and Te perturbs jt-delocalization and electronic properties. The alteration in jt-delocalization is evidenced from downfield shifts in H NMR spectra. The extent of shift in monoheteroatom is more than diheteroatom-substituted porphyrins (1979JA7055, 19840MR561). The large heteroatoms... 

Moreover, the high stabilization energy of cyclopentadienyl anion (comparable with that of benzene 31.19 kcal mol 1) demonstrates the aromatic character of this species, in agreement with the 4n + 2 Huckel rule. 

Systems such as cyclopentadienyl anion, benzene and tropylium cation with (4N + 2) 7t-electrons (N=Q, 1, 2,. ..) will thus have a closed shell, that is, four electrons in the degenerate pair of the highest occupied MOs in their ground configuration, and that is especially favourable energetically. This is the basis of the well-known Huckel rule of aromaticity. 

The Huckel rule is strictly applicable only to monocyclic compounds, but the general concept of aromaticity can be extended beyond simple mono-cyclic compounds to include polycyclic aromatic compounds. Naphthalene, with two benzene-like rings fused together, anthracene, 1,2-benz-pyrene, and coronene are all well-known compounds, BenzoLa]pyrene is particularly interesting because it is one of the cancer-causing substances that has been isolated from tobacco smoke. 

Benzene is described by molecular orbital theory as a planar, cyclic, conjugated molecule with six it electrons. According to the Huckel rule, a molecule must have 4 + 2 it electrons, where n = 0,1, 2, 3, and so on, to be aromatic. Planar, cyclic, conjugated molecules with other numbers of ir electrons are antiaroraatic. 

According to Huckel s rule, aromatic compounds are cyclic, fully conjugated, planar, and have (4n+2) tt electrons. Antiaromatic compounds are cyclic, fully conjugated, planar, and have 4n tt electrons,... 

This chapter deals with heteromacrocycles rather than smaller-ring heterocycles. Traditionally, heterocycles are three- to eight- or nine-membered rings that contain one or more noncarbon heteroatoms. Many, if not most, of the known heterocycles are aromatic compounds in which the noncarbon atoms contribute electrons to meet Huckel rule requirements. The crown ether situation contrasts with that of traditional heterocycles. The bulk of crown ether compounds contain 12 or more members and are aliphatic rather than aromatic. Those heterocycles that have cation binding properties usually contribute one or at most two donors to a cation s primary solvation... 

The compound [18]-annulene is large enough to be planar and obeys the HUckel rule (4n + 2 = 18, with n=4). It is a brownish red fairly stable reactive solid. NMR evidence shows that it has aromatic character. The an-nulene with n= 7, [30]-annulene, can also exist in a planar form but is highly unstable. See also pseudoaromatic. 

Larger annulenes permit the incorporation of irons double bonds into the rings hence, isomeric annulenes warrant consideration beginning with the cyclodecapen-taenes. [10]Annulene should, by the Huckel rule, possess aromatic stabilization if it were planar. All the isomeric cyclodecapentaenes suffer serious strain that prevents the planar geometry from being adopted. The trans,cis,trans,cis,cis-isomer, which has minimal angle strain, suffers a severe nonbonded repulsion between the two internal hydrogens ... 

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