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
anisaldehyde
(anise)

thymol

HC CH CHO

(thyme)

OH

OMe

CHO

OH
OMe

eugenol
(cloves)

cuminaldehyde
(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

toluene

aniline

CH3

O CH3

anisole

phenol

CH3

CH3

COCH
COOH 3

OH

Acetophenone

COOH

CH3
CH3

o-xylene

m-xylene

CH3
p-xylene

benzoic
acid

ortho, meta and para Positions

CH3

m-nitrotoluene
3-nitrotoluene

R
o-

m-

NO2

1
6

ortho
meta

1-methyl-3-nitrobenzene

Cl

3
4

para

p-dichlorobenzene

p-

Cl

1,4-dichlorobenzene

Learn Nomenclature Either on Your Own

Br

CH3
methylbenzene
(toluene)

NO2

1-bromo-3-nitrobenzene

CH3

CH3

(p-xylene)

Cl
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
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.

(Bz)

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 CCC 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
cyclohexene

+ 3 H2

+ H2

RESONANCE
ENERGY
36 kcal/mol

-49.8 kcal/mol
-28.6 kcal/mol

cyclohexane

-85.8 kcal/mol
(calculated)

 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 1.39, meskipun ikatan CC sp 2
adalah 1.47 dan C=C adalah 1.33
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

HHH

HH H

H
Do these other rings have the
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

benzene

14

naphthalene

14
anthracene

18

kriteria
kriteria untuk
untuk Aromatisitas
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

Aromatic Compounds Have Special Properties

Aromatic compounds:
1) Must be cyclic and fully conjugated
2) Must have 4n+2

electrons in the system

3) Must have the entire system planar

4) Will have no unpaired electrons in
the

system molecular orbitals

Characteristic Properties:
1) Special chemical stability
2) Give substitution reactions instead of addition
3) Show a ring currrent in the NMR
(Chapter 13, Section 13.8)

planar
system

Ring Current in Benzene

Circulating

electrons

Deshielded

A proton placed in the

middle of the ring would
be shielded!
Bo

Secondary magnetic field

generated by circulating
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
R

Benzene
R Cl

+ HCl

+ HCl

no
reaction

+ Cl2

no
reaction

H
R Cl

Cl2
Cl

R Br

Br2

Br2

Br
R

+RCO3H

+ RCO3H

no
reaction

no
reaction

Benzene is a Weak Base and Poor Nucleophile

Stronger
base

Readily donates electrons

to an electrophile.

Donation of electrons would

interrupt ring resonance
(36 kcal / mole).

alkene

Weaker
base

H
benzene

A strong electrophile is
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
substitution

catalyst
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+

slow

(+)

E
H

+ HX

+
: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
state 1

(+)

benzenium
intermediate

Transition
state 2
intermediate
Ea
activation
energy

H
E+

H
slow
STEP 1

fast
STEP 2

HALOGENATION

Formation of the Chloronium Ion Complex

..

..

..
: Cl
..

..
Cl :
..

Cl

Al

: Cl :
..

..
Cl :
..

sp2

Al
Cl

: Cl :

Cl
chloronium
ion complex

.. ..
Cl
: Cl
..
..

: Cl :
..

Al Cl :
..
: Cl :
..

..

: Cl :
..
.. + .. Al Cl :
: Cl : Cl
..
..
..
:
: Cl
..

Chlorination of Benzene
AlCl4-

Cl2 + AlCl3

+
[ Cl AlCl4 ]

chloronium
ion complex

Cl

benzenium
ion

Cl

+ HAlCl4

HCl + AlCl3

Formation of a Carbocation Complex

..

..

..
CH3 Cl :
..

: Cl :
Al

: Cl :
..

..
Cl:
..

Other aliphatic
R-Cl may be used

CH3

: Cl :
..
..
Cl
Al Cl :
..
..
: Cl :
..

..

carbocation

: Cl :
.. ..
+
CH3 : Cl Al Cl :
..
..
:
: Cl
..

Friedel-Crafts Alkylation
-

AlCl4

CH3Cl + AlCl3

-]
[ CH+
AlCl
3
4

CH3

CH3

+ HAlCl4
HCl + AlCl3

REARRANGEMENTS ARE COMMON IN

FRIEDEL-CRAFTS ALKYLATION
AlCl3

CH3CH2CH2

CH3CH2CH2 Cl

Cl

H3C
H3C

CH

AlCl3

Cl

AlCl3

carbocation rearrangement
CH3
+ CH3CH2CH2

Cl

AlCl3

CH
CH3

Formation of an Acylonium Complex

..

O
CH3 C

..
Cl :
..

: Cl :
Al

: Cl :
..

..
Cl:
..

Other acid chlorides

(RCOCl) may be used

CH3 C

O
CH3 C

acylium ion

..

: Cl :
..
..
Cl Al Cl :
..
..
: Cl :
..

..

: Cl :
.. ..
Al Cl :
: Cl
..
..
:
: Cl
..

(acylonium ion)

Rearrangements DO NOT occur

Friedel-Crafts Acylation
-

CH3 C Cl + AlCl
3

+
[ CH3 C
AlCl4- ]

AlCl4

C CH3
O

C CH3
O

+ HAlCl4
HCl + AlCl3

Formation of Nitronium Ion

..
O:

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

..

..

..+ + O :
H O N
H :O:

.. -

..

H O:
H

O:
N+
O:

..

nitronium ion

..

:O
N+

:O
..

Powerful
Electrophile
Reacts with benzene.

Nitration of Benzene
H

..

:O

N+

: O..

:O
.. H
+ ..
N O:
+
:O
..: H

HNO3
H2SO4

..

:O

N ..
+O
.. :

Fuming Sulfuric Acid

H2SO4 . SO3

..

O:

.. + S O:
..
O:
..

sulfur
trioxide

H2SO4

..

O:

..
+S O H
..
O:
..

Sulfonation of Benzene
-

HSO4
O
+S
O

H2SO4 . SO3

OH

H3O+

can be
reversed
in boiling water
or steam (acidic)

O
S OH
O

O
S OH
O
+ H2SO4

REMOVAL OF THE SULFONATE GROUP

O

O H

S OH

heat or steam

S O+
H
O
H
O
H

excess H2O
H

H
O

+S

O-

O
H2O
H2SO4

O
S O
O