Documente Academic
Documente Profesional
Documente Cultură
August Kekulé
“In variably, my device works
as I imagined it should.
In twenty years there has not been
single exception.”
NIKOLA TESLA
“Imagination is more important
than knowledge.”
ALBERT EINSTEIN
AROMATIC COMPOUNDS
Introduction to
14.1
aromatic Compounds
Friedel-Craft acylation
electrophilic substitution
oxidation of
activating and alkylbenzene
deactivating group
substitution of
ortho-para and meta director toluene
DISCOVERY OF BENZENE
Empirical formula = CH
named “benzin”
H C H
C C
or
C C
H C H
H
equivalent to
resonance hybrid
Cyclic Planar
Conta
in par
numb ticula
er of r
m p l etely electr ∏
Co ed on
j ug a t ob
con eys H
RuleÜckel’s
THE CRITERIA FOR AROMATICITY
HÜckel’s Rule
* cyclic, planar and completely
conjugated compounds that
contain [4n+2] ∏ electron
(n=0,1,2…..) are said to be
aromatic
Erich HÜckel
(1896-1980)
Benzene
aromatic
Benzene is aromatic because:
contains 6∏ electrons
(obeys HÜckels Rule)
[4n+2] ∏ = [4(1) + 2]∏
cyclic, planar and has double
= 6 ∏ electrons
bond in the ring
THE CRITERIA FOR AROMATICITY
EXAMPLE
Aromatic
naphthalene
4n+2= 4(2)+ 2
10 ∏ electrons
Nomenclature of benzene
14.2
and its derivatives
EXAMPLE:
CH3
Common: toluene
IUPAC: methylbenzene
MONO SUBSTITUTED BENZENE
Benzene is the parent name and the substituent
is indicated by a prefix.
F Cl Br
NO2 CH2CH3
nitrobenzene ethylbenzene
IUPAC rules allow some common names
to be retained.
CH3 OH NH2
COOH CHO
1,2–dinitrobenzene 1,3–dinitrobenzene
or or
o–dinitrobenzene m–dinitrobenzene
NO2
1
2
3
4
NO2
1,4–dinitrobenzene
or
p–dinitrobenzene
DISUBSTITUTED BENZENE
Two Different Substituents
Cl
Br
1 2 Br Br
3 I
4
2–bromo–1–chloro–3–iodobenzene
Br
1,2,4–tribromobenzene
C atom bearing the subtituent that define the
new parent name is numbered as C1.
OH
COOH
1
2 NO2 1
6 2
3 5 3
4 OH
HO 4
NO2
3,5–dihydroxybenzoic acid
2,4–dinitrophenol
3
Br 4 2 CH3
1 CH3
4–bromo–1,2–dimethylbenzene
3
Br 4 2 CH3
1 CH3
4–bromo–1,2–dimethylbenzene correct
4–bromo–o–dimethylbenzene
1 CH2
3 4 5 6 7
2 CH–CH –CH2–CH2–CH2–CH3
2
2–phenylheptane
Phenyl = C6H5– = Ph
14.2-12
1 2 3 4 2 1
CH2–C C–CH3 CH2–CH2–OH
1–phenyl–2–butene 2–phenylethanol
14.2-13
BENZYL GROUP
CH2—
CH2Br CH2OH
Br2 / CCl4
no addition of Br2
(no decolorization)
Br
FeBr3
+ Br2
benzene bromobenzene
H2O
butylbenzene benzoic acid
14.3-04
ELECTROPHILIC SUBSTITUTION
Most characteristic reaction of benzene.
A H atom is replaced by an electrophile.
H E
+ E+ + H+
electrophile
14.3-05
X2, FeX3 X halogenatio
(X = Cl Br) + HX n
HONO2
NO2
nitratio
+ H2O n
H2SO4
O
O
RCCl , AlCl3 Friedel-
C–R Crafts
+ HCl Acylation
14.3-07
GENERAL MECHANISM
H H
H
H H H
E E E
H H H
+ H H H
+ +
H H H H H H
H H arenium ion H
14.3-08
ARENIUM ION
+
E+ E
H
H H
E
H H E
+ H
H H H H
H H
STEP 2 E
E
H + H+
+
14.3-11
HALOGENATION
Reactants: benzene and halogens (Cl2 or Br2).
Conditions:
Lewis acid such as FeCl3 and FeBr3
+ Br2 no reaction
(decolorization not observed)
Br
FeBr3
+ Br2 + HBr
bromobenzene
14.2-13
MECHANISM
STEP 1 Formation of Br+
δ + δ –
Br–Br + FeBr3 Br—Br–FeBr3 Br+ + FeBr4–
complex
STEP 3 Loss of H+
Br FeBr4– Br
H + HBr + FeBr3
+
14.3-14
FUNCTION OF LEWIS ACIDS
HNO3 NO2
H2SO4
nitrobenzene
+ H+ + HSO4–
12.5-49
MECHANISM
H2O + NO2+
nitronium ion
STEP 2 Formation of arenium ion
NO2
H
+ NO2+ +
STEP 3 Loss of H+
NO2 HSO 4
–
NO2
H + H2SO4
+
12.5-51
FRIEDEL–CRAFT ALKYLATION
Reactants: benzene and haloalkane.
Conditions:
Catalyst: Lewis acid such as AlCl3.
R
AlCl3
+ R–X + HCl
alkylbenzene
Alkylation = transfer an
alkyl group to benzene
12.5-52
12.5-53
EXAMPLE:
Cl
CH(CH3)2
AlCl3
+ CH3CHCH3 + HCl
2–chloropropane
isopropylbenzene
C(CH3)3
AlCl3
+ (CH3)3C–Cl + HCl
2–chloro–2–methylpropane
tert–butylbenzene
12.5-54
MECHANISM
STEP 1 Formation of carbocation
+ -
: :
: :
(CH3)2CHCl: + AlCl3 (CH3)2CH–Cl–AlCl3
(CH3)2CH+ + AlCl4–
carbocation
STEP 2 Formation of arenium ion
CH(CH3)2
H
+ +
CH(CH3)2 +
STEP 3 Loss of H+
AlCl4–
CH(CH3)2
CH(CH3)2
H
+ + HCl
OTHER FACTS ABOUT 12.5-55
FRIEDEL–CRAFT ALKYLATION
Rearrangement can occur, especially when
1o haloalkanes are used.
CH2CH2CH2CH3
EXAMPLE: 35
%
CH3CH2CH2CH2Cl butylbenzene
CH3
AlCl3 +
CHCH2CH3 65
%
Rearrangement: sec–butylbenzene
H
+ +
CH3—CH2—CH—CH2 CH3—CH2—CH—CH3
1o carbocation 2o carbocation
12.5-56
FRIEDEL–CRAFT ACYLATION
Reactants: benzene and acid chloride.
Product: ketone.
Conditions:
Catalyst: Lewis acid such as AlCl3.
EXAMPLE:
O
O
AlCl3 CCH3
+ CH3C—Cl + HCl
acetyl chloride
acetophenone
12.5-57
ACYL GROUP
O
RC—
acyl group
EXAMPLE:
O
O
–C—
CH3C—
acetyl group benzoyl group
Acylation = transfer an
acyl group to benzene
12.5-59
MECHANISM
STEP 1 Formation of acylium ion
:O: :O:
R–C–Cl + AlCl3 R–C–Cl–AlCl3
: :
R–C+═O R–C≡O+ + AlCl4–
acylium ion
Formation of arenium ion R
STEP 2
C=O
+ R–C+═O H
+
STEP 3 Loss of H+
R AlCl4– R
C=O
C═O
H
+ + HCl
12.5-61
SUBSTITUENT EFFECT
EXAMPLE:
NO2 Cl H OH
relative rate
6 x 10–8 0.033 1 1000
of nitration
reactivity
12.5-63
EFFECT ON ORIENTATION
Ortho–para directors
Tend to direct the incoming group into
ortho and para positions.
Meta directors
Tend to direct the incoming group into
meta position.
EXAMPLE: ortho-para director
CH3 CH3 CH3 CH3
HNO3 NO2
+ +
H2SO4 NO2
(59 (37 (4
%)
NO2
%) %)
12.5-64
CLASSIFICATION OF SUBSTITUENTS
DIRECTING ACTIVATORS
Increasing activation
●● ●● ●●
—NH2 —NHR —NR2
●●
—OH
●●
●● General
—OR structure: ●
●●
—R or —Z●
●●
—NHCOR
Alkyl groups or have
nonbonded electron pair
—R on the atom bonded to
benzene ring
12.5-66
EXAMPLE:
DIRECTING DEACTIVATORS
●● ●●
—F ●
● —Cl●
●
●● ●●
●● ●●
—Br●● — I●
●
●● ●●
General structure
●●
—X ●
● (halogens)
●●
12.5-68
EXAMPLE:
Cl Cl Cl
NO2
HNO3
+
H2SO4
(35 (64
chlorobenzene %) %) NO2
12.5-69
META– DIRECTING ACTIVATORS
—CHO
—COR
General
—COOR
structure:
—COOH —Y (δ + or δ –)
—CN
Have a full or partial
—SO3H positive charge on the
atom bonded to
—NO2 benzene ring
+
—NR3
Increasing deactivation
12.5-69
EXAMPLE:
NO2
NO2
HNO3
H2SO4
NO2
nitrobenzene (93
%)
12.5-70
INDUCTIVE EFFECT
Due to:
Electronegativity of the atoms in the
substituent.
Polarisability of the substituent.
EXAMPLE:
Cl CH3
Cl— CH3—
electron–withdrawing electron–donating
12.5-71
Activating Groups
CH3
Release electrons to the ring NO2
Deactivating Groups
Cl
Withdraw electrons from the ring NO2
CF3 CH3
NO2 NO2
NO2
+ +
+
benzylic H
CH3
CH3 CH(CH3)2
EXAMPLE: 12.5-76
CH3 COOH
KMnO4
heat
toluene benzoic acid
Na2Cr2O7
O2 N CH3 O2 N COOH
heat
p–nitrotoluene p–nitrobenzoic acid
KMnO4
CH3 CH(CH3)2 HOOC COOH
heat
isopropyl toluene terepththalic acid
12.5-77
KMnO4
CH3 CH(CH3)2 HOOC COOH
heat
KMnO4
CH3 C(CH3)3 HOOC C(CH3)3
heat
12.5-78
HALOGENATION OF TOLUENE
EXAMPLE: (dichloromethyl)benzene
CH3 CH2Cl CHCl2 CCl3
Cl2 Cl2 Cl2
heat or heat or heat or
light light light
toluene benzyl chloride (trichloromethyl)benzene
HALOGENATION OF TOLUENE
CH3
CH3
CH3
Br2 Br2 +
FeBr3
toluene Br2
●
CH2 12.5-79
benzylic
radical
benzene toluene
benzo[a]pyrene