18.

11 Diazotization
Chemists synthesize aryl diazonium salts from aryl amines.
An aryl diazonium salt has the formula ArN2

An aryl diazonium salt is made from an aryl amine.

NH2

NaNO2, HCl H2O, 05 C

C l Benzene diazonium chloride

The electrophile used to react with the amine to form the aryl diazonium salt is the mild

NO electrophile. The following

mechanism shows how the aryl diazonium salt forms from HCl and NaNO 2. The

NO ion is resonance-stabilized, so it forms relatively easily.

NaNO2

+ HCl

HO

+ NaCl

+
HO

H O

N O

H H

HO H

+ H2O

Diazotization is the name of the process that forms a diazonium salt.

Af ter th e

se

fashion

with the amine nitrogen. The intermediate then water forms diazonium salt; thus, completing the diazotization process. Compare following diazotization process the substitution and elimination reactions Chapters and 13. of 12 with the loses and the

N O el ec tro ph ile fo rm s, it re ac ts in ac id/ ba

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N H
2

O H H

O H
2
N N

O H

Azo coupling is the electrophilic substitution reaction of a diazonium salt with an activated aromatic ring to form a product with the structure ArN=NAr.

Once formed, diazonium salts can be used as synthetic intermediates for a number of substituted aromatic compounds. For example, nucleophiles displace the N 2 group, so aryl diazonium salts can be used in reactions to prepare a number of substituted aromatic compounds. Section 18.12 (page 000) discusses the reaction of diazonium salts with nucleophiles. Diazonium salts can also be used as electrophiles to substitute onto another aromatic system. This type of electrophilic aromatic substitution reaction is called azo coupling. Although diazonium salts are relatively weak electrophiles, they do react well with strongly activated aromatic rings. Chemists most frequently use the OH and the NR2 groups to activate the ring. The products formed in azo coupling reactions contain the azo functional group ( N=N) and have the general structure of ArN=NAr. The general mechanism for the reaction follows a similar mechanism to the other electrophilic substitution reactions studied in this chapter.

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H
2

O

N N N N

OH

OH

OH

4-Phenylazophenol An azo compound

Most azo compounds are highly colored and make excellent dyes. These dyes, called azo dyes, are usually more stable and retain their bright colors better than most other dyes. Following are a few examples of azo dyes.

OH

+
O2 N

COOH N N O H COO H

O2N Alizarin yellow

(82%) N N
N(CH )
32

+ HO3S
N N
N(CH3)2

HO3S
Methyl orange (70%)

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HO

HO + O2N N N

O2N Para red (76%)