Organic Chemistry, 5th Edition L. G. Wade, Jr.

Chapter 16 Aromatic Compounds

Jo Blackburn Richland College, Dallas, TX Dallas County Community College District 2003, Prentice Hall

Discovery of Benzene
Isolated in 1825 by Michael Faraday who determined C:H ratio to be 1:1. Synthesized in 1834 by Eilhard Mitscherlich who determined molecular formula to be C6H6. Other related compounds with low C:H ratios had a pleasant smell, so they were classified as aromatic. => 2 Chapter 16

Kekul Structure
Proposed in 1866 by Friedrich Kekul, shortly after multiple bonds were suggested. Failed to explain existence of only one isomer of 1,2-dichlorobenzene.
H H C C H C C C H
Chapter 16 3

C H

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Resonance Structure
Each sp2 hybridized C in the ring has an unhybridized p orbital perpendicular to the ring which overlaps around the ring.

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Chapter 16 4

Unusual Reactions
Alkene + KMnO4 diol (addition) Benzene + KMnO4 no reaction. Alkene + Br2/CCl4 dibromide (addition) Benzene + Br2/CCl4 no reaction. With FeCl3 catalyst, Br2 reacts with benzene to form bromobenzene + HBr (substitution!). Double bonds remain. =>
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Unusual Stability
Hydrogenation of just one double bond in benzene is endothermic!

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Chapter 16 6

Annulenes
All cyclic conjugated hydrocarbons were proposed to be aromatic. However, cyclobutadiene is so reactive that it dimerizes before it can be isolated. And cyclooctatetraene adds Br2 readily. Look at MOs to explain aromaticity. =>
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MO Rules for Benzene

Six overlapping p orbitals must form six molecular orbitals. Three will be bonding, three antibonding. Lowest energy MO will have all bonding interactions, no nodes. As energy of MO increases, the number of nodes increases. =>
Chapter 16 8

MOs for Benzene

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Chapter 16 9

Energy Diagram for Benzene

The six electrons fill three bonding pi orbitals. All bonding orbitals are filled (closed shell), an extremely stable arrangement.

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Chapter 16 10

MOs for Cyclobutadiene

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Chapter 16 11

Energy Diagram for Cyclobutadiene

Following Hunds rule, two electrons are in separate orbitals. This diradical would be very reactive. =>
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Polygon Rule
The energy diagram for an annulene has the same shape as the cyclic compound with one vertex at the bottom.

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Aromatic Requirements
Structure must be cyclic with conjugated pi bonds. Each atom in the ring must have an unhybridized p orbital. The p orbitals must overlap continuously around the ring. (Usually planar structure) Compound is more stable than its openchain counterpart. =>
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Anti- and Nonaromatic

Antiaromatic compounds are cyclic, conjugated, with overlapping p orbitals around the ring, but the energy of the compound is greater than its open-chain counterpart. Nonaromatic compounds do not have a continuous ring of overlapping p orbitals and may be nonplanar. =>
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Hckels Rule
If the compound has a continuous ring of overlapping p orbitals and has 4N + 2 electrons, it is aromatic. If the compound has a continuous ring of overlapping p orbitals and has 4N electrons, it is antiaromatic.
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Chapter 16 16

[N]Annulenes
[4]Annulene is antiaromatic (4N e-s) [8]Annulene would be antiaromatic, but its not planar, so its nonaromatic. [10]Annulene is aromatic except for the isomers that are not planar. Larger 4N annulenes are not antiaromatic because they are flexible enough to become nonplanar. =>
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MO Derivation of Hckels Rule

Lowest energy MO has 2 electrons. Each filled shell has 4 electrons.

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Cyclopentadienyl Ions
The cation has an empty p orbital, 4 electrons, so antiaromatic. The anion has a nonbonding pair of electrons in a p orbital, 6 e-s, aromatic.

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Chapter 16 19

Acidity of Cyclopentadiene
pKa of cyclopentadiene is 16, much more acidic than other hydrocarbons.
H H + pKa = 16 _ OC(CH3)3 H + HOC(CH3)3 pKa = 19

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Chapter 16 20

Tropylium Ion
The cycloheptatrienyl cation has 6 p electrons and an empty p orbital. Aromatic: more stable than open chain ion
H OH H , H2O
+

H +

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Chapter 16 21

Dianion of [8]Annulene
Cyclooctatetraene easily forms a -2 ion. Ten electrons, continuous overlapping p orbitals, so it is aromatic.

+ 2K

+ 2K

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Chapter 16 22

Pyridine
Heterocyclic aromatic compound. Nonbonding pair of electrons in sp2 orbital, so weak base, pKb = 8.8.

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Pyrrole
Also aromatic, but lone pair of electrons is delocalized, so much weaker base.

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Chapter 16 24

Basic or Nonbasic?
N N

Pyrimidine has two basic nitrogens.

Imidazole has one basic nitrogen and one nonbasic.
N N
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N H

N N H

Purine?

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Other Heterocyclics

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Fused Ring Hydrocarbons

Naphthalene

Anthracene Phenanthrene
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Chapter 16 27

Reactivity of Polynuclear Hydrocarbons

As the number of aromatic rings increases, the resonance energy per ring decreases, so larger PAHs will add Br2.
H Br

Br
H Br

H H
Chapter 16

Br

(mixture of cis and trans isomers)

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Fused Heterocyclic Compounds

Common in nature, synthesized for drugs.

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Allotropes of Carbon
Amorphous: small particles of graphite; charcoal, soot, coal, carbon black. Diamond: a lattice of tetrahedral Cs. Graphite: layers of fused aromatic rings.

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Some New Allotropes

Fullerenes: 5- and 6-membered rings arranged to form a soccer ball structure. Nanotubes: half of a C60 sphere fused to a cylinder of fused aromatic rings.

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Common Names of Benzene Derivatives

OH CH3 NH2 OCH3

phenol
H C CH2

toluene
O C CH3

aniline
O C H

anisole
O C OH

styrene

acetophenone

benzaldehyde
Chapter 16

benzoic acid

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Disubstituted Benzenes
The prefixes ortho-, meta-, and para- are commonly used for the 1,2-, 1,3-, and 1,4positions, respectively.
Br Br o-dibromobenzene or 1,2-dibromobenzene

NO2 HO p-nitrophenol or 4-nitrophenol

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Chapter 16 33

3 or More Substituents
Use the smallest possible numbers, but the carbon with a functional group is #1.
OH
O2N NO2

O2N

NO2

NO2 1,3,5-trinitrobenzene
Chapter 16

NO2 2,4,6-trinitrophenol

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Common Names for Disubstituted Benzenes

CH3 CH3 O OH C CH3 CH3 m-xylene H3C CH3 mesitylene OH

o-toluic acid

H3C

p-cresol

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Phenyl and Benzyl

Phenyl indicates the benzene ring attachment. The benzyl group has an additional carbon.
Br
CH2Br

phenyl bromide

benzyl bromide
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Chapter 16 36

Physical Properties
Melting points: More symmetrical than corresponding alkane, pack better into crystals, so higher melting points. Boiling points: Dependent on dipole moment, so ortho > meta > para, for disubstituted benzenes. Density: More dense than nonaromatics, less dense than water. Solubility: Generally insoluble in water. =>
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IR and NMR Spectroscopy

C=C stretch absorption at 1600 cm-1. sp2 C-H stretch just above 3000 cm-1. 1H NMR at 7- 8 for Hs on aromatic ring. 13C NMR at 120- 150, similar to alkene carbons.
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Mass Spectrometry

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Chapter 16 39

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UV Spectroscopy

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Chapter 16 40

End of Chapter 16

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