hidrokarbon rantai

hidrokarbon rantai tertutup, berbentuk

terbuka cincin

Contoh senyawa hidrokarbon alisiklik Contoh hidrokarbon aromatik

Hidrokarbon aromatik :
Senyawa siklik karbon dan hidrogen yang memiliki
ikatan tak jenuh.
Rumus umum : CnHn

Cincin benzen
 benzen merupakan contoh sederhana senyawa aromatik
 fasanya cair, titik didih 80o C
 diisolasi pertama kali : 1825 oleh Michael Faraday
 strukturnya merupakan “teka-teki” bagi ahli kimia,
R.M : C6H6
 memiliki ikatan rangkap tetapi TIDAK menunjukkan
reaktivitas seperti alkena
 struktur yang diajukan August Kekule (1829 – 1896) :
 H
Oleh karena benzen TIDAK H H
bereaksi seperti alkena
maka ikatan rangkapnya H H

mempunyai karakter yang H

berbeda
Struktur Kekule tidak
sepenuhnya tepat ! H

-
C
H- C C-H
O atau O
Struktur baru yang diajukan H- C
C
C-H

:
-
H

delokalisasi elektron
Penamaan Senyawa Aromatik
1. Menurut aturan IUPAC :
Bila sebuah H diganti oleh atom/gugus lain, diberi nama
sebagai turunan benzen :
CH2CH3 NO3 Br Cl

etilbenzen nitrobenzen bromobenzen klorobenzen

2. Beberapa nama umum yang diadopsi dari sistem IUPAC :

CH3 OH COOH NH2

toluen fenol asam benzoat anilin

3. Jika terdapat lebih dari 1 substituen, dilakukan penomoran
(jumlahnya serendah mungkin), diurutkan secara alfabet
CH3 CH3 CH3

1 CH3
1 2

3
Cl 4 Cl

CH3

1-bromo-3-kloro benzen 1,2,4-trimetil benzen 3,5-dikloro toluen

atau 2,4-dimetil toluen

4. Jika hanya 2 substituen, dapat diberi awalan orto-, meta-,

para- Br
Br
Br
1 Br
2 1 1

3
Br 4

Br
o-dibromo benzen m-dibromo benzen p-dibromo benzen
5. Benzen sebagai substituen fenil :

CH3

CH2 CH3

fenil benzil p-tolil o-tolil

1 2 3 4 5
CH3CH2CHCH2CH3

CH2

3-fenilpentana difenilmetana

28
Sifat Fisik Hidrokarbon Aromatik

 Hidrokarbon alifatik dan alisiklik, benzen dan hidrokarbon

aromatik lain bersifat nonpolar.
 Tak larut dalam air, larut dalam pelarut organik seperti: dietil
eter, karbon tetraklorida, atau heksana.
 Benzen bersifat toksik dan karsinogenik, sehingga kadang
diganti dengan toluen.
 Titik leleh p-substitusi lebih tinggi dari o- dan m-, p-isomer lebih
simetris
 Nama Struktur Tl (oC) Td (oC)

Benzen 5,5 80

Toluen -95 111

CH3

CH3
o-xilen -25 144

CH3

m-xilen CH3 -48 139

CH3

p-xilen 13 138
CH3 CH3
Kestabilan cincin benzen

Kalor hidrogenasi:

Pt
+ H2 + 28,6 kkal/mol

sikloheksena sikloheksana

Pt
+ 3H2 + 49,8 kkal/mol
o
225 ,
35 atm
benzen sikloheksana
Ikatan dalam benzen
Rumus Kekule

H
H
C C

H C C H

C C

H H
benzen pada 1865 benzen pada 1872 benzen pada 1940

Cincin planar dari 6 karbon
hibridisasi sp2
Masing-masing karbon
mempunyai orbital p
Enam orbital p tumpang
tindih menghasilkan siklik
sistem 
Stabilitas senyawa aromatik
3 x sikloheksena
ditunjukkan oleh DH

360 kJ/mol
231 kJ/mol

208 kJ/mol
120 kJ/mol
 3 x sikloheksena

* panas hidrogenasi =
152 kJ/mol lebih
kecil, artinya benzen
lebih stabil
360 kJ/mol
*152 kJ/mol = energi
resonansi benzen e
208 kJ/mol
Konyugasi siklik versus konyugasi nonsiklik

3H2

Pt

Panas hidrogenasi = 208 kJ/mol

3H2

Pt

Panas hidrogenasi = 337 kJ/mol

 Aromaticity; Unusual Stability Associated with
Fully Conjugated Cyclic Systems

Requirements for Aromaticity

1. Cyclic Compound
2. Planar Compound
3. Fully Conjugated System
4. 4n + 2  electrons (Huckel’s Rule)
Heterocyclic Aromatic Compounds

•• •• ••
N O S
N •• ••
•• H

Pyridine Pyrrole Furan Thiophene

N •
N •
••
Isoquinoline
Quinoline
Reactions of Arenes: A Preview

1. Some reactions involve the ring.

a) Electrophilic aromatic substitution
b) b) Nucleophilic aromatic substitution

2. In other reactions the ring is a

substituent.
Benzylic Hydrogens are Reactive Sites

H • Free Radical
Halogenation of Alkyl
Benzenes
H C H • Oxidation of Alkyl
Benzenes
• Nucleophilic
Substitution of Benzylic
Halides
Free-radical chlorination of toluene

Cl2
CH3 CH2Cl
light
or
H H heat Cl H

H C C H H C C H
UV
H + Cl2 H + HCl
 Oxidation of Alkylbenzenes

Site of Oxidation is Benzylic Carbon

CH3

or
Na2Cr2O7
O
H2SO4
CH2R COH
H2O

or heat

CHR2
 O

CH3 COH
Na2Cr2O7
H2SO4

H2O
heat

NO2 NO2
O

CH(CH3)2 COH
Na2Cr2O7
H2SO4

H2O
heat

CH3 COH

O
Reactions of Arenes:
Electrophilic Aromatic Substitution

H E
+ –
+ E Y + H Y

part 1
Aromatic Compounds React
Differently Than Alkenes

Cl
Addition
+ Cl2

Cl

Cl
FeCl3 Substitution
+ Cl2
Electrophilic Aromatic Substitution Reaction
X
X2, FeX3
Halogenation
(X = Cl, Br)

NO2
HONO2 Nitration

H2SO4

SO3 SO3H
Sulfonation
H2SO4

RCl, AlCl3 R
Friedel- Crafts Alkilation
(R can rearrange)

O O
R C Cl, AlCl3 C R
Friedel-Crafts Acylation
 Electrophilic Aromatic Substitution Mechanism

Step 1: attack of electrophile

on -electron system of aromatic ring

E+
H H H H E

H H H +
H
H H H H

highly endothermic
carbocation is allylic, but not aromatic
 Electrophilic Aromatic Substitution Mechanism

Step 2: loss of a proton from the carbocation

intermediate

E H H H H
+ H E H
H
H H H H
H+

highly exothermic
this step restores aromaticity of ring
 Nitration of Benzene

NET REACTION

H H2SO4 NO2

+ HONO2
+ H2O

+
Electrophile is
•• •• •
O N O
nitronium ion
•• •
Step 1a; Formation of Strong Electrophile

H
O O
H O N + H+ H O N
O + O

H
O +
H O N H2O + O N O
+ O
-
Step 1b: attack of nitronium cation
on -electron system of aromatic ring
NO2+
H H H H NO2

H H H +
H
H H H H

Step 2: Water molecule will abstract a proton

from the carbocation intermediate

H H
H H NO2
H NO2
H +
H H H H+
H H
 Sulfonation of Benzene

H heat SO2OH

+ HOSO2OH
+ H2O

•• •• –
•
••
O O
+
•• •
Several electrophiles present: S
a major one is sulfur trioxide

•• O
••
Halogenation of Benzene
NET REACTION

H FeBr3 Br

+ Br2
+ HBr

Electrophile is a Lewis acid-Lewis base

complex between FeBr3 and Br2.

+
•• •• •• •• –
•• Br Br •• + FeBr3 •• Br Br FeBr3
•• •• •• ••

Lewis base Lewis acid Complex

Friedel-Crafts Alkylation of Benzene

H AlCl3 C(CH3)3

+ (CH3)3CCl
+ HCl

H3C

Electrophile is +
tert-butyl cation C CH3

H3C
 Role of AlCl3

acts as a Lewis acid to promote ionization

of the alkyl halide
+
•• –
••
(CH3)3C Cl •• + AlCl3 (CH3)3C Cl AlCl3
•• ••

+ –
••
(CH3)3C + •• Cl AlCl3
••
Rearrangements in Friedel-Crafts Alkylation

Carbocations are intermediates.

Therefore, rearrangements can occur

H C(CH3)3
AlCl3
(CH3)2CHCH2Cl
+

Isobutyl chloride tert-Butylbenzene

(66%)
 Friedel-Crafts Acylation of Benzene

O
H AlCl3 CCH2CH3

+ CH3CH2CCl
+ HCl

Electrophile is an acyl cation

+ +
••
CH3CH2C O •• CH3CH2C O ••
Acylation-Reduction

permits primary alkyl groups to be attached

to an aromatic ring

O
H2NNH2, KOH,
O triethylene glycol,
H heat
CR
RCCl
OR
AlCl3 Zn(Hg), HCl

CH2R
 Example: Prepare isobutylbenzene

(CH3)2CHCH2Cl CH2CH(CH3)3

AlCl3 isobutylbenzene

No! Friedel-Crafts alkylation of benzene using isobutyl

chloride fails because of carbocation rearrangement.

C(CH3)3

Actual Product
Use Acylation-Reduction Instead

(CH3)2CHCCl
+

AlCl3 CH2CH(CH3)3
Zn(Hg)
HCl

CCH(CH3)2
Lokasi penempatan substituen ke-dua ditentukan
oleh substituen pertama -> apakah pada posisi orto,
meta atau para.
Summary of Substituen Effects on Orientation
o- and p- director m-director
strongly
activating
H2N RHN R2N RC
O
HO RO2C
RO HO3S
RC HN HC
O O
HO2C

N C
R O2N
X +
R3N
strongly
deactivating
 Multiple Subsistent Effects

CH3 CH3

Br2 Br

FeBr3

NO2 NO2

86-90%

1. If both constituents direct to the same spot;

then that location is major site of substitution.

 Multiple Subsistent Effects

CH3 CH3 O

O
AlCl3 CCH3

+ CH3CCl

CH3 CH3

99%
 2. If the 2 groups direct to different positions;
regioselectivity is controlled by the
most activating substituent

NHCH3

NHCH3
Br2 Br

strongly FeBr3
activating

Cl

Cl
87%
If the 2 groups direct to different sites;
and activating effects are similar...

CH3 CH3

HNO3
NO2

H2SO4

C(CH3)3 C(CH3)3

88%

3. Substitution occurs ortho to the smaller group

Steric effects control regioselectivity when
electronic effects are similar

CH3 CH3

HNO3

H2SO4
CH3 CH3

NO2

98%

4. Position between two substituents is last

position to be substituted
5. If 2 deactivating groups are on
the benzene ring; substitution is
rare