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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) :

Oleh karena benzen TIDAK bereaksi seperti alkena maka ikatan rangkapnya mempunyai karakter yang berbeda Struktur Kekule tidak sepenuhnya tepat !
H- C

H H H

H H

C C-H C-H

Struktur baru yang diajukan :

H- C

O
C H

atau

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 1 CH3 1 2 CH3 CH3

3 Cl 4 CH3 Cl

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-, paraBr Br


Br 1 2 Br 1 1 3 Br 4 Br

o-dibromo benzen

m-dibromo benzen

p-dibromo benzen

5. Benzen sebagai substituen

fenil :
CH 3

CH2

CH3

fenil

benzil

p-tolil

o-tolil

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 Benzen

Struktur

Tl (oC) 5,5

Td (oC) 80

Toluen
CH3

-95

111

o-xilen

CH3

-25
CH3

144

m-xilen

CH3

-48
CH3

139

p-xilen
CH3 CH3

13

138

Kestabilan cincin benzen

Kalor hidrogenasi:
Pt + 28,6 kkal/mol

+ H2 sikloheksena

sikloheksana

+ 3H2 benzen

Pt 225o, 35 atm sikloheksana + 49,8 kkal/mol

Gambar 10.5

Ikatan dalam benzen

Rumus Kekule
H H
C C C C C

H benzen pada H 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 ditunjukkan oleh DH

3 x sikloheksena

360 kJ/mol 231 kJ/mol 120 kJ/mol 208 kJ/mol

3 x sikloheksena

* panas hidrogenasi = 152 kJ/mol lebih kecil, artinya benzen lebih stabil *152 kJ/mol = energi resonansi benzen e

360 kJ/mol

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.
2. 3.

4.

Cyclic Compound Planar Compound Fully Conjugated System 4n + 2 electrons (Huckels Rule)

Heterocyclic Aromatic Compounds


N
N

Pyridine

H Pyrrole Furan Thiophene

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 H C H
Free Radical Halogenation of Alkyl Benzenes Oxidation of Alkyl Benzenes
Nucleophilic

Substitution of Benzylic Halides

Free-radical chlorination of toluene

Cl2 CH3 light or heat


H UV H + Cl2 H + HCl H

CH2Cl

H H C

H C

Cl C

H C H

Oxidation of Alkylbenzenes

Site of Oxidation is Benzylic Carbon


CH3 or

Na2Cr2O7 H2SO4

CH2R
or

H2O heat

COH

CHR2

O CH3 Na2Cr2O7 H2SO4 H2O heat NO2 CH(CH3)2 Na2Cr2O7 H2SO4 H2O heat CH3 COH O NO2 O COH

COH

Reactions of Arenes: Electrophilic Aromatic Substitution

+
+ E

E + H Y

part 1

Aromatic Compounds React Differently Than Alkenes


Cl + Cl2 Cl
Addition

FeCl3 + Cl2

Cl
Substitution

Electrophilic Aromatic Substitution Reaction


X2, FeX3 (X = Cl, Br) NO2 X Halogenation

HONO2 H2SO4 SO3 H2SO4 RCl, AlCl3 (R can rearrange) O R C Cl, AlCl3

Nitration

SO3H

Sulfonation

R Friedel- Crafts Alkilation O 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
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 E H+

H
H

H H H H

highly exothermic this step restores aromaticity of ring

Nitration of Benzene
NET REACTION

H + HONO2

H2SO4

NO2 + H2O

Electrophile is nitronium ion

+ N

Step 1a; Formation of Strong Electrophile

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

H O H O + N O H2O + O + N

Step 1b: attack of nitronium cation on -electron system of aromatic ring


NO2+

H
H H

H
H H H

H
+

NO2

H H H

Step 2: Water molecule will abstract a proton from the carbocation intermediate

H
H +

NO2

H
H
H

H
NO2
H H+

Sulfonation of Benzene

H + HOSO2OH

heat

SO2OH + H2O

Several electrophiles present: a major one is sulfur trioxide

+ S

Halogenation of Benzene
NET REACTION H + Br2 FeBr3 Br + HBr

Electrophile is a Lewis acid-Lewis base complex between FeBr3 and Br2. + FeBr3

Br

Br

FeBr3

Br

Br

Lewis base

Lewis acid

Complex

Friedel-Crafts Alkylation of Benzene

H + (CH3)3CCl

AlCl3

C(CH3)3 + HCl

H3C

Electrophile is tert-butyl cation


H3C

+ C CH3

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
AlCl3 C(CH3)3

(CH3)2CHCH2Cl

Isobutyl chloride

tert-Butylbenzene (66%)

Friedel-Crafts Acylation of Benzene


O O H + AlCl3 CCH2CH3 + HCl

CH3CH2CCl

Electrophile is an acyl cation

+ CH3CH2C

CH3CH2C

+ O

Acylation-Reduction
permits primary alkyl groups to be attached to an aromatic ring

O H RCCl AlCl3

O CR

H2NNH2, KOH, triethylene glycol, heat


OR Zn(Hg), HCl

CH2R

Example: Prepare isobutylbenzene


(CH3)2CHCH2Cl AlCl3 CH2CH(CH3)3 isobutylbenzene

No! Friedel-Crafts alkylation of benzene using isobutyl chloride fails because of carbocation rearrangement.
C(CH3)3

Actual Product

Use Acylation-Reduction Instead


O

(CH3)2CHCCl

AlCl3

Zn(Hg) HCl
O CCH(CH3)2

CH2CH(CH3)3

Lokasi penempatan substituen kedua ditentukan oleh substituen pertama -> apakah pada posisi orto, meta atau para.

Summary of Substituen Effects on Orientation


strongly activating H2N HO RO RC HN O o- and p- director RHN R2N m-director RC O RO2C HO3S HC O HO2C N C R X O2N
+

R3N strongly deactivating

Multiple Subsistent Effects


CH3 Br2 FeBr3 CH3 Br

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 O AlCl3 + CH3CCl

CH3

O CCH3

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 activating

FeBr3

Cl Cl 87%

If the 2 groups direct to different sites; and activating effects are similar...
CH3 HNO3 CH3 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 HNO3 CH3

H2SO4 CH3

CH3 NO2 98%

4. Position between two substituents is last position to be substituted