Course Title: Organic Chemistry-I

Course code: CHM-553, CHM-507

Semester: MSc 1st , BS 5th

By: Dr. Maryam/ Dr. Umme Kalsoom

Assistant Professor
Department of Chemistry
GCWUF
Learning Objectives:

• Acidity of Phenols.
• Effect of Electron Withdrawing and Electron Donating Groups on the
Acidity of Phenols.
Acidity of Phenols:
• Acidity of Phenols in Comparison with Carboxylic Acids and Alcohols:

• When the phenols are compared with carboxylic acids and alcohols, the order
of acidity is found to be:
 Acidity of Phenols:

• Reason of Lower Acidity of Phenols than Carboxylic Acids:

• In case of acetic acid , the CH3COO- anion is stabilized due to delocalization

of negative charge on two oxygen atoms.

• In case of phenol the oxygen atom of a phenoxide ion is adjacent to the

aromatic ring and the negative charge is partially delocalized by the aromatic
pi cloud, hence phenols are intermediate in acidity between acetic acid and
C2H5OH.
Acidity of Phenols:

• Reason of Greater Acidity of Phenols than Alcohols:

• In case of C2H5OH, the C2H5O- anion is not stabilized by resonance effect.

The negatively charge resides entirely on oxygen and is not delocalized.
• Moreover, -C2H5 is an electron donating group, it makes C2H5O- anion less
stable.
Acidity of Phenols:

• Effect of Electron Withdrawing Groups on the Acidity of Substituted Phenols:

• The presence of electron withdrawing groups in the nucleus increases the
acidity of the phenols.
• The Effect of Inductive Effect on the Acidity of Nitro-Phenol:

• In
  case of nitro phenol, the inductive effect would fall off with distance on
going o m p nitro phenols.
Acidity of Phenols:

• The Effect of Resonance on the Acidity Nitro-Phenol:

• There would be an electron withdrawing mesomeric effect when the nitro

group is in o- or p-, but not in meta position.
• This would promote ionization of substituted phenol by stabilization through
delocalization of the resultant anion.
Acidity of Phenols:

• Why ortho and para Nitrophenols are Stronger Acids than Phenol itself?

• Introduction of a –R group at ortho and para position makes a phenoxide ion

more stable through dispersion of negative charge in a much better way.
• Thus ortho and para nitrophenols are stronger acid than phenol itself.
Acidity of Phenols:

• meta Nitrophenol is Less Acidic than the ortho and para Nitrophenols:

• –R group at the meta position, however, cannot take part in resonance.

• And so meta nitrophenoxide ion is not so stable and for this reason meta
nitrophenol is less acidic than the ortho and para nitrophenols.
Acidity of Phenols:
• Comparison of the Acidity of para-Nitrophenol with ortho-Nitrophenol:

• When we compare para nitrophenol with ortho-nitrophenol, the para

nitrophenol is more acidic in character.
• In ortho-nitrophenol the nitro group is adjacent to –OH group and H-bonding
takes place which makes it difficult to remove the proton.

• So H-bonding makes ortho-nitrophenol weaker in comparison with para-

nitrophenol.
 Acidity of Phenols:
• Order of Acidity of ortho, meta and para-Nitrophenol in Comparison with
Phenol:

• So, the order of Acidity of ortho, meta and para-Nitrophenol in Comparison

with Phenol is:
 Acidity of Phenols:

• Effect of Introduction of Further Nitro Groups on the Acidity of Nitrophenol:

• Introduction of further NO2 groups promotes acidity markedly.

• Thus 2,4,6-trinitrophenol (picric acid) is found to be very strong acid.

Phenol pKa value

C6H5OH 9.95
O-O2NC6H4OH 7.23
m-O2NC6H4OH 8.35
p-O2NC6H4OH 7.14
2,4-(O2N)2C6H3OH 4.01
2,4,6-(O2N)3C6H2OH 1.02
Acidity of Phenols:
• Effect of Electron Donating Groups on the Acidity of Substituted Phenols:

• If we introduce electron donating alkyl groups into the benzene nucleus, the
effect produced is very small.

• Methyl group makes the phenol weaker by electron releasing effect and it is
clear that the difference in pKa values is very small.
Acidity of Phenols:
• Effect of the Substitution of the Groups due to which Negative Charge Comes
at Position 1:
• It is a well known fact that whenever by any phenonmenon (resonance or
hyperconjugation) negative charge comes at position 1 with respect to groups
which is under observation, it makes the acids or phenols weaker than at position 2
and 6.
Acidity of Phenols:
• Why o- Cresol is Weaker Acid than p-Cresol?

• Resonance effect (due to hyperconjugation) is same at ortho- and para-

positions, i.e, negative charge comes at 1, 3 and 5 position.
• But inductive effect at ortho-position is slightly more than p-position.
• Hence o- cresol is weaker than p-cresol.
Acidity of Phenols:
• Comparison of the Acidity of meta- Cresol with ortho and para- Cresol:
• In case of m-cresol negative charge comes at 2,4 and 6 positions by
hyperconjugation.
• But in this case inductive effect is slightly less than at ortho position but
slightly more than at para position.
• Hence, m-cresol is more acidic than o- and p- cresols.
• Moreover, there is also H-bonding in ortho-cresol which makes it relatively
weaker acid, than m-cresol and p- cresol.
 Acidity of Phenols:
• Order of Acidity of ortho, meta and para-Cresol in Comparison with Phenol:

• So, the order of Acidity of ortho, meta and para-Cresol in Comparison with
Phenol is:

Phenol > m-cresol > p- cresol > o-cresol

References:
• Bansal, R. K. 1990. A Text Book of Organic Chemistry. 2nd Edition, Wiley
Easteren Ltd.
• Haq Nawaz Bhatti. Advanced Organic Chemistry.