Title: Arenes and Aromaticity
1Chapter 11
2Aromatic Compounds
- Arenes hydrocarbons based on the benzene ring
as a structural unit. - Aromatic Compounds Compounds possessing more
stability than would be predicted due to having
conjugated double bonds.
3Benzene
- Benzene has been known since 1825. It was
discovered by Michael Faraday. The empirical
formula was determined by Eirlhardt Mitscherlich.
Structure worked out by August Kekule in 1866.
4Resonance Picture of Benzene
- The two equivalent Kekule structures represent a
resonance hybrid shown by the right hand
structure.
5Stability of Benzene
6The Orbital Hybridization View of Benzene
7Molecular Orbitals of Benzene
8Nomenclature of Benzene Derivatives
- Monosubstituted Benzene Compounds are often named
by attaching the name of the substitutent as a
prefix of benzene. - Some Monosubstituted Benzene Derivatives have
long standing common names.
9Some benzene derivatives have long standing
common names.
10Disubstituted Benzene Derivatives
- ortho- 1,2 disubstituted benzene
- meta- 1,3 disubstituted benzene
- para- 1,4 disubstituted benzene
11Trisubstituted Benzene Derivatives
- o,m,p are not used when three or more
substituents are on the benzene ring. Instead
the ring is numbered and the base name is that of
the ranking substituent. The substituents are
named in alphabetical order. The numbering is
such that the next substituted position is given
the lowest number. - Ex Try pick one p. 467 27 and p. 468 28 b.
12Benzene as a Substituent
- Phenyl- C6H5-
- Benzyl- C6H5CH2-
- Biphenyl
13Polycyclic Aromatic Compounds
- These compounds are composed of benzene rings
fused together. They have substantial resonance
energy. (See 11.30) - Napthalene
- Anthracene
- Phenanthrene
14Physical Properties of Arenes
- Arenes are similar to hydrocarbons in physical
properties. - Nonpolar
- Insoluble in Water
- Less Dense than Water
15Reactions of Arenes
- Two main Classes of Reaction
- Reactions of the Ring itself
- Reduction
- Electrophilic Aromatic Substitution
- 2. Reactions in which the ring influences
reactivity of a functional unit to which it is
attached.
16Birch Reduction
- Reduction of the benzene ring by treatment with
sodium and methanol in liquid ammonia. It is
used to synthesize dienes.
17Birch Reduction Mechanism
18Free Radical Halogenation of Alkylbenzenes
- Benzylic Radicals are especially stable.
Therefore free radical attack favors the benzylic
position. The benzylic radical is analogous to
the allylic radical.
19Free Radical Halogenation
Br2
p-Nitrotoluene
20Spin Density Representation of Benzyl Radical
21lowM.O. View of Benzyl Radical (lowest energy
M.O.)
22NBS Bromination (lab prep)
23Oxidation of Alkyl Benzenes
or
or
24Nucleophilic Substitution of Benzylic Halides
- Benzylic halides make ideal substrates for SN2
reactions because they react readily toward good
nucleophiles and cannot undergo competing
elimination.
25Primary Benzylic Halides
acetic acid
(78-82)
26Preparation of Alkenylbenzenes
- Industrial Prep Dehydrogenation of Ethylbenzene
630C
ZnO
H2
27Laboratory Preparation of Alkenylbenzenes
- Acid catalyzed dehydration or base promoted
elimination reactions of appropriate leaving
groups will produce alkneylbenzenes
28Dehydration of Benzyl Alcohols
KHSO4
heat
(80-82)
29Dehydrohalogenation
30Addition Reactions of Alkenylbenzenes
(92)
31Addition Reactions of Alkenylbenzenes
Br2
CH
CH2
Br
Br
(82)
32Addition Reactions of Alkenylbenzenes
(75-84)
33Polymerization of Styrene
polystyrene
34Polymerization of Styrene (Mechanism)
35Huckels Rule
- Planar, monocyclic, fully conjugated polyenes,
only with (4n2) p electrons will have a special
stability (be aromatic). - Planar, monocyclic, fully conjugated polyenes
with (4n) p electrons are especially unstable and
are therefore antiaromatic.
36(No Transcript)
37Annulenes
- Annulenes are planar, monocyclic, completely
conjugated polyenes. That is, they are the
kind of hydrocarbons treated by Hückel's rule.
- Annulenes are named in this manner
- x annulene where x of carbons.
- Many have been prepared to test Huckels rule.
3810Annulene
predicted to be aromatic by Hückel's rule,but
too much angle strain when planar and all double
bonds are cis 10-sided regular polygon has angles
of 144
3910Annulene
incorporating two trans double bonds intothe
ring relieves angle strain but introducesvan der
Waals strain into the structure andcauses the
ring to be distorted from planarity
4014Annulene
H
H
H
H
14 ? electrons satisfies Hückel's rule van der
Waals strain between hydrogens insidethe ring
Therefore it is nonplanar.
4116Annulene
16 ? electrons does not satisfy Hückel's
rule alternating short (134 pm) and long (146 pm)
bonds is an antiaromatic 4n p-electron system
4218Annulene
18 ? electrons satisfies Hückel's rule resonance
energy 418 kJ/mol bond distances range between
137-143 pm
43Aromatic Ions
- Some nonaromatic compounds will form stabilized
aromatic ions.
44Aromatic Ions
Cyclopentadiene is unusually acidic for a
hydrocarbon. Increased acidity is due to
stability of cyclopentadienide anion.
pKa 16 Ka 10-16
45Heterocyclic Aromatic Compounds
Examples
Pyridine
Pyrrole
Furan
Thiophene
46Pyridine
6 ? electrons in ring lone pair on nitrogen is in
ansp2 hybridized orbitalnot part of ??system
of ring