BAB 10

Benzena dan aromatisitas;

Substitusi elektrofilik aromatis
 Outline
Nomenklatur Turunan Benzena
Kestabilan cincin benzena
Aromatis dan persyaratannya
Substitusi Aromatis Elektrofilik
Gugus pemberi vs. penarik elektron
Pengarah orto/para vs. meta
Pengaktif vs. Pendeaktif
Reaksi rantai samping turunan benzena
 Senyawa Aromatis

• Aromatis pada awal abad ke 19 digunakan untuk

menjelaskan beberapa senyawa parfum

• Sekarang dikelompokkan sebagai sifat kimia

(senyawa takjenuh yang mengalami reaksi
substitusi daripada adisi).

• They are distinguished from aliphatic compounds

by electronic configuration.
 A LOT OF NICE-SMELLING COMPOUNDS
(SPICES IN PARTICULAR) HAVE BENZENE RINGS
cinnamaldehyde
(cinnamon)
CHO HC CH CHO thymol
anisaldehyde (thyme)
(anise)
OH

OMe OH CHO
OMe
eugenol cuminaldehyde
(cloves) (cumin)

CH2 CH CH2

Hence, compounds having benzene rings eventually came

to be know as “AROMATIC COMPOUNDS.

Today chemists have a different definition of “AROMATIC”

which we will discuss later in the chapter.
Nomenklatur Turunan Benzena

Benzena adalah nama induk untuk beberapa

benzena monosubstitusi; nama substituen
ditambahkan sebagai awalan
 SOME SPECIAL NAMES
CH3 NH2 O CH3 OH COCH
COOH 3

toluene aniline anisole phenol Acetophenone

CH3 CH3 CH3 COOH

CH3

CH3
o-xylene m-xylene CH3 benzoic
acid
p-xylene
 ortho, meta and para Positions
CH3

m-nitrotoluene
R 3-nitrotoluene
NO2
1
o- 6 2 ortho 1-methyl-3-nitrobenzene

meta Cl
m-
5 3
4
para p-dichlorobenzene
p-
1,4-dichlorobenzene
Cl
 Learn Nomenclature Either on Your Own

Br
CH3
methylbenzene
(toluene)
NO2

1-bromo-3-nitrobenzene
CH3 CH3

Cl (p-xylene)

1-chloro-3-methylbenzene CH3

1,4-dimethylbenzene
– Bila lebih dari dua substituen, harus digunakan
penomeran
– Nomor substituen harus serendah mungkin
– Substituen harus dituliskan secara alfabetis
– Jika satu susbtituen digunakan untuk nama induk benzena, maka
substituen tersebut berada pada posisi 1.
• Gugus C6H5- sbg substituen
• Fenil disingkat sebagai Ph atau ø
• Hidrokarbon dengan rantai jenuh dan cincin benzena
diberinama berdasarkan stuktur unit yang terbesar sebagai
nama induknya
• Jika rantainya tidak jenuh, maka rantai ini sebagai nama
induknya dan benzena sebagai substituen.

• Gugus fenilmetil disebut: benzil

 Struktur Benzene yg spesifik
• All its C-C bonds are the same length: 139 pm
between single (154 pm) and double (134 pm) bonds
• Electron density in all six C-C bonds is identical
• Structure is planar, hexagonal with C–C–C bond angles 120°
• Each C is sp2 and has a p orbital perpendicular to the plane
of the six-membered ring
BENZENE - DETERMINATION OF RESONANCE ENERGY
RE sbg Indikator kestabilan
cyclohexatriene
(hypothetical)

+ 3 H2

benzene

RESONANCE
cyclohexene + 3 H2 ENERGY
36 kcal/mol
+ H2
-49.8 kcal/mol
-85.8 kcal/mol
(calculated)
-28.6 kcal/mol

cyclohexane
• Teori Modern pada Struktur Benzena
– Penjelasan Resonansi pada struktur Benzena
• Struktur I dan II merupakan kontributor resonansi yang sama
terhadap struktur benzena yang sesungguhnya
• Benzena sangat stabil karena memiliki dua struktur ekuivalen yang
sama dan merupakan resonansi yang penting
• Setiap ikatan C-C adalah 1.39Å, meskipun ikatan C–C sp2 adalah
1.47Å dan C=C adalah 1.33 Å
• Hibrid ini sering dinyatakan sebagai lingkaran segienam (III)
• Penjelasan Orbital Molekul pd struktur Benzena
• C pada benzena mempunyai hibridasi sp2 dengan orbital p pada
keenam atom C (a)
• The p orbitals overlap around the ring (b) to form a bonding
molecular orbital with electron density above and below the plane
of the ring (c)

• There are six p molecular orbitals for benzene

 AROMATICITY
QUESTION:
Are all fully-conjugated, cyclic systems aromatic?
36 kcal/mole RE

? ? ?

KNOWN
AROMATIC H H
H H

H H
HHH
? ?
HH H
H H

Do these other rings have the H H

same kind of stability as benzene? H H
 AROMATICITY
..
HUCKEL 4n+2 RULE
Prediction: Compounds that have 4n+2 pi electrons in
a cyclic array will be aromatic.

4n+2 series = 2, 6, 10, 14, 18, 22, 26, 30 …….. etc.

The rule was derived by observation of
POLYCYCLIC AROMATIC COMPOUNDS

6 10 14

benzene naphthalene anthracene

14 18
 kriteria untuk Aromatisitas

1. Sistem harus siklis

2. Sistem harus planar (flat)
3. Setiap atom pada cincin harus menjadi bagian
dari sistem pi yang diperpanjang
4. Sistem pi yang diperpanjang harus mempunyai
jumlah elektron pi yang sesuai dengan hukum
Huckel (4n+2)
Aromatic Compounds Have Special Properties

Aromatic compounds:

1) Must be cyclic and fully conjugated

2) Must have 4n+2 p electrons in the system
3) Must have the entire system planar
4) Will have no unpaired electrons in
the p system molecular orbitals
planar
Characteristic Properties: system
1) Special chemical stability

2) Give substitution reactions instead of addition

3) Show a ring currrent in the NMR

(Chapter 13, Section 13.8)
 Ring Current in Benzene

Circulating p electrons

Deshielded
H H
A proton placed in the
middle of the ring would
be shielded!

Bo Secondary magnetic field

generated by circulating p
electrons deshields aromatic
protons
 Struktur dan Kestabilan Benzena
• Benzena bereaksi lambat dengan Br2 menghasilkan
bromobenzena (dimana Br menggantikan H)

• Reaksi substitusi lebih umum terjadi daripada adisi yang umum

terjadi pada senyawa mengandung gugus C=C, menunjukkan
bahwa benzena memiliki energi halangan yang besar
 The “Double Bonds” in a Benzene Ring Do Not React Like Others

Alkene Benzene

R R Cl
no
+ HCl + HCl reaction
H

R R Cl no
+ Cl2 + Cl2 reaction
Cl

R R Br
no
+ Br2 + Br2
reaction
Br

R R O
+ RCO3H no
+ RCO3H reaction
 Benzene is a Weak Base and Poor Nucleophile

Stronger + Readily donates electrons

base H to an electrophile.

alkene

Weaker + Donation of electrons would

base
H interrupt ring resonance
(36 kcal / mole).

A strong electrophile is
benzene required - and often a
catalyst.
 Benzene Reactivity
Benzene requires a strong electrophile and a catalyst
…..and then it undergoes substitution reactions, not addition.

Cl
FeCl3
+ Cl2 + HCl

catalyst substitution
compare:

Cl
+ Cl2
Cl
no catalyst addition
Electrophilic Aromatic Substitution

• Halogenasi
• Nitrasi
• Alkilasi Friedel-Crafts
• Asilasi Friedel-Crafts
• Sulfonation
 MECHANISM
All of the reactions follow the same pattern of mechanism.
The reagents combine to form a strong electrophile E+ ,and
its partner (:X ), which react as follows:

ELECTROPHILIC AROMATIC SUBSTITUTION

(+) E
H E
E+ H + HX
slow (+) +
:X
intermediate
benzenium ion* restores
ring resonance
resonance structures are shown
by the (+) symbols

* also called a benzenonium ion

ENERGY PROFILE FOR AROMATIC SUBSTITUTION
(+) E
Transition benzenium
H
state 1 + intermediate
(+)

Transition
state 2

intermediate

Ea
activation
H energy
E
E+ +
H

slow fast
STEP 1 STEP 2
HALOGENATION
Formation of the Chloronium Ion Complex

.. ..
: Cl :
..d+ ..
: Cl :
.. .. .. d- ..
: Cl
.. Cl :
.. Al Cl : : Cl Cl Al Cl :
.. .. .. ..
: Cl : : Cl :
.. ..

Cl sp2 ..
Al Cl : Cl :
.. + .. - ..
:Cl : Cl
..
Al Cl :
..
..
: Cl :
Cl ..
chloronium
ion complex
Chlorination of Benzene

AlCl4-
H
Cl2 + AlCl3
Cl
+ - +
[ Cl AlCl4 ]
benzenium
ion

chloronium
ion complex Cl
+ HAlCl4

HCl + AlCl3
Formation of a Carbocation Complex

.. ..
: Cl : d+ : Cl :
.. .. .. d- ..
CH3 Cl : Al Cl: CH3 Cl Al Cl :
.. .. .. ..
: Cl : : Cl :
.. ..

Other aliphatic
R-Cl may be used ..
: Cl :
+ .. - ..
CH3 : Cl Al Cl :
.. ..
: Cl
..
:
carbocation
Friedel-Crafts Alkylation
-
AlCl4
H
CH3Cl + AlCl3
CH3
[ CH+3 AlCl4- ] +

CH3
+ HAlCl4

HCl + AlCl3
REARRANGEMENTS ARE COMMON IN
FRIEDEL-CRAFTS ALKYLATION

AlCl3 + -
CH3CH2CH2 Cl CH3CH2CH2 Cl AlCl3

H3C + -
CH Cl AlCl3
H3C
carbocation rearrangement

CH3

AlCl3 CH
+ CH3CH2CH2 Cl CH3
Formation of an Acylonium Complex

O .. ..
: Cl : O : Cl :
.. .. d+ .. d- ..
CH3 C Cl : Al Cl: CH3 C Cl Al Cl :
.. .. .. ..
: Cl : : Cl :
.. ..

Other acid chlorides ..

(RCOCl) may be used O : Cl :
.. - ..
CH3 C : Cl
..
Al Cl :
..
+
: Cl
..
:
acylium ion
(acylonium ion)
Rearrangements DO NOT occur
Friedel-Crafts Acylation
-
AlCl4
O H
CH3 C Cl + AlCl
3
C CH3
AlCl4- ]
+
[ CH3 C +
O
O

C CH3
O
+ HAlCl4

HCl + AlCl3
 Formation of Nitronium Ion

.. .. ..
O:
.. + O:
H2SO4 ..+ + O: ..
H O N H O N H O: N+
..
: O: H : ..
O:
.. :
.. - H O
-
nitronium ion

..
:O
Powerful
N+ Electrophile

Reacts with benzene.

: ..
O
Nitration of Benzene
H

H :O
.. H
..
:O HNO3 + ..
N O:
N+ +
H2SO4 :O
..: -
: O..

..
:O
N ..
.. :
+ O
-
Fuming Sulfuric Acid
H2SO4. SO3

.. ..
O: H2SO4 O:
.. - ..
+ S O: +S O H
.. ..
O: O:
.. ..
sulfur
trioxide
Sulfonation of Benzene
-
HSO4
H
H2SO4. SO3
O
O
S OH
+S OH O
O

H3O+
can be D O
reversed
in boiling water S OH
or steam (acidic) O
+ H2SO4
REMOVAL OF THE SULFONATE GROUP

O O H O
S OH H S O-
+
O O H O H
heat or steam
H
excess H2O

H
H O
O
S O -
+S O-
O
O

H2O

H2SO4