1.

Benzene

Aromatic compounds 2. Salicylic Acid

CO O H OH

3. Acetyl Salicylic Acid (Aspirin)

4.Ibuprofen (Advil !otrin)

CO O H O CCH3 O

CO O H

" (. 1 1 1)$ric*loro)2 2)bis(p) c*lorop*enyl)et*ane (++$)

Cl

#. $A%&'
O NH O O OH OHO O O O O O O O OH

Cl Cl Cl Cl

,. $etra*ydrocannabinol

-. !et*yl salicylate (flavor for .inter/reen)

OH

OH
O

CO O CH3

0.1anillin.
O

12. 3ap*t*alene

O CH3 OH

11. +iazepam (valium)

NH N O

12. 3apro4en

CO O H CH3O

13. 3 3)+iet*yl)m)toluamide
O C N(CH2CH3)2

14. 5ocaine
H3C N O

O O

H3C

1#. 3icotine

1(. Benzo6a7pyrene

N CH3

Aromatic Compounds 5onditions t*at must be satisfied to considered aromatic8 $*e 1. 2. 3. 4. 5yclic 9lanar All atoms in t*e cyclic structure must *ave an un*ybridized p) orbital must follo. :uc;el<s rule8 4n=2 > pi electrons .*ere n> 2 1 2?. (.*ole number)

Nomenclature: A. !onosubstituted Benzene8

Br

3&2

3:2

53

5&&:

S&3:

&

B. +isubstituted Benzene
5:3 Br 3&2 5l 3:2 5&&:

5. 9olysubstituted Benzene
& 53 5l &23 &23 3&2 S&3: 5l

5l

Reactions: 1. @lectrop*ilic Aromatic Substitution : = @= @ = Aenerated from :=

@lectrop*iles

%2 Ce%3 :3&3 :2S&4

=

= 3&2

S&3:
=

S&3 :2S&4 B% Al%3 & B5% Al%3

& B5
=

Electrophilic Aromatic Substitution A. :alo/enation

%2 Ce%3
A. 3itration

% = :%

:3&3 :2S&4

3&2 = :2&

B. Sulfonation

S&3 :2S&4
5. Criedel 5raft<s Al;ylation

S&3:

B% Al%3
+. Criedel 5raft<s Acylation

B = :%

& B5% Al%3

& 5B = :%

Limitations of Friedel Crafts Reactions 1. $*ere is dan/er of polysubstitution 2. Bearran/ement may occur 3. Aryl can not be used as t*e *alide component because t*ey do not form carbocations readily. 4. Aromatic rin/s less reactive t*an *alobenzene do not under/o Criedel 5rafts reactions. #. Aromatic rin/s .it* )3:2 )3:B and D3B2 do not under/o Criedel 5rafts Beactions Substituent Effects in Electrophilic Aromatic Substitution (EAS) 1. Substituents affect reactivity to.ards @AS Activatin/ Aroups) electron releasin/ +eactivatin/ Aroups) electron .it*dra.in/ 2. Substituents affect t*e orientation of t*e reaction o, p) +irectors m- +irectors 3. Substituents can be classified as Activatin/ o, p) +irectors +eactivatin/ o, p) +irectors +eactivatin/ m- +irectors

&t*er Beactions 2. &4idation of Al;yl benzene

B E!n&4 :2&
3. Beduction :2F9t *i/* $ *i/* 9 4. Beduction of Aryl Eetone a. 5lemmensen Beduction
& B

5&&:

Gn(:/) :5l

b. Holff)Eis*ner Beduction
& B 3:23:2 base B

#. Al;ali Cusion of Aromatic Sulfonates

S&3: 1. 3a&: 2.:3&
=

&:

= 3a:S&3

(. Beduction of Aromatic 3itro /roup

3&2
1. Sn5l2 :3& 2.:3&
=

3:2
=

,. 3ucleop*ilic Aromatic Substitution (a) Addition @limination to activated aryl *alide

5l &23 3&2 1. &: *i/* $ 9 2. :3& 3&2
= )

&: &23 3&2

3&2

(b) via benzyne intermediate for unactivated aryl *alides -. Benzylic Bromination

5:2

B 3BS (9*5&2)2 55l4

Br

5:B

3BS8 3)Bromosuccinimide & 3 & Br

Substituent @ffects in @lectrop*ilic Aromatic Substitution Activatin/ o,p)directors Stron/ly Activatin/ !oderately Activatin/ Hea;ly Activatin/ )3:2 )3:B )3B2 )&: )&) )&B )3:5&B )B )9* (p*enyl)

+eactivatin/ o,p)directors )C Hea;ly +eactivatin/ )5l )Br )I +eactivatin/ m)directors )5:& )5&2B !oderately +eactivatin/ )5&2: )5&B )S&3: Stron/ly +eactivatin/ )53 )3&2 )3B3 )5C3 )55l3