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Chapter 14. Aromatic Compounds. About The Authors. These PowerPoint Lecture Slides were created and prepared by Professor William Tam and his wife, Dr. Phillis Chang.

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chapter 14

Chapter 14

Aromatic Compounds

about the authors
About The Authors

These PowerPoint Lecture Slides were created and prepared by Professor William Tam and his wife, Dr. Phillis Chang.

Professor William Tam received his B.Sc. at the University of Hong Kong in 1990 and his Ph.D. at the University of Toronto (Canada) in 1995. He was an NSERC postdoctoral fellow at the Imperial College (UK) and at Harvard University (USA). He joined the Department of Chemistry at the University of Guelph (Ontario, Canada) in 1998 and is currently a Full Professor and Associate Chair in the department. Professor Tam has received several awards in research and teaching, and according to Essential Science Indicators, he is currently ranked as the Top 1% most cited Chemists worldwide. He has published four books and over 80 scientific papers in top international journals such as J. Am. Chem. Soc., Angew. Chem., Org. Lett., and J. Org. Chem.

Dr. Phillis Chang received her B.Sc. at New York University (USA) in 1994, her M.Sc. and Ph.D. in 1997 and 2001 at the University of Guelph (Canada). She lives in Guelph with her husband, William, and their son, Matthew.

slide3

The Discovery of Benzene

  • Benzene:
  • In 1825, Faraday isolated benzene from a compressed illuminating gas that had been made by pyrolyzing whale oil
slide4

In 1834, a German chemist, Eilhardt Mitscherlich, synthesized benzene by heating benzoic acid with calcium oxide

slide5

In 19th century, organic compounds were classified as being either aliphaticor aromatic

  • Aliphatic
    • The chemical behavior of a compound was “fatlike”
  • Aromatic
    • The compound had a low hydrogen-to-carbon ratio and it was “fragrant”
slide6

Nomenclature of BenzeneDerivatives

  • Naming monosubstituted benzenes
    • In many simple compounds, benzene is the parent name and the substituent is simply indicated by a prefix
slide7

For other simple and common compounds, the substituent and the benzene ring taken together may form a commonly accepted parent name

slide8

Naming disubstituted benzenes

    • When two substituents are present, their relative positions are indicated by the prefixes ortho-, meta-, and para- (abbreviated o-, m-, and p-) or by the use of numbers
slide11

Naming benzene rings with more than two groups

    • If more than two groups are present on the benzene ring, their positions must be indicated by the use of numbers
    • The benzene ring is numbered so as to give the lowest possible numbers to the substituents
slide12

When more than two substituents are present and the substituents are different, they are listed in alphabetical order

slide13

When a substituent is one that, together with the benzene ring gives a new base name, that substituent is assumed to be in position 1 and the new parent name is used

slide14

When the C6H5 group is named as a substituent, it is called a phenyl group

  • A hydrocarbon composed of one saturated chain and one benzene ring is usually named as a derivative of the larger structural unit. However, if the chain is unsaturated, the compound may be named as a derivative of that chain, regardless of ring size
slide23

These 1,2-dibromobenzenes do not exist as isomers

X

There is no such equilibrium between benzene ring bond isomers

slide25

p-electrons above and below ring

The Thermodynamic Stabilityof Benzene

  • Since p bonds are formed from side-way overlap of p orbitals, p electron clouds are above & below the plane of the double bond
slide27

Modern Theories of the Structureof Benzene

6A. The Resonance Explanation of theStructure of Benzene

  • All bond lengths the same (1.39 Å) (compare with C–C single bond 1.54 Å, C=C double bond 1.34 Å)
  • Extra stabilization due to resonance  aromatic
slide28

p-electrons above and below ring

  • 3-D structure
  • Planar structure
  • All carbons sp2 hybridized
slide31

Hückel’s Rule: The 4n + 2 pElectron Rule

  • Hückel’s rule is concerned with compounds containing one planar ring in which each atom has a porbital as in benzene
  • Planar monocyclic rings containing 4n + 2 p electrons, where n = 0, 1, 2, 3, and so on (i.e., rings containing 2, 6, 10, 14 . . . etc. p electrons), have closed shells of delocalized electrons like benzene and have substantial resonance energies
slide32

Hückel’s rule states that planar monocyclic rings with 2, 6, 10, 14 . . . delocalized electrons should be aromatic

slide33

7A. How To Diagram the Relative

Energies of p Molecular Orbitalsin

Monocyclic Systems Based on

Hückel’sRule

slide34

The p molecular orbitals that cyclooctatetraene would have if it were planar. Notice that, unlike benzene, this molecule is predicted to have two nonbonding orbitals, and because it has eight p electrons, it would have an unpaired electron in each of the two nonbonding orbitals. Such a system would not be expected to be aromatic.

slide35

The bonds of cyclooctatetraene are known to be alternately long and short; X-ray studies indicate that they are 1.48 and 1.34 Å, respectively

slide36

7B. The Annulenes

  • Hückel’s rule predicts that annulenes will be aromatic if their molecules have 4n + 2 p electrons and have a planar carbon skeleton
slide40

7C. NMR Spectroscopy: Evidence forElectron Delocalization inAromatic Compounds

  • The 1H NMR spectrum of benzene consists of a single unsplit signal at d 7.27
  • The signal occurs at relatively high frequency, which is compelling evidence for the assertion that the p electrons of benzene are delocalized
slide41

The circulation of p electrons in benzene creates an induced magnetic field that, at the position of the protons, reinforces the applied magnetic field. This reinforcement causes the protons to be strongly deshielded and to have a relatively high frequency (d ~ 7) absorption

slide43

(d 9.3)

(d -3.0)

slide44

7D. Aromatic Ions

pka = 36

pka = 16

slide47

7E. Aromatic, Antiaromatic, andNonaromatic Compounds

  • An aromatic compound has its p electrons delocalized over the entire ring and it is stabilized by the p-electron delocalization
slide48

One way to evaluate whether a cyclic compound is stabilized by delocalization of p electrons through its ring is to compare it with an open-chain compound having the same number of p electrons

  • Based on sound calculations or experiments
    • If the ring has lower p-electron energy, then the ring is aromatic
    • If the ring and the chain have the same p-electron energy, then the ring is nonaromatic
    • If the ring has greater p-electron energy than the open chain, then the ring is antiaromatic
slide50

Other Aromatic Compounds

8A. Benzenoid Aromatic Compounds

  • Benzenoid polycyclic aromatic hydrocarbons consist of molecules having two or more benzene rings fused together
slide53

Heterocyclic Aromatic Compounds

  • Cyclic compounds that include an element other than carbon are called heterocyclic compounds
slide56

Aromaticity

    • Evidence: 1H NMR shift
slide59

Non-basic nitrogen

basic nitrogen

slide60

Aromatic Compounds in Biochemistry

  • Two amino acids necessary for protein synthesis contain the benzene ring
slide62

Nicotinamide adenine dinucleotide, one of the most important coenzymes in biological oxidations and reductions, includes both a pyridine derivative (nicotinamide) and a purine derivative (adenine) in its structure

slide63

Spectroscopy of AromaticCompounds

11A. 1H NMR Spectra

  • The ring hydrogens of benzene derivatives absorb downfield in the region between d 6.0 and d 9.5 ppm

11B. 13C NMR Spectra

  • The carbon atoms of benzene rings generally absorb in the d 100–170 ppm region of 13C NMR spectra