Alchohols, Phenols and Ethers (Theory)

 Alcohols and phenols are formed when a hydrogen atom in a hydrocarbon, aliphatic and
aromatic respectively, is replaced by –OH group.
 The substitution of a hydrogen atom in a hydrocarbon by an alkoxy or aryloxy group
(R–O/Ar–O) yields another class of compounds known as ‘ethers’.
 In alcohols, the oxygen of the –OH group is attached to carbon by a sigma (σ ) bond formed
by the overlap of an sp 3 hybridized orbital of carbon with an sp3 hybridized orbital of
oxygen.
 The bond angle in alcohols is slightly less than the tetrahedral angle (109°-28′). It is due to
the repulsion between the unshared electron pairs of oxygen.

 In phenols, the –OH group is attached to the sp2 hybridized carbon of an aromatic ring.
 The carbon–oxygen bond length (136 pm) in phenol is slightly less than that in methanol.
This is due to
(i) partial double bond character on account of the conjugation of unshared
electron pair of oxygen with the aromatic ring and
(ii) the sp2 hybridised state of carbon to which oxygen is attached.
 In ethers, the four electron pairs, i.e., the two bond pairs and two lone pairs of electrons on
oxygen are arranged approximately in a tetrahedral arrangement.
 The bond angle is slightly greater than the tetrahedral angle due to the repulsive interaction
between the two bulky (–R) groups.
 The C–O bond length (141 pm) is almost the same as in alcohols.
 Mechanism of Acid Catalysed Dehydration :
1) Step 1: Protonation of alkene to form carbocation by electrophilic attack of H3O +

2) Step 2: Nucleophilic attack of water on carbocation

3) Step 3: Deprotonation to form an alcohol.

Acid catalysed dehydration follows Markovnikov Rule.

 Hydroboration Oxidation follows Anti-Markovnikov Rule.
 Catalytic Hydrogenation (Addition of Hydrogen (Reduction) using Catalysts) of Aldehydes,
Ketones, and Carboxylic Acids (Carbonyl compounds) yields Alcohols.
Aldehydes yield primary alcohols whereas ketones give secondary alcohols.
 Reducing Agents :

i. LiAlH4 – Lithium Aluminium Hydride

ii. NaBH4- Sodium borohydride
iii. Pt/Ni/Pd, H2
 Carboxylic acids are reduced to primary alcohols in excellent yields by lithium
aluminum hydride, a strong reducing agent.
 However, LiAlH4 is an expensive reagent, and therefore, used for preparing special
chemicals only.
 Commercially, acids are reduced to alcohols by converting them to the esters
followed by their reduction using hydrogen in the presence of catalyst (catalytic
hydrogenation).

 Aldehydes/ Ketones + Grignard Reagent  (1. Nucleophilic Addition) Adduct (2.On

Hydrolysis)  alcohol
The reaction produces primary alcohol with methanal, secondary alcohol with other
aldehydes and tertiary alcohol with ketones.

 Phenol, also known as carbolic acid.

 Methods of preparation of Phenols
 From Haloarenes
 From benzene Sulphonic acid
 From Diazonium salts
 From Cumene
Chlorobenzene is fused with NaOH at 623K and 320 atmospheric pressure. Phenol is
obtained by acidification of sodium phenoxide.

1. Phenol is manufactured from the hydrocarbon, cumene. Cumene (isopropylbenzene)

is oxidised in the presence of air to cumene hydroperoxide. It is converted to phenol
and acetone by treating it with dilute acid. Acetone, a by-product of this reaction, is
also obtained in large quantities by this method.

 Alcohols are versatile compounds. They react both as nucleophiles and electrophiles. The bond
between O–H is broken when alcohols react as nucleophiles.

1. bond between O–H is broken when alcohols react as nucleophiles.

Reactions
  Alcohols and phenols react with active metals such as sodium, potassium, and
aluminum to yield corresponding alkoxides/phenoxides and hydrogen.
 phenols react with aqueous sodium hydroxide to form sodium phenoxides.
 The above reactions show that alcohols and phenols are acidic in nature. In fact,
alcohols and phenols are Brönsted acids i.e., they can donate a proton to a stronger
base (B:)
 The acidic character of alcohols is due to the polar nature of O–H bond.
 Order of acidic strength of Alchohols :
Phenols >Water >Primary alcohols > Secondary alcohol > Tertiary alcohol
 phenols are stronger acids than alcohols and water.
 Esterification:
[Alchohols/Phenols + Acid anhydride/ Acid chloride/Carboxylic acids  Esters ]
 The reaction with carboxylic acid and acid anhydride is carried out in the
presence of a small amount of concentrated sulphuric acid.
 The reaction is reversible, and therefore, water is removed as soon as it is
formed.
 The reaction with acid chloride is carried out in the presence of a base
(pyridine) so as to neutralize HCl which is formed during the reaction. It
shifts the equilibrium to the right-hand side.
 Acetylation of Salicylic Acid
The introduction of acetyl (CH3CO) group in alcohols or phenols is known as
acetylation. Acetylation of salicylic acid produces aspirin.

2. The bond between C-O is broken when alchohols react as electrophiles.

Reactions

 Reaction with hydrogen halides:

ROH + HX → R–X + H2O
Alchols react with hydrogen halide to form alkyl halides.
LUCAS TEST :
Lucas reagent = conc.HCl and ZnCl2
Alcohols are soluble in Lucas reagent while their halides are immiscible and produce
turbidity in solution.
case of tertiary alcohols, turbidity is produced immediately as they form the halides
easily.
Primary alcohols do not produce turbidity at room temperature.

 Reaction with phosphorus trihalides:

  Dehydration
Alchohols undergo dehydration (removal of a molecule of H2O) to form alkenes on
treating with a protic acid (H2SO4, H3PO4) or catalysts like anhyd. ZnCl2
Order of relative ease of dehydration:
Tertiary > Secondary > Primary
 Oxidation
Also known as Dehydrogenation ( removal of dihydrogen from the molecule)
Oxidising agent:
 CrO3 (Chromic anhydride)
 Pyridinium chlorochromate (PCC)
 Cu, 573K
 Acidified/ Alkaline KMnO4 (primary alc to COOH)
 Jones reagent (K2Cr2O7 and CrO3)
Oxidation of primary alcohols gives Aldehydes, secondary alcohols gives Ketones and
Tertiary alcohols give Alkenes.
Alcohols (On oxidation) Aldehydes(On oxidation)Carboxylic acids
Oxidation of :
 Primary alcohol  Aldehyde
 Secondary alcohol  Ketone
 Tertiary alcohol  Alkene

3.Reactions of phenols
 Electrophilic Substitution – Nitration, Halogenation
 Kolbe’s reaction
Sodium phenoxide is more reactive than phenol towards electrophilic aromatic
substitution. Hence, it undergoes electrophilic substitution substitution with CO2 a
weak electrophile.
 Riemer-Tiemann reaction
On treating phenol with chloroform in the presence of sodium hydroxide, a –CHO
group is introduced at ortho position of benzene ring. This reaction is known as
Reimer - Tiemann reaction.
 Alcohol + Zn dust Benzene + ZnO
 Oxidation of phenol with chromic acid (Na2Cr2O7 and H2SO4) produces a
conjugated diketone known as benzoquinone.
 Ethers
 Williamson synthesis
It is an important laboratory method for the preparation of symmetrical and
unsymmetrical ethers. In this method, an alkyl halide is allowed to react with
sodium alkoxide

 Ethers are the least reactive of the functional groups. The cleavage of the C-O
bond in ethers takes place under drastic conditions with an excess of hydrogen
halides. The reaction of dialkyl ether gives two alkyl halide molecule.
 The order of reactivity of hydrogen halides is as follows:
HI > HBr > HCl

 Electrophilic Substitution Reactions

  Halogenation

 Friedal Crafts reaction

Anisole undergoes Friedel-Crafts reaction, i.e., the alkyl and acyl
groups are introduced at ortho and para positions by reaction with
alkyl halide and acyl halide in the presence of anhydrous aluminium
chloride (a Lewis acid) as catalyst.
 Nitration

 PHYSICAL PROPERTIES
1) The boiling points of alcohols and phenols increase with the increase in the number
of carbon atoms (increase in van der Waals forces).
2) In alcohols, the boiling points decrease with the increase of branching in the carbon
chain (because of a decrease in van der Waals forces with a decrease in surface
area).
3) The high boiling points of alcohols are mainly due to the presence of intermolecular
hydrogen bonding in them which is lacking in ethers and hydrocarbons.
Hence, boiling points of alcohols and phenols are higher in comparison to other
classes of compounds.
4) Solubility of alcohols and phenols in water is due to their ability to form hydrogen
bonds with water molecules.
The solubility decreases with increase in size of alkyl/aryl (hydrophobic) groups.
5) The weak polarity of ethers do not appreciably affect their boiling points which are
comparable to those of the alkanes of comparable molecular masses but are much
lower than the boiling points of alcohols as shown in the following cases

6)