aromatic chemistry - j. hepworth, d. waring, m. waring (rsc, 2002) ww

[...]... acceptable ways of naming the three positional isomers that are possible for disubstituted benzene rings The substituent 11 Aromatic Chemistry 12 6; borth0 meta 4 para 24 25 positions 1, 2-, 1, 3- and 1, 4- are sometimes replaced by the terms ortho-, meta- and para- (abbreviated to 0-, m- and p-, respectively) (see 24 and 25) You are advised to become familiar with both systems so that you can use them interchangeably... Scheme 2.9 21 22 Aromatic Chemistry 66+& c-c-c-c-c1 4 6 influences both the electron density at the various ring positions and the stability of the intermediate carbocation The outcome can be understood by superimposing the electronic effects of the substituents on the slow, rate-determining step of the general mechanism for electrophilic aromatic substitution discussed above In a o-bond between two... the benzene ring is named as a substituent and in these cases the name for C,H ,- is phenyl, abbreviated to Ph The name for C,H,CH ,- is benzyl or Bn, whilst the benzoyl substituent is C,H,CO- or Bz These substituents can also be named systematically as shown in Figure 1.16 Figure 1.16 Aromaticity 13 14 Aromatic Chemistry Aromatic Substitution 2.1 Introduction In Chapter 1 it was stated that the principal...Aromaticity zene or its This stabilizing feature dominates the chemistry of benzene and its derivatives Figure 1.1 Hydrogenation of cyclohexene, cyclohexadiene and benzene 1.3.1 Valence Bond Theory of Aromaticity X-ray crystallographic analysis indicated that benzene is a planar, regular hexagon in which all the carbon-carbon bond lengths are 139 pm, intermediate between the single C-C bond... (and so on) n;-electrons This series of numbers is represented by the term 4n + 2, where n is an integer, and gave rise to Hiickel’s 4n + 2 rule that refers to the number of nelectrons in the p-orbital system In the case of benzene, n = 1, and thus the system contains six n-electrons that are distributed in MOs as shown above 5 6 Aromatic Chemistry This rule is now an important criterion for aromaticity... chloride ions from the 3,4-dichlorocyclobutene derivative creates a 2n-electron aromatic system, the square, stable cyclobutenyl dication (Scheme 1.2) Me FMe 2SbFsCl- I., Scheme 1.2 I Me Me I.4.2 6.n-Electron Systems We have seen that benzene fits into this category, but there are a number of other stable aromatic systems that contain six n-electrons Cyclopentadiene is surprisingly acidic (pKa ca 16) for... delocalized aromatic set of six n-electrons Scheme 1.3 Figure 1.9 The cyclopentadienyl anion 13 is an efficiently in which all the carbon-carbon bond lengths are equal (Figure 1.9) It forms stable compounds, of which ferrocene (14) is an example, which undergo aromatic substitution reactions such as sulfonation and acetylation In contrast, it is the derived from cycloheptatriene that possesses the aromatic. .. of’pyridine Similarly, the five-membered heterocycle pyrrole (18) is aromatic, although this molecule obeys Huckel’s rule only because the nitrogen atom contributes two electrons to the n-cloud In this respect, pyrrole is analogous to the cyclopentadienyl anion As a consequence, the nitrogen atom does not retain a lone pair of electrons and pyrrole is not basic 1.4.3 1OX-, 147~and 18lt-Electron Systems The... Those systems that contain 4n n;-electrons are unstable and are referred to as antiaromatic compounds The reason for the success of the Hiickel rule in predicting aromaticity lies in the derivation of the 71: MOs For cyclic conjugated molecules, the energy levels of the bonding MOs are always arranged with one lowest-lying MO followed by degenerate pairs of orbitals The anti-bonding orbitals are arranged... the range 6 6. 5-8 .5 ppm Alkenyl hydrogen atoms are also deshielded, but to a lesser extent and normally resonate in the region 6 4. 5-5 .5 ppm The local field inside the ring opposes the applied field and this effect is apparent in the ' H N M R spectra of the annulenes (see p 11) 1.4.1 2n-Electron Systems Aromatic systems that obey Hiickel's 4n + 2 rule where n = 0 and so possess two n-electrons do exist . Atomic and Molecular Spectroscopy Organic Synthetic Methods J R Hunson Aromatic Chemistry Quantum Mechanics for Chemists S E Dann J M Soddon & J D Gale J A4 Hollas J D. Acidic Groups Reactions of Aromatic Acids Acidity of Aromatic Acids Compounds with More Than One Acidic Group Side-chain Acids Introduction Aromatic Alcohols Aromatic Aldehydes Aromatic. SERIES Stereochemistry D G Morris Reactions and Characterization of Solids Main Group Chemistry W Henderson d- and f-Block Chemistry C J Joncs Structure and Bonding J Burvc.fr Functional