Aromatic compounds electron pairs

Section 11 23 Huckel s rule can be extended to heterocyclic aromatic compounds Unshared electron pairs of the heteroatom may be used as tt electrons as necessary to satisfy the 4n + 2 rule... 

Aromatic compound (Section 113) An electron delocalized species that is much more stable than any structure wntten for It in which all the electrons are localized either in cova lent bonds or as unshared electron pairs... 

Charge-Transfer Compounds. Similat to iodine and chlorine, bromine can form charge-transfer complexes with organic molecules that can serve as Lewis bases. The frequency of the iatense uv charge-transfer adsorption band is dependent on the ionization potential of the donor solvent molecule. Electronic charge can be transferred from a TT-electron system as ia the case of aromatic compounds or from lone-pairs of electrons as ia ethers and amines. 

The simplest examples of this type of compound are enamines derived from the quinuclidine skeleton (67). The formulation of enamines of qflmuclidine in a inesomeric form would violate Bredt s rule. Actually, the ultraviolet spectrum of 2,3-benzoquinuclidine shows that there exists no interaction of aromatic ring tt electrons and the nitrogen-free electron pair (160,169). The overlap of the olefinic tt orbital and the lone pair orbital on nitrogen is precluded. 

The formation of 151 from the phosphonate 171 could be proved only by indirect means. Electron-rich aromatic compounds such as N,N-diethylaniline and N,N,N, N -tetraethyl-m-phenylenediamine U0 1I9> and N-methylaniline 120> are phosphorylated in the para- and in the ortho- plus para-positions by 151. Furthermore, 151 also adds to the nitrogen lone pair of aniline to form the corresponding phosphor-amidate. Considerable competition between nucleophiles of various strengths for the monomeric methyl metaphosphate 151 — e.g. aromatic substitution of N,N-diethylaniline and reaction with methanol or aromatic substitution and reaction with the nitrogen lone pair in N-methylaniline — again underline its extraordinary non-selectivity. 

In addition to those compounds which contain hetero-atoms having lone electron pairs and which are therefore characterized as bases , there exist analogous interactions with molecules which do not possess any lone pairs. It is however known from the chemistry of unsaturated compounds, particularly of aromatics, that solutions of such compounds. 

Formation of an intimate ([cation-radical]-radical) pair, [ArH V N02] This pair is, essentially, a single-electron transfer complex, indicative of one-electron oxidation of an aromatic compound by nitronium. 

An equivalent description in many respects consists of a primary transfer of an electron from a nucleophile molecule close to the meta-position of the excited aromatic compound and subsequent bond formation between the partners of the radical pair so formed. 

Two additional examples of aromatic compounds containing heteroatoms eire shown in Figure 6-14. In both compounds, the heteroatom has two lone pairs. However, only one of the pairs is in a p-orbital perpendiculcir to the plane of the ring. The other electron pair is in the plane of the ring. 

The aromatic 7r-electron system of thienothiophenes and related compounds containing two condensed rings comprises electrons from three carbon-carbon double bonds and unshared electron pairs from two heteroatoms, and thus is similar to that of naphthalene. 

Quinoline is a base since, as for pyridine, the lone pair of electrons on the nitrogen atom is not utilized in its internal resonance. Although it is an aromatic compound, the valence bond description of quinoline shows two of the neutral contributors, A and C (see Scheme 3.1), to the resonance hybrid as quinonoid in character, whereas in B either the carbo-cycle or the heterocycle must exist in the form of a 1,3-diene. The presence of the pyridine nucleus is reflected by the inclusion of doubly charged canonical forms. 

The definition of aromaticity conceived by Hiickel strictly applies to monocyclic ring systems, but indole, constructed from the fusion of benzene and pyrrole, behaves as an aromatic compound, like quinoline and isoquinoline. The ring fusion, however, affects the properties of both components. This is reflected in the valence bond description of indole, shown in Scheme 7.1, where one canonical representation shows electron density shared between N-1 and C-3 in the pyrrole unit (implying enamine character). Note that although other canonical forms can be drawn, where the lone-pair electrons are delocalized into the benzenoid ring, their energy content is relatively high and they are of limited importance. 

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