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Nidal Blake Zianga

What is the role of pH in azo coupling reaction of diazonium with phenol and aniline?

Amos Ekeson  Follow

Deprotonation of the phenol and protonation of aniline result in species that easily react with a diazonium cation in the intended manner.

Let's have a look at the species involved. On the one hand, there is the diazonium cation:

diazonium cation

Deprotonation of phenol yields phenolate, for which a resonance structure with a negative charge in para position to the substituent can be written:

phenolate

We conclude: Deprotonation of the phenol means activation!

phenolate reaction with diazonium cation

In the case of aniline, the lone pair on the nitrogen atom is the preferred centre for the reaction with the diazonium cation:

aniline reaction with diazonium

This isn't what we want! Protonation of aniline avoids this side reaction.

We conclude: Protonation of aniline means "masking" the wrong centre!

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Doug Crawford  Follow
In the case of phenol, Why lone pairs of oxygen are not the preferred center for reaction with diazonium cation??More
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Jerry Larson  Follow
Klaus, could you add to your post to answer the comments? Theyre good questions, and making a new post for them seems unnecessary.More
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Iffat Ara Sharmeen  Follow
orthocresols answer hereMore
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Glen Broderick  Follow
If aniline is protonated, then wont the benzene ring be deactivated in aniline? NH3+ is supposed to be a strong deactivating group. This deactivation should then prevent azo coupling because azo coupling reactions need highly activated groups.More
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Ivelina Georgieva  Follow
answers why HCl is being used to form the azobenzene.More
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Cars and Trucks  Follow

Deprotonation of the phenol and protonation of aniline result in species that easily react with a diazonium cation in the intended manner.

Let's have a look at the species involved. On the one hand, there is the diazonium cation:

diazonium cation

Deprotonation of phenol yields phenolate, for which a resonance structure with a negative charge in para position to the substituent can be written:

phenolate

We conclude: Deprotonation of the phenol means activation!

phenolate reaction with diazonium cation

In the case of aniline, the lone pair on the nitrogen atom is the preferred centre for the reaction with the diazonium cation:

aniline reaction with diazonium

This isn't what we want! Protonation of aniline avoids this side reaction.

We conclude: Protonation of aniline means "masking" the wrong centre!

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John Waldeck  Follow
In the case of phenol, Why lone pairs of oxygen are not the preferred center for reaction with diazonium cation??More
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Fraser Robertson  Follow
what is the role of Ph in the answer given?More
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Doug Robb  Follow
If aniline is protonated, then wont the benzene ring be deactivated in aniline? NH3+ is supposed to be a strong deactivating group. This deactivation should then prevent azo coupling because azo coupling reactions need highly activated groups.More
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Jim Shepherd  Follow
orthocresols answer hereMore
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GardenC  Follow
Klaus, could you add to your post to answer the comments? Theyre good questions, and making a new post for them seems unnecessary.More
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