Why phenols are acidic in nature.

Phenols are acidic in nature due to the formation of stable phenoxide ion in
aqueous medium.
Phenols are more acidic than alcohols.
Acidity is explained by the measure of ability of compound to donate the
protons.
Phenols are acidic in nature due to the resonance stabilization of the phenoxide
ion formed after the release of a proton (H⁺) from the hydroxyl group (-OH)
attached to the benzene ring. The oxygen atom in the -OH group donates its
lone pair of electrons into the aromatic ring, creating a resonance structure
where the negative charge is delocalized across the ortho and para positions of
the benzene ring. This delocalization stabilizes the phenoxide ion, making it
easier for the phenol to lose a proton compared to alcohols, where no such
resonance stabilization occurs. Additionally, the sp² hybridization of the carbon
atom in the benzene ring, to which the -OH group is attached, further enhances
the acidity by withdrawing electron density, facilitating proton release.
 Give one example of Diazocoupling reaction.
Diazonium salt reacts readily with phenols and dialkyl anilines to form highly
coloured derivatives known as azo compounds.
Such a reaction is known as diazo coupling reaction.
 What is Kolbe’s reaction?

Mainly used for the synthesis of phenolic acid

Sodium salt of phenol treated with carbondioxide at 120-140˚C followed by acid
hydrolysis results in the formation of salicylic acid.
Write the effects of substitution on acidity of Phenols.
The acidity of phenols is strongly influenced by the nature and position of
substituents on the benzene ring.

1. Electron-Withdrawing Groups (EWG)

Effect: Increase acidity.
pull electron density away from the oxygen atom through inductive or
resonance effects.
This stabilizes the negative charge on the phenoxide ion, making
deprotonation easier.

p-Nitrophenol>Phenol
 2. Electron-Donating Groups (EDG)
Effect: Decrease acidity.
Reason: EDGs
push electron density towards the oxygen atom by +I (inductive) or +R
(resonance) effects.
This increases electron density on the oxygen, destabilizing the phenoxide ion,
making deprotonation harder.

p-Cresol (p-CH )<Phenol

3. Position of Substituent
Ortho and para positions:
EWGs at ortho and para positions increase acidity more than at meta because
they can show resonance effect in addition to inductive effect.
EDGs at ortho and para decrease acidity strongly due to resonance donation.
Meta position:
Only inductive effect works here (no resonance involvement), so the effect is
weaker.
3​
Write Diazotisation reaction with example.

The conversion of primary aromatic amines into diazonium salts is known as

diazotization.
It occur when primary amines react with nitrous acid and HCl in the presence of
0-5˚C.
 Explain Williamson synthesis.
Involves the treatment of sodium alkoxide with an alkyl halide to synthesis
symmetrical and unsymmetrical ether.
Sodium alkoxide is obtained by treating alcohol with sodium metal.

Displacement of halide ion from alkyl halide by an alkoxide that follows SN2
reaction, alkyl halide used in this reaction must be primary if secondary , tertiary
alkyl halide are used the reaction may lead to alkene formation.

C2H5ONa + CH3Br C2H5–O–CH3 + NaBr

Mechanism:
Formation of alkoxide ion:
A strong base (like NaOH or Na metal) removes a proton from an alcohol:

Nucleophilic substitution (SN2):

The alkoxide ion attacks an alkyl halide by backside attack, displacing the halide ion:
 Write Sandmeyer’s reaction.

Sandmeyer Reaction is a method used to replace the diazonium group (-N₂⁺) in an

aromatic diazonium salt with a halide or cyanide using a copper(I) salt as a catalyst.

Benzene diazonium salt in the presence of copper halide undergoes substitution

and the diazo group is replaced by hydrogen.
This mechanism also involves the transfer of one electron and loss of nitrogen gas.
TOPIC-13
REACTIONS AND MECHANISM-II
HOFMANN REARRANGEMENT
Mainly used for the conversion of amide to amine.
Amide on treatment with bromide in alkaline medium results in the formation of primary amine.
Mechanism:
Involves migration of alkyl group so the reaction is called as rearrangement reaction which
occurs through isocyanate intermediate.
Example

Loading…
Step 1:
Bromine reacts with amide to form N-bromoamide
Step 2:
1,2 migration of alkyl group in alkaline medium and formation of isocyanate intermediate

Loading…
Step 3:
Hydrolysis of isocyanate intermediate results in the formation of carbamic acid that undergoes
decarboxylation to produce amine
SANDMEYER’S REACTION
Reaction of benzene diazonium salt with cuprous halide under cold conditions in the formation of
aryl chloride, aryl bromide .
EXAMPLE
MECHANISM
Benzene diazonium salt in the presence of copper halide undergoes substitution and the diazo
group is replaced by hydrogen.
This mechanism also involves the transfer of one electron and loss of nitrogen gas.
AMINE
Given by –NH2
Classifications:
-Aliphatic amines: Methyl amine
-Aromatic amines: Aniline
Hybridization:
Loading…
-Methyl amine: C-H:sp3-s
C-N: sp3-sp3
N-H: sp3-s
-Aniline: sp2
Basicity of amines:
Explained by basicity constant
Basicity constant is defined as the reaction of amines with mineral acids to form ammonium salts
that show basic in nature.
Kb= [R-NH3] [OH-]/ [R-NH2]
Steric hindrance
Based on the greater number of electron releasing alkyl groups
Methyl amine > dimethyl amine > trimethyl amine
EFFECT OF SUBSTITUENTS ON
BASICITY
Eg: Aniline
Electron withdrawing groups: These destabilize cation and decrease electron density and decrease
basicity.
Eg: -NO2, -Cl, -COOH
Electron releasing groups: These stabilize cation and increase electron density and increase
basicity.
Eg: -CH3, -OCH3, -NH2
Diazotisation and coupling
The conversion of primary aromatic amines into diazonium salts is known as diazotization.
It occur when primary amines react with nitrous acid and HCl in the presence of 0-5˚C.
Eg: Benzene diazonium chloride
MECHANISM
Formation of benzene diazonium chloride
SYNTHESIS
In a beaker take 5ml of aniline and 50ml dilute HCl
Place it on ice bath and mix by using stir.
Maintain the temperature of 0-5˚C.
In another beaker take 10g sodium nitrite and dissolve in 50ml distilled water
Slowly add NaNo2 with constant stirring.
Maintain the temperature of 0-5˚C.
The solution of benzene diazonium chloride is obtained.
DIAZOCOUPLING REACTION
Diazonium salt reacts readily with phenols and dialkyl anilines to form highly coloured
derivatives known as azo compounds.
Such a reaction is known as diazo coupling reaction.
Example
Mechanism
Attack of electrophile:
Loss of proton and formation of product:
PHENOLS
Aromatic organic compound with molecular formula C6H5OH
White crystalline solid
Volatile in nature.
These are aromatic alcohols
Consists of hydroxyl group directly bonded to phenyl group.
Hybridization :
-O-H: SP3
-C-H: SP2
Acidity of phenols
Phenols are acidic in nature due to the formation of stable phenoxide ion in aqueous medium.
Phenols are more acidic than alcohols.
Acidity is explained by the measure of ability of compound to donate the protons.
EFFECT OF SUBSTITUENTS ON
ACIDITY
Electron withdrawing groups: These stabilize Phenoxide ion and increase ionization and increase
acidity.
Eg: -NO2, -Cl, -COOH
Electron releasing groups: These destabilize Phenoxide ion and decrease ionization and decrease
acidity.
Eg: -CH3, -OCH3, -NH2
WILLIAMSON SYNTHESIS
Involves the treatment of sodium alkoxide with an alkyl halide to synthesis symmetrical and
unsymmetrical ether.
Sodium alkoxide is obtained by treating alcohol with sodium metal.
Eg: R-X +R’-ONa+------------R-OR’
Mechanism:
Displacement of halide ion from alkyl halide by an alkoxide that follows SN2 reaction, alkyl
halide used in this reaction must be primary if secondary , tertiary alkyl halide are used the
reaction may lead to alkene formation.
RX +R’-ONa+------------R-OR’ +Na X
FRIES REARRANGEMENT
Phenols treated with acid chloride or acid anhydride forms phenolic esters which on heating with
catalyst followed by hydrolysis result in rearrangement to form ortho para acyl phenols.
Example:
Loading…
KOLBE REACTION
Mainly used for the synthesis of phenolic acid
Sodium salt of phenol treated with carbondioxide at 120-140˚C followed by acid hydrolysis results
in the formation of salicylic acid.
Eg:
MECHANISM
The electrophile gets added to phenoxide ion at ortho position.
REIMER TIEMAN’S REACTION
This reaction involves the treatment of phenol with chloroform in aqueous NaOH solution
followed by acid hydrolysis that result in the formation of salicyaldehyde.
Mainly used for the synthesis of phenolic aldehyde.
Eg:
THANK YOU