KOT 222 ORGANIC CHEMISTRY II

CHAPTER 16 AROMATIC COMPOUNDS

Benzene
An aromatic compound. 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.
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Kekul Structure of Benzene

Proposed in 1866 by Friedrich Kekul, shortly after multiple bonds were suggested. Showing localized double-bonds. Failed to explain existence of only one isomer of 1,2-dichlorobenzene.
Cl Cl

X
Cl Cl
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Resonance Structure of Benzene

Benzene is actually a resonance hybrid between the two Kekul structures. The pi electrons are delocalized, with a bond order of 1.5 between adjacent carbon atoms

Orbital Representation of Benzene

Benzene is a flat ring of sp2 hybrid carbon atoms with their unhybridized p orbitals all aligned and overlapping. The conjugation and delocalization of the electrons give greater stability.

Unusual Reactions of Benzene

Benzene as a cyclic conjugated triene is predicted to react as polyenes. But, its reactions are unusual. 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.

Unusual Stabilities of Benzene

The hydrogenation of the first double bond of benzene is endothermic.

Annulenes
Cyclic hydrocarbons with alternating single and double bonds (uncharged, even no. of C atoms).

Assumptions: All are aromatic. Have similar stabilities as benzene. But, not all are aromatic.
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The MOs of Benzene

Six overlapping p atomic orbitals form six MOs. Three will be bonding, three antibonding. The intermediate energy levels are degenerate, two MOs at each level. Lowest energy MO will have all bonding interactions, no nodes. As energy of MO increases, the number of nodes increases.
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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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The MOs of Cyclobutadiene

There are four MOs: the lowest-energy bonding orbital, the highest-energy antibonding orbital, and two degenerate nonbonding orbitals.

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Energy Diagram for Cyclobutadiene

Four pi electrons fill the MOs.

Following Hunds rule, two electrons are in separate degenerate orbitals. This diradical with the highest-lying electrons in nonbonding MOs would be very reactive.
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Polygon Rule
The energy diagram for an annulene has the same polygonal shape as the cyclic compound with one vertex (all-bonding MO) at the bottom. The nonbonding line cuts horizontally through the center of the polygon. The pi electrons fill the MOs follows the aufbau principle and Hunds rule.

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Aromatic Requirements
1. Structure must be cyclic with conjugated pi bonds. 2. Each atom in the ring must have an unhybridized p orbital. 3. The unhybridized p orbitals must overlap to form a continuous ring. (Usually planar structure.) 4. Delocalization of pi electrons over the ring must lower the electronic energy
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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.
CH3 CH3

antiaromatic

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Hckels Rule
If the compound has a planar and continuous ring of overlapping p orbitals and has 4N + 2 electrons, it is aromatic. If the compound has a planar and continuous ring of overlapping p orbitals and has 4N electrons, it is antiaromatic. Otherwise, the system/compound is nonaromatic.

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Benzene

Six pi electrons. (4N+2) system Aromatic

Cyclobutadiene

Four pi electrons. (4N) system Antiromatic

Cyclooctatetraene

(4N) system Antiromatic

Nonaromatic
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Larger Annulenes
Larger 4N annulenes are not antiaromatic because they are flexible enough to become nonplanar.

[12] annulene

[16] annulene

Larger 4N+2 annulenes depend on whether the molecule can adopt the necessary planar conformation.
H H

All-cis nonaromatic

Two trans nonaromatic

naphthalene aromatic

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MO Derivation of Hckels Rule

In a cyclic conjugated system, the lowest-energy MO is filled with two electrons. Each of the additional shells has two degenerate MOs, with space for four electrons.

A diradical, unstable.
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Aromatic Ions
Hckels rule also applies to systems having odd numbers of C atoms and bearing positive or negative charges. 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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Acidity of Cyclopentadiene
Unusually acidic (pKa of 16). Loss of a proton converts the nonaromatic diene to the aromatic cyclopentadienyl anion.

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Cyclopentadienyl cation Huckels rule predicts that the cyclopentadienyl cation, with four pi electrons, is antiaromatic. The cyclopentadienyl cation is not easily formed.

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Cycloheptatrienyl Ions
The cycloheptatrienyl cation (tropylium ion) is easily formed.
H OH H , H2O
+

H +

6 pi electron, (4N+2) system, aromatic

The cycloheptatrienyl anion is difficult to form.

H H
B

8 pi electron, 4N system, antiaromatic

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Cyclooctatetraene Dianion
Cyclooctatetraene is nonaromatic. Its dianion is easily prepared with planar, regular octagonal structure aromatic.

Continuous overlapping p orbitals. (4N+2) system.

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Heterocyclic Aromatic Compounds

A heterocyclic compound is a cyclic compound in which one or more of the ring atoms is an atom other than carbon
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Pyridine
Aromatic nitrogen analogue of benzene. It has six delocalized electrons in its pi system. The two non-bonding electrons on nitrogen are in an sp2 orbital, and they do not interact with the pi electrons of the ring.

These electrons are in the sp2 orbital perpendicular to 28 the p orbital.

Protonation of pyridine: Pyridine is basic, with non-bonding electrons available to abstract a proton.

aromatic

aromatic
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Pyrrole
An aromatic five-membered heterocycle. Nonbonding electrons on N atom involve in the pi bonding system, so much weaker base.

No unhybridized p orbital needed for aromaticity

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Basic or Nonbasic?
N atom with it nonbonding electrons involve in the pi bonding system is nonbasic.
N N

Pyrimidine has two basic nitrogens. Imidazole has one basic nitrogen and one nonbasic. Purine? 3 basic, 1 nonbasic
Most nonbasic nitrogens have three single bonds. Most basic nitrogens have a double bond in 31 the ring.

N H

N N H N

Other Heterocyclics

All are aromatic

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Polynuclear Aromatic Hydrocarbons

Compounds composed of two or more fused benzene rings. Naphthalene

Anthracene

Phenanthrene

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Reactivity of Polynuclear Hydrocarbons

As the number of aromatic rings increases, the resonance energy per ring decreases. These large PAHs can undergo addition reactions.
6 5
8 7 6 5 H 10 Br 4 H 9 Br 1 2 3

7 8 9 Br H

4 3 2 1 H 10 Br

(mixture of cis and trans isomers)

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Larger Polynuclear Aromatic Hydrocarbons

Formed in combustion (tobacco smoke). Many are carcinogenic. Epoxides form, combine with DNA base.

pyrene

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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 of Carbon

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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Fused Heterocyclic Compounds

Common in nature, synthesized for drugs.

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Common Names of Benzene Derivatives

OH CH3 NH2 OCH3

phenol

toluene
O C CH2 C CH3

aniline
O C H

anisole
O C OH

styrene

acetophenone

benzaldehyde

benzoic acid
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Disubstituted Benzenes
The prefixes ortho-, meta-, and para- are commonly used for the 1,2-, 1,3-, and 1,4- positions, respectively.

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3 or More Substituents
Use the smallest possible numbers, but the carbon with a functional group that define the base name is #1.
OH

O 2N

NO 2

O2N

NO2

NO 2 1,3,5-trinitrobenzene

NO2 2,4,6-trinitrophenol

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Common Names for Substituted 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

Benzene ring as a substituent on another molecule is called as phenyl group.
CH2 C C CH3

Br
Ph CH 2 C C CH 3

1-phenyl-2-butyne
phenyl bromide

Benzyl group: seven-carbon unit consisting of a benzene ring and a methylene group.

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Physical Properties of Benzene and Its Derivatives

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
The most common fragmentation of alkylbenzene derivative is the cleavage of a benzylic bond.

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UV Spectroscopy
Benzene has three absorptions.
max at 184 nm
Moderate band Characteristic band Additional conjugated double bond cause bathochromic shift.

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