FRIEDEL CRAFTS REACTIONS

FRIEDEL CRAFTS ALKYLATION

Benzene rects with alkyl halides in presence of a lewis acid, anhydrous aluminium chloride to yield alkyl benzenes. This reaction is called Friedel Crafts alkylation reaction. This reaction is an aromatic electrophilic substitution reaction

AlCl3 R X

R HX
.

Mech : When alkyl halide is primary, a simple carbocation does not form. Instead, AlCl3 forms a complex with the alkyl halide and this complex acts as the electrophile.

R CH 2

Cl Al Cl3

This complex is not a simple carbocation but it acts as carbocation and it transfers positive alkyl group to the aromatic ring. These carbocations also undergo rearrangements.

Step 1 :

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Step 2 :

Step 3 :

Note : Friedel-Crafts alkylations are not just restricted to alkyl halides and AlCl3 but many other pairs of reagents that can form carbocations (or carbocation like species) also participate in this reaction, which include the following.. a mixture of an alkene and an acid.

CH(CH3) 2
OC CH3 CH CH 2 HF

propene

Isopropyl benzene

A mixture of an alcohol and an acid can also be used.

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FRIEDEL CRAFTS REACTIONS

FRIEDEL CRAFTS ACYLATION Benzene rects with acyl halides in presence of a lewis acid, anhydrous aluminium chloride to yield acyl benzenes. This reaction is called Friedel Crafts acylation reaction. This reaction is an aromatic electrophilic substitution reaction.

Friedel-Crafts acylations can also be carried out with carboxylic acid anhydrides. eg.

O O H3C C
AlCl3 O

CH3

O OH

H3C O
Mech :

H3C

In Friedel-Crafts acylation reactions, the electrophile is mostly an acylium ion

Step 1 :

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Step 2 :

O R C
Cl AlCl3 R

O AlCl4

R CO

Step 3 ;

R C O

Step 4 :

R H R O O AlCl 4
HCl AlCl3

Step 5 :

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Step 6 :

LIMITATIONS OF FRIEDEL - CRAFTS REACTIONS : 1. When carbocation formed from an alkyl halide, alkene, or alcohol can rearrange to a more stable carbocation, major product is obtained from the more stable carbocation.

2.

Friedel Crafts reaction gives poor yield when aromatic ring has powerful withdrawing groups like COOH, -COR , - CF3 , - SO3H etc and also when aromatic ring has - NH 2 , NHR, NR 2 groups. Any substituent more electron withdrawing or deactivating than a halogen i.e., any meta directing group makes the aromatic ring more electron deficient to undergo F.C reactions. Eg :

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3.

Aryl and Vinylic halides cannot be used as the halide component in F.C reactions because they do not form carbocations readily.

4.

Polyalkylations occur : Alkyl groups are electron releasing groups, and once an alkyl group is introduced into the benzene ring, it activates the ring towards further substitution.

5.

Polyacylations do not occur : Acyl group is an electron withdrawing group. Moreover, when it forms a complex with AlCl3, it becomes even more electron withdrawing, which prevents further substitution.

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