Chemical Reactions of

Alcohols
Chapter - Alcohols, Phenols and Ethers Explained by - Gopika Arora
Subject - Chemistry Undergraduate, IIT Delhi
Class - 12

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 Topics to be covered
● Reactions involving cleavage of O-H bond

● Reactions involving cleavage of C-O bond 5

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 Reactions involving cleavage of O-H bond
● Acidity of alcohols and phenols-
1. Reaction with metals
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2. Acidity of alcohols
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3. Acidity of phenols
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● Esterification
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Reaction with metals
● Alcohols and phenols react with active metals like Na, K and Al to give
corresponding alkoxides/ phenoxides and hydrogen

Phenols also
react with aq
NaOH to give
These reactions prove that alcohols and sodium
phenols are Bronsted acids (give proton to phenoxides
stronger base)
Acidity of alcohols
● Acidic due to polar nature of O-H bond
● e- releasing grp increases e- density and decreases acid strength
(primary>secondary>tertiary alcohol)
● They're weaker acids than water
Acidity of phenols
● Acidic as seen from reaction with metals
● Due to resonance, the O oh –OH group of phenol is positive
● Stronger acids than water as seen by reaction with aq NaOH
● Stronger acids than alcohols as the phenoxide acid is much more stable than alkoxide
due to resonance
● In substituted phenols, e- withdrawing grps enhance acidic strength and vice versa
Esterification
● Alcohols and phenols react with carboxylic acids, acid chlorides and acid anhydrides
to from esters
● Reaction with anhydride is performed in presence of some conc H2SO4 and water is
removed as soon as it’s formed as it is a reversible reaction
● Reaction with acid chloride is done in presence of pyridine to neutralize HCl formed
● Introduction of acetyl (CH3CO) group is called acetylation. Acetylation of salicylic
acid produces aspirin
Reactions involving cleavage of C-O bond
● With hydrogen halides
● With phosphorous trihalides
● Dehydration
● oxidation
With hydrogen halides
● Alcohols react with hydrogen halides to form alkyl halides
● The difference in reactivity of 3 classes of alcohols distinguishes them(Lucas test-
conc HCl and ZnCl2)
● Primary alcohols don’t produce turbidity at RT, secondary take some time and
tertiary produce turbidity immediately by reacting to from halides
With phosphorous trihalides
● Alcohols are converted to alkyl bromides by reaction with PBr3
Dehydration
● From alkenes on treating with protic acid or catalysts like anhydrous ZnCl2 or
alumina by dehydration (losing water molecule)
● Relative ease of dehydration – tertiary>secondary>primary
Oxidation
● Involves formation of C=O with cleavage of O-H and C-H bonds
● Also called dehydrogenation due to loss of dihydrogen
● Depending on agent, primary alcohol is oxidized to aldehyde and in turn to
carboxylic acid
● Tertiary alcohols don’t undergo unless under strong conditions when C-C cleavage
takes place and acids of less C atoms are formed
● Strong oxidizing agents like a KMnO4 give acid directly
● CrO3 and PCC(pyridinium chlorochromate) (better for primary alcohols) give
aldehydes
 Thank you

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