Alcohols and Phenols

Introduction:
Alcohols, phenols, and ethers are classes of organic compounds that share structural
similarities with water and are therefore considered its derivatives.

 Alcohols: Formed when a hydrogen atom in an alkane is replaced by a -OH

group.
 Phenols: Formed when a hydrogen atom on a benzene ring is replaced by a -
OH group.
 Ethers: It is a linkage between two carbon atoms through an oxygen atom.

Classification of Alcohols:
Alcohols can be classified based on the number of carbon atoms attached to the
carbon atom bearing the -OH group:

 Primary (1°): The carbon atom attached to the -OH group is bonded to only
one other carbon atom. Example: CH3-CH2-OH (Ethanol)
  Secondary (2°): The carbon atom attached to the -OH group is bonded to two
other carbon atoms. Example: CH3-CH(OH)-CH3 (Isopropanol)

 Tertiary (3°): The carbon atom attached to the -OH group is bonded to three
other carbon atoms. Example: (CH3)3C-OH (tert-Butanol)

CH2OH (Benzyl Alcohol)

Alcohol

Aliphatic Aromatic

Polyhydric
(Mannitol, Monohydric
Glycerol)
𝜶
Primary Alcohol
1o
R CH2OH
𝜶
Secondary Alcohol R1
CHOH
2o R2
𝜶 R1
Tertiray Alcohol
3o
COH R2
R3

Reactivity of the -OH Group:

 The oxygen atom in the -OH group of alcohols is sp³ hybridized.
 The C-O and O-H bonds are highly polarized, with a partial negative charge
on the oxygen atom.
Chemical Properties of Alcohols:
Alcohols undergo reactions involving either the breaking of the C-O bond or the O-
H bond.

1. Reactions in which the C-O bond breaks:

 Order of reactivity:
Tertiary alcohol > Secondary alcohol > Primary alcohol
 Mechanism: A nucleophile attacks the carbon atom of the C-O bond,
breaking it.

2. Reactions in which the O-H bond breaks:

 Order of reactivity:
CH3OH > Primary alcohol > Secondary alcohol > Tertiary alcohol
 Mechanism: An electrophile attacks the oxygen atom of the O-H bond,
breaking it.

(i) Oxidation of alcohol:

Catalytic oxidation of primary and secondary alcohols in the presence of
K2Cr2O7 and H2SO4 converts them into aldehydes and ketones respectively. Tertiary
alcohols resist oxidation and instead undergo elimination reactions in the presence
of acidified K2Cr2O7.

C2H5OH + [O] → CH3CHO + H2O

If reaction of tertiary alcohols takes place in presence of K₂Cr₂O₇ and H₂SO₄, instead
of oxidation we obtain an elimination reaction and we get alkene as our result.

On heating with concentrated H2SO4, Alcohols change into alkenes.

Example:

𝑯𝒆𝒂𝒕
C2H5OH ⎯⎯⎯⎯⎯⎯⎯ CH2=CH2 + H2O
𝑪𝒐𝒏𝒄 𝑯𝟐 𝑺𝑶𝟒
𝑯𝒆𝒂𝒕
C3H7OH ⎯⎯⎯⎯⎯⎯⎯ CH3-CH=CH2 + H2O
𝑪𝒐𝒏𝒄 𝑯𝟐 𝑺𝑶𝟒

(ii) Reactions of alcohols in which C-O bond cleavage occurs:

 C2H5OH + PCl5 → C2H5Cl + HCl + POCl3
 3C2H5OH + PCl3 → 3C2H5Cl + H3PO3

 C2H5OH + SOCl2 → C2H5Cl + SO2 + HCl

 C2H5OH + NH3 → C2H5NH2 + H2O

 C2H5OH + HCl → C2H5Cl + H2O

(iii) Reactions of alcohols in which O-H bond cleavage occurs:

C2H5-OH + 2Na → C2H5O-Na+ + H2

(iv) Iodoform test:

Ethanol gives iodoform with iodine in the presence of NaOH. Formation of yellow
crystals indicates that the alcohol is ethanol. Methanol does not give the iodoform
test.
 Ethanol:
C2H5OH + 4I2 + 6NaOH → CHI3 + HCOONa + 5NaI + 5H2O
Iodoform

 Methanol:
CH3OH + I2 + NaOH → No yellow ppt.

(v) Esterification:
Here, the -OH group of the carboxylic acid is replaced by the RO- (alkoxide) group
of the alcohol in a nucleophilic substitution reaction.
 Example:
𝑯𝟐 𝑺𝑶𝟒
C2H5OH + CH3COOH ↔ CH3COOC2H5 + H2O

(vi) Dehydration:
Alcohols, when treated with H2SO4 at different temperatures, produce different
products:
 Example:
𝑪𝒐𝒏𝒄 𝑯𝟐 𝑺𝑶𝟒
o C2H5OH ⎯⎯ CH2=CH2 + H2O
𝟏𝟖𝟎𝒐 𝑪
𝑪𝒐𝒏𝒄 𝑯𝟐 𝑺𝑶𝟒
o 2C2H5OH ⎯⎯ C2H5-O-C2H5 + H2O
𝟏𝟒𝟎𝒐 𝑪

Methanol does not produce any alkene on reaction with conc. H2SO4 because it has
no β-hydrogen. Therefore, β-elimination reaction does not take place.

Distinction between primary, secondary, and tertiary alcohols:

Primary, secondary, and tertiary alcohols can be distinguished by their reactivity with
halogen acids in the presence of anhydrous ZnCl2.
For example, when an alcohol is treated with a solution of ZnCl2 in conc. HCl:
 Tertiary alcohol: Forms an oily layer immediately.
 Secondary alcohol: Forms an oily layer in five to ten minutes.
 Primary alcohol: Forms an oily layer only on heating.
1. Tertiary Alcohol:

2. Secondary Alcohol:
 3. Primary Alcohol:
R-CH2-OH + HCl → (ZnCl2, Heat) → R-CH2-Cl + H2O

Phenols
Definition:
Phenols are aromatic compounds containing one or more -OH groups directly
attached to a carbon atom of the benzene ring.

Physical Properties:
 Appearance:
Colorless, crystalline, deliquescent solid with a characteristic phenolic odor.
 Melting Point: 41°C
 Boiling Point: 182°C
 Solubility:
Sparingly soluble in water at room temperature, forming a pink solution.
Completely soluble above 68.5°C.
 Toxicity:
Poisonous and used as a disinfectant.
Simplest Phenol:
 Carbolic acid (benzenol) (C6H5OH): The simplest phenol, first obtained
from coal tar by Runge in 1834.
Types of Phenols
 Phenol: C₆H₅OH

 1,2-Dihydroxybenzene: o-Hydroxy phenol (Catechol)

 1,3-Dihydroxybenzene: m-Dihydroxy phenol (Resorcinol)

 1,4-Dihydroxybenzene: p-Hydroxy phenol (Hydroquinone)

 2-Nitrophenol: o-Nitrophenol

 3-Nitrophenol: m-Nitrophenol
  2,4,6-Trinitrophenol: Picric acid

Reac ons of Phenol:

 Phenol exhibits reac ons characteris c of both the -OH group and the
aroma c ring.
Reac ons of Phenol's Hydroxyl Group
Reac on Equa on Remarks

Salt Forma on C₆H₅OH + NaOH → C₆H₅ONa + H₂O Phenoxides are

formed in basic
media
Ester Reac on takes
Forma on C₆H₅OH + CH₃COCl → C₆H₅OCOCH₃ + HCl place in basic
media

Reduc on with Benzene is

Zn C₆H₅OH + Zn (dust) → C₆H₆ + ZnO obtained
1. Salt forma on:

2. Zn reduc on:
 Electrophilic Aroma c Subs tu on Reac ons of Phenol

Reac on Remarks
Nitra on At room temp., a mixture of o- and p-nitrophenol is
formed with dilute HNO₃.
At higher temp., picric acid (2,4,6-trinitrophenol) is
formed with concentrated HNO₃.
Sulfona on A mixture of ortho and para products is formed at 15-
20°C by the introduc on of HSO3
Halogena on White precipitate of 2,4,6-tribromophenol is obtained.
Hydrogena on Unsatura on of the ring is removed.
Reac on with Condensa on polymeriza on of phenol with
Formaldehyde formaldehyde produces Bakelite, used in manufacturing
switch bu ons.

1. Nitra on:
2. Sulfona on:
3. Halogena on:

4. Hydrogena on:
Relative Acidity of Water, Ethanol, and Phenol:
 Phenol: Weakly acidic, unable to affect litmus paper or evolve CO2 from
carbonates. Its Ka is 1.3 x 10^-10, and its pKa is approximately 10.
 Ethanol: Very weakly acidic.
 Water: Amphoteric, meaning it can act as both an acid and a base.

Reason for Phenol's Acidity:

The acidity of phenols, compared to alcohols, is attributed to the formation of stable
phenoxide ions after the loss of a proton. The phenoxide ion is resonance stabilized,
allowing the negative charge to spread throughout the benzene ring and become
dispersed. This delocalization of charge contributes to the stability of the phenoxide
ion.
Example:
Phenol reacts with NaOH or Na metal to form a salt, demonstrating its acidic nature.

Relative Acidic Strength:

The relative acidic strength of alcohol, phenol, water, and carboxylic acid is as
follows:

Compound Formula Ka (approx) pKa (approx)

Carboxylic acids R-COOH 10^-5 5
Phenol Ar-OH 10^-10 10
Water H-OH 10^-14 14
Alcohols R-OH 10^-16 to 10^-18 16-18

Difference between Alcohols and Phenols

Feature Alcohols Phenols
Hydroxyl group Attached to an alkyl group Attached to an aryl group
(R-OH) (Ar-OH)
Derivatives Hydroxyl derivatives of Hydroxyl derivatives of
alkanes benzene
 General formula R-OH C6H5OH (carbolic acid)
Monohydric/Polyhydric Can be both Monohydric or Not monohydric or
Polyhydric polyhydric
Appearance Generally colorless liquids Colorless, crystalline,
deliquescent solid
Smell Characteristic sweet smell Characteristic phenolic color
and burning taste
Solubility Readily soluble in water, Sparingly soluble in water,
decreasing with increasing forming a pink solution
chain length

Reactions C-O bond cleavage and O-H Reactions due to -OH group
bond cleavage and reactions due to benzene
ring

Resonance Alkoxide ions have no Phenolate ions have

resonance structures resonance structures
Acidity Less acidic (pKa = 16 -20) Acidic (pKa = 10)