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Nuryanti, M.

Si

Reaksi Senyawa
Aromatik
Benzene and its Derivatives
History of Benzene
• Michael Faraday isolated a compound from coal gas
(1825) with the molecular formula C6H6
• Although very unsaturated, the compound was quite
unreactive: no reaction

KMnO4

Br2
C6H6 no reaction

H2 , 1 atm

Pt
no reaction
Unusual Reactions
• Alkene + KMnO4  diol (addition)
Benzene + KMnO4  no reaction.
• Alkene + Br2/CCl4  dibromide (addition)
Benzene + Br2/CCl4  no reaction.
• With FeCl3 catalyst, Br2 reacts with
benzene to form bromobenzene + HBr
(substitution!). Double bonds remain.
Electrophilic Aromatic Substitution

4
Reactions of Benzene
• The most characteristic reaction of aromatic
compounds is substitution at a ring carbon.
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
• Other functional groups that can be added to the
benzene ring is the sulfonyl group, and alkyl
group and an acyl group.
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


Mechanism
Step 1: Attack on the electrophile forms the sigma complex.

Step 2: Loss of a proton gives the substitution product.

Chapter 17 9
Bromination of Benzene
• Requires a stronger electrophile than Br2.
• Use a strong Lewis acid catalyst, FeBr3.
+ -
Br Br FeBr3 Br Br FeBr3
H
H H
H
H H + - _
Br
Br Br FeBr3 + + FeBr4
H H
H H
H
H

Br
+ HBr

Chapter 17 10
Brominasi benzen
Diagram energi

Keadaan
transisi

Pereaksi
Energi

Intermediet Produk

=
Koordinat reaksi >
Klorinasi dan Iodinasi
• Klorinasi serupa dengan brominasi. Katalis yang digunakan AlCl3.

• Iodinasi membutuhkan agen pengoksidasi asam, seperti asam nitat,


yang akan mengoksidasi iodin menjadi ion I+.

+ +
H + HNO3 + 1/2 I2 I + NO2 + H2O
Chlorination and Bromination
• Step 1: Formation of the electrophile (a
chloronium ion).
• Fe3+ (a Lewis acid) reacts with chlorine (a Lewis base) to
induce the formation of Cl+, the chloronium ion.
• Step 2: Reaction of the electrophile (the
chloronium ion and a nucleophile to form a new
covalent bond.

• Step 3: Proton transfer to FeCl4– forms HCl,


regenerates the Lewis acid catalyst, and gives
chlorobenzene.
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
Nitration
• The electrophile, NO2+, is generated in two steps.
• Step 1: Add a proton (from a strong acid like sulfuric acid) to
nitric acid to make water as a leaving group.

• Step 2: Water breaks off forming the nitronium ion, NO2+.

• Finish reaction by having NO2+ use pi electrons to


create new bond and have proton transfer back into
solution.
Nitrasi Benzen
Elektrofil

Untuk membentuk elektrofil ion NO2+digunakan H2SO4 dengan HNO3.

O O H O
_
H O S O H H O N H O N + HSO4
+
O O O

H O O
H O N H2O + N+
+
O O
E+
Nitrasi Benzen
Mekanisme
Nitronium-cation
+
HNO3 + H2SO4 NO2 + HSO4- + H2O
H

Proceeds through a -complex

O2N O2N O2N


+ H H O2N
-H H
+
CH +
HC
+
CH
Nitration of Toluene
• Toluene reacts 25 times faster than benzene.
The methyl group is an activating group.
• The product mix contains mostly ortho and para
substituted molecules.

Chapter 17 21
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
-
Sigma Complex

Intermediate is
more stable if
nitration
occurs at the
ortho
or para
position.

=>

Chapter 17 24
Substitution on Anisole

Chapter 17 25
The Amino Group
Aniline, like anisole, reacts with bromine water
(without a catalyst) to yield the tribromide.
Sodium bicarbonate is added to neutralize
the HBr that’s also formed.

Chapter 17 26
Summary of Activators

Chapter 17 27
• For ortho-para directors, ortho-para attack forms a
more stable cation than meta attack.
• Also, ortho-para products are formed faster than meta
products.
• -OCH3 is ortho-para directing.
• For meta directors, meta attack forms a more stable
cation than ortho-para attack.
• Also, meta products are formed faster than ortho-para
products.
• -NO2 is meta directing.
Ortho Substitutionon Nitrobenzene

Chapter 17 30
Para Substitution on Nitrobenzene

Chapter 17 31
Meta Substitution on Nitrobenzene

Chapter 17 32
• Note that activating (and ortho/para) directors
have lone pairs that can participate in resonance
structures.
Summary of Deactivators

Chapter 17 34
More Deactivators

Chapter 17 35
Sigma Complex for Bromobenzene

Ortho and para attacks produce a bromonium ion


and other resonance structures.

No bromonium ion
possible with meta attack.

Chapter 17 36
Summary of Directing Effects

Chapter 17 37
• In a multi-step synthesis, the order of steps is crucial.
Multiple Substituents
The most strongly activating substituent will
determine the position of the next
substitution. May have mixtures.
OCH3 OCH3 OCH3
SO3H
SO3
+
H2SO4
O2N O2N O2N
SO3H

Chapter 17 39
Catalytic Hydrogenation
• Elevated heat and pressure are required.
• Possible catalysts: Pt, Pd, Ni, Ru, Rh.
• Reduction cannot be stopped at an
intermediate stage.
CH3 CH3

3 H2, 1000 psi


Ru, 100°C
CH3 CH3

Chapter 17 40
Side-Chain Oxidation
Alkylbenzenes are oxidized to benzoic acid by
hot KMnO4 or Na2Cr2O7/H2SO4.
_
CH(CH3)2 COO
-
KMnO4, OH
_
H2O, heat COO
CH CH2

Chapter 17 41
Benzylic Oxidation
• Benzene is unaffected by strong oxidizing
agents such as H2CrO4 and KMnO4.
• The benzylic hydrogens are quite acidic.
• An alkyl group with at least one hydrogen on the
benzylic carbon is oxidized to a carboxyl group (and
thus a benzoic acid).
• Halogen and nitro substituents are unaffected by
these reagents.
• If there is more than one one-carbon branch,
each is oxidized to a -COOH group.

• Terephthalic acid is one of the two monomers


required for the synthesis of poly(ethylene
terephthalate) (recycling code 1), a polymer that
can be fabricated into Dacron polyester fibers,
Mylar films as well as soda bottles.
Side-Chain Halogenation
• Benzylic position is the most reactive.
• Chlorination is not as selective as
bromination, results in mixtures.
• Br2 reacts only at the benzylic position.
Br
CH2CH2CH3 CHCH2CH3
Br2, h

Chapter 17 44
Sulfonation
• The electrophile, HSO3+, is generated in two steps.
• Step 1: Add a proton (one molecule of sulfuric acid protonates
another sulfuric acid) to make water as a leaving group.

• Step 2: Water breaks off forming the sulfonium ion, HSO3+.


• HSO3+ attacks pi electrons in aromatic ring to create
new bond.
• Proton on ring is transferred back into solution.

benzenesulfonic acid

• Sulfonic acids are very acidic (like sulfuric acid).


• The conjugate bases (sulfonates) are used in detergents.
Sulfonasi
Mekanisme

Gunakan SO3 dan asam sulfat berasap untuk menghasilkan ion HSO3+

+
SO3 + H2SO4 HSO 3 + HSO4-
H

Proceeds through a -complex

HO 3S HO 3S HO 3S
+ H H HO 3S
-H H
+
CH +
HC
+
CH
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
Nitrasi Toluena
Mekanisme dan Sigma kompleks
serangan pada posisi orto

3o lebih Intermediat lebih


disukasi
serangan pada posisi para stabil jika nitrasi
terjadi pada posisi
orto atau para

3o lebih
serangan pada posisi meta disukasi
Nitrasi Toluena
Diagram
Energi
Subtitusi Pada Nitrobenzen
• Nitrobenzen bereaksi 100.000 kali lebih lambat dibanding benzen.
• Gugus metil berperan sebagai pendeaktivasi.
• Campuran produk mengandung molekul disubtitusi dengan posisi meta
lebih banyak.
• Subtituen pendeaktivasi mendeaktivasi pada semua posisi, tetapi posisi
meta kurang dideaktivasi.
Subtitusi Pada Nitrobenzen
serangan pada posisi
Mekanisme orto
dan Sigma
kompleks

sangat tidak stabil

serangan pada posisi


para

sangat tidak stabil

serangan pada posisi


meta
Subtitusi Pada Nitrobenzen
Diagram
Energi
Substitusi Nukleofilik Aromatis
• Nukleofilik mengganti gugus pergi pada cincin aromatis.
• Subtituen penarik elektron akan mengaktivasi cincin terhadap subtitusi
nukleofilik.
Contoh :
Mekanisme Subtitusi Nukleofilik
Tahap 1. Serangan Nu- (OH-) memberikan sigma yang distabilkan
resonansi

Tahap 2. Lepasnya Nu- (Cl-) memberikan produk