Chem 2261 Notes

Chemistry of Benzene and Its Derivatives

(Bruice, Chapter 15)

Aromatic Compounds and the Concept of Aromaticity

Benzene and Other Compounds Possessing Cyclic Six Electron (Aromatic) Systems Aromatic compounds are those possessing a planar, continuous cyclic system which contains a total of 4n+2 electrons. Benzene and its derivatives are the best known examples. Benzene has six electrons (corresponding to 3 bonds) delocalized among a cyclic array six overlapping p-orbitals system of benzene. Other cyclic systems containing six electrons are cyclopentadienyl anion, tropyllium cation, cyclobutadienyl dianion. These structures, like benzene, are aromatic. Aromaticity confers a special stability on these systems.

benzene

cyclopentadienyl anion

tropyllium cation
N

cyclobutadienyl dianion

Pyridine, pyrrole, furan, and imidazole are examples of aromatic heterocyles:

N pyridine NH pyrrole O furan NH

imidazole

Other Cyclic 4n+2 Electron (Aromatic) Systems

2 electrons +

= =

+ NH 18 electrons N N HN

10 electrons

Antiaromatic Systems Planar, continuous cyclic systems which contain a total of 4n electrons are especially unstable and are said to be antiaromatic.
For 8 electrons delocalization is destablilizing For 4 electrons delocalization is destablilizing distorts to square delocalized antiaromatic UNSTABLE rectangular localized non-aromatic more stable

=
planar, delocalized antiaromatic UNSTABLE

distorts to nonplanar, localized non-aromatic more stable

Classify the following molecules as aromatic, antiaromatic, or non-aromatic:

N+

Chem 2261 Notes

Chemistry of Benzene and Its Derivatives

(Bruice, Chapter 15)

Electrophilic Aromatic Substitution

General
H E+ B H E E
E = D, Cl, Br, SO3H, NO2, R (alkyl), O=C-R (acyl), etc.

aromatic

resonance delocalized

aromatic

Resonance delocalization of cationic intermediate:

H E H E H E H E

resonance structures

hybrid structure

Specific Reactions
All electrophilic aromatic substitution reactions follow the same general mechanism. The only thing that varies is the specific electrophile which gets attached to the aromatic ring. Some specific electrophilic aromatic substitution reactions are described below. a) Sulfonation
H conc. H2SO4 SO3H Electrophile = OH S+ O O
+SO H 3

overall H replaced by SO3H

+SO H 3

H SO3H

SO3H

Sulfonation differs subtly from most other electrophilic aromatic substitution reactions in that it is reversible (note equilibrium arrows). b) Nitration
H HNO3 H2SO4 NO2
+

Electrophile = O N O NO2+

overall H replaced by NO2

NO2+

H NO2

NO2

How are the electrophiles generated in the sulfonation and nitration reactions above?

Chem 2261 Notes c) Halogenation

H X2 FeX3 (X = Br or Cl) H X X FeX3 B X

Chemistry of Benzene and Its Derivatives

(Bruice, Chapter 15)

Electrophile =

X X FeX3 equivalent to X+

overall H replaced by X (X = Br or Cl)

H X

d) Friedel-Crafts Alkylation
H R-Cl AlCl3 R Electrophile = R Cl AlCl3 R Cl AlCl3 H R Cl AlCl3 B H R R overall H replaced by R R = alkyl group

Carbocation rearrangement competes with substitution (see discussion of incipient primary carbocations on p.647 of your textbook):
H Cl AlCl3 Cl AlCl3 H Cl AlCl3 minor (35%) MAJOR (65%) major electrophile Cl AlCl3

e) Friedel-Crafts Acylation
H O R Cl AlCl3 O C R
+

R
+

Electrophile =

R C O acylium ion

O overall H replaced by R RCO = acyl group (R = alkyl group) O R Cl AlCl3

O H

While Friedel-Crafts acylation can be used to make aryl ketones, it cannot be used to make corresponding aldehydes due to the instability of formyl choride. 3

Chem 2261 Notes

H O H Cl AlCl3 O H

Chemistry of Benzene and Its Derivatives

(Bruice, Chapter 15)

O is not possible because H Cl is unstable

However, benzaldehyde (and other aryl aldehydes) can be prepared by means of the GattermanKoch formylation reaction whereby formyl chloride is generated in situ under conditions where it will react in an electrophilic aromatic substitution reaction upon its generation.
H O CO/HCl high pressure AlCl3/CuCl H

The product of a Friedel-Crafts acylation can be reduced to a compound where the carbonyl group (C=O) is replaced by a methylene group (CH2). This can be accomplished through either Clemmenson reduction or Wolff-Kishner reduction.
O Clemmensen reduction Zn/Hg, HCl H R H EtOH, R

H2NNH2 HO, Wolff-Kishner reduction

Note that Clemmenson or Wolff-Kishner Reduction can be used in conjunction with FriedelCrafts Acylation to prepare alkyl benzene products which could not be made directly by FriedelCrafts Alkylation. For example:
O H O Cl AlCl3

As was shown above, attempted synthesis of butylbenzene by reaction of benzene with chorobutane/AlCl3 is thwarted by carbocation rearrangement leading instead to sec-butylbenzene as the major product. The acylation/reduction sequence provides a way around this problem. Alkylbenzenes can also be prepared from aryl halides by coupling reactions (see Chapter 11, p.454460). For example:
Br + R Cu R M R + R Cu + M+ Br-

How Some Substituents on a Benzene Ring Can Be Chemically Changed

a) Benzylic Halogenation with NBS A benzylic hydrogen can be replaced with a halogen by radical substitution reactions described in Chapter 12 (p.484-487).
H X2 or h X = Cl or Br X H NBS or h Br

Chem 2261 Notes

Chemistry of Benzene and Its Derivatives

(Bruice, Chapter 15)

b) Conversion of Alkyl Groups or Benzylic Alcohols to Carboxyl Groups with Cr+6 or Mn+7 Reagents Methyl, primary alkyl, and secondary alkyl groups are converted to carboxyl (CO2H) groups by Cr+6 and Mn+7 oxidizing agents.
Me or R R R Mn+7 or Cr+6 reagent CO2H

or

KMnO4 and H+, Na2Cr2O7 are commonly used oxidizing agents

The first step in these oxidation reactions is the removal of a benzylic hydrogen, so tertiary alkyl groups are unaffected by Cr+6 and Mn+7 oxidizing agents.
R R tertiary alkyl group R Mn+7 or Cr+6 reagent

NO REACTION
R R

The same reagents will oxidize benzylic alcohols to benzoic acids.

OH R OH OH Mn+7 or Cr+6 reagent CO2H

or

or

c) Oxidation of Benzylic Alcohols to Ketones or Aldehydes with MnO2

H H OH MnO2 1 benzyl alcohol aldehyde 2 benzyl alcohol H O H R OH MnO2 ketone R O

d) Reduction of Nitro Groups to Amino Groups A nitro substituent can be reduced to an amino substituent. Either a metal (tin, iron, or zinc) pul an acid (HCl) or catalytic hydrogenation can be used to carry out this reaction.
NO2 1. Sn, HCl 2. NaOH NH2

H2 Pd/C