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)

HC CH CHO
OH

thymol (thyme)

OMe

OH OMe
eugenol (cloves)

CHO
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 CH3 NH2
O CH3

OH

COCH3 COOH

toluene

aniline
CH3

anisole

phenol

Acetophenone

CH3 CH3

CH3

COOH

CH3

o-xylene

m-xylene

CH3
p-xylene

benzoic acid

ortho, meta and para Positions

CH3

R
1

m-nitrotoluene 3-nitrotoluene
NO2
2

o-

ortho meta

1-methyl-3-nitrobenzene

m5 4 3

Cl

para

p-

p-dichlorobenzene

1,4-dichlorobenzene

Cl

Learn Nomenclature Either on Your Own

CH3
methylbenzene (toluene)

Br

NO2

1-bromo-3-nitrobenzene

CH3

CH3

Cl
1-chloro-3-methylbenzene

(p-xylene)

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.

Gugus fenilmetil disebut: benzil (Bz)

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)
+ 3H2

benzene cyclohexene
+ H2
+ 3H2

RESONANCE ENERGY 36 kcal/mol

-49.8 kcal/mol -28.6 kcal/mol -85.8 kcal/mol (calculated)

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 1.39, meskipun ikatan CC sp2 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 H H H

H H H H

?
H
Do these other rings have the same kind of stability as benzene?

.. 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 benzene 10 naphthalene 14 anthracene

AROMATICITY

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

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 p electrons Deshielded

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
R R Cl

Benzene

+ HCl
H

+ HCl
R Cl

no reaction
no reaction

Cl2 Cl

+ Cl2
R Br

Br2 Br

Br2

no reaction

+ RCO3H

+ RCO3H

no reaction

Benzene is a Weak Base and Poor Nucleophile

Stronger base

H
alkene

Readily donates electrons to an electrophile.

Weaker base

H
benzene

Donation of electrons would interrupt ring resonance (36 kcal / mole). 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
+

Cl2

FeCl3
catalyst

+ HCl
substitution

compare:

Cl2
no catalyst

Cl Cl
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

H E+
slow

(+) E

E H
+ HX
:X

(+)

intermediate benzenium ion* resonance structures are shown by the (+) symbols

restores ring resonance

* also called a benzenonium ion

ENERGY PROFILE FOR AROMATIC SUBSTITUTION

(+) E Transition state 1
H

(+)

benzenium intermediate

Transition state 2

intermediate Ea activation energy

E+
E

H slow STEP 1 fast STEP 2

HALOGENATION

Formation of the Chloronium Ion Complex

..

.. .. Cl : ..
..d+ .. Cl : Cl .. .. : Cl : .. dAl Cl : .. : Cl : ..

.. : Cl ..

.. Cl : ..

: Cl :
Al

: Cl : ..

Cl Al Cl

sp2

Cl
chloronium ion complex

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

..

Chlorination of Benzene
H

AlCl4
Cl

Cl2 + AlCl3

+ [ Cl AlCl4 ]

benzenium ion

chloronium ion complex

Cl

+ HAlCl4

HCl + AlCl3

Formation of a Carbocation Complex

..

.. .. Cl: ..
d+
CH3

.. CH3 Cl : ..

: Cl :
Al

: Cl : ..
Other aliphatic R-Cl may be used

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

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

..

Friedel-Crafts Alkylation
H AlCl4 CH3

CH3Cl + AlCl3
[ CH+ AlCl4- ] 3 +

CH3

+ HAlCl4
HCl + AlCl3

REARRANGEMENTS ARE COMMON IN FRIEDEL-CRAFTS ALKYLATION

AlCl3
+

CH3CH2CH2

Cl

CH3CH2CH2 Cl H3C H3C

+

AlCl3
-

CH

Cl

AlCl3

carbocation rearrangement
CH3
+ CH3CH2CH2

Cl

AlCl3

CH CH3

Formation of an Acylonium Complex

O CH3 C

.. Cl : ..

: Cl :
Al

..

.. .. Cl : ..
CH3 C

d+

: Cl : ..

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

Other acid chlorides (RCOCl) may be used

O CH3 C
+

acylium ion
(acylonium ion)

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

..

Rearrangements DO NOT occur

Friedel-Crafts Acylation
O CH3 C Cl + AlCl 3

AlCl4 C CH3 O

+ [ CH3 C AlCl4 ]
O

C CH3 O

+ HAlCl4 HCl + AlCl3

Formation of Nitronium Ion

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

..

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

..

..
H O: H

..

O: N+ O

.. :
nitronium ion

:O
N+
Powerful Electrophile
Reacts with benzene.

..

: .. O

Nitration of Benzene
H

:O

..

HNO3 H2SO4

N+

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

:O .. :O ..

N .. + O: ..

Fuming Sulfuric Acid

H2SO4 . SO3

.. + S O: .. O: ..
sulfur trioxide

O:

..

H2SO4

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

O:

..

Sulfonation of Benzene
HSO4 O
+S H2SO4 . SO3

O S OH O

OH

O
H3O+ D

can be reversed in boiling water or steam (acidic)

O S OH O
+ H2SO4

REMOVAL OF THE SULFONATE GROUP

O S OH O O H H O S O+ H O H O H

heat or steam

excess H2O
H H O OO S O O

+S
O

H2O H2SO4