11.

Alcohols, Phenols and Ethers

Classification of alcohols and phenols: Mono, di, tri or polyhydric

On the basis of hybridisation Csp OH

3

Primary, secondary and tertiary Allylic alcohols Benzylic alcohols

Csp OH
2

Vinylic alcohol

Phenol

Classification of ethers: Simple or symmetrical C2H5OC2H5, C6H5OC6H5 Mixed or unsymmetrical C2H5OCH3, CH3OC6H5 Common names of some phenols:

Alcohols and phenols: Preparation of alcohols From alkenes Acid catalysed hydration

[According to Markovnikovs rule] Hydroboration oxidation

 From carbonyl compounds By reduction of aldehydes and ketones. Aldehydes give 1 and ketones give 2 alcohols.
RCHO H2
Pd

RCH2OH

By reduction of carboxylic acids and esters

RCOOH RCOOR
i LiAlH 4 ii H 2 O

RCH 2OH RCH 2OH R OH

H2

catalyst catalystic hydrogenation

From Grignard reagents

Methanol gives 1 , other aldehydes give 2 , and ketones give 3 alcohols. Preparation of phenols From haloarenes

From benzenesulphonic acid

 From diazonium salts

From cumene

Physical properties of alcohols and phenols Boiling points: The boiling points of alcohols and phenols increase with increase in number of carbon atoms as it involves increase in van der Waals forces. The boiling points of alcohols decrease with increase of branching. This is because van der Waals forces decrease with decrease in surface area. Solubility: Alcohols and phenols form H-bonds, so they are soluble in water. Their solubility decreases with increase in size of alkyl/aryl groups. Chemical reactions: Alcohols react both as nucleophiles and electrophiles Reactions that involve cleavage of O H bond Acidity of alcohols and phenols Reaction with metals
2ROH 2Na 2R O Na H 2 Sodium alkoxide

 Acidity of alcohols The increasing order of acidity of alcohols is

Acidity of phenols Phenols are more acidic than alcohols and water. Electron-withdrawing groups increase the acidity of phenols while electron-releasing groups decrease the acidity of phenols. Esterification
R/ArOH R COCl
Pyridine

R/ArOCOR

HCl

Acetylation of salicylic acid

Reactions that involve cleavage of C O bond in alcohols Reaction with hydrogen halide
ROH HX RX H2O

Lucas test Used for distinguishing between 1, 2 and 3 alcohols. (Lucas reagent Concentrated HCl and ZnCl2) Reaction with phosphorus trihalide
3R OH PX3 3R X H3PO3 X Cl,Br

 Dehydration Treated with concentrated H2SO4 or H3PO4 or Anhyd. ZnCl2, or Al2O3

The order of increasing reactivity towards dehydration is 1 alcohol < 2 alcohol < 3 alcohol Oxidation (also known as dehydrogenation) It involves formation of a carbonoxygen double bond. Oxidising agent Acidified KMnO4
Alcohol
directly

Carboxylic acid

Oxidising agent Anhyd. CrO3 1 alcohol Aldehyde alcohol Ketone Pyridinium chlorochromate (PCC) 1 alcohol Aldehyde Oxidising agent Heated Cu at 573 K 1 alcohol Aldehyde alcohol Ketone 3 alcohols do not undergo oxidation Reactions of phenols: Electrophilic aromatic substitution reaction Nitration

The o-isomer is steam volatile due to intramolecular H-bonding while the p-isomer is less volatile due to intermolecular H-bonding. So, they can be separated by steam distillation.

 Halogenation

Kolbes reaction

ReimerTiemann reaction

Reaction of phenol with zinc dust

 Oxidation

Ethers: Preparation of ethers By dehydration of alcohols

Williamson synthesis

But in case of 2 and 3 halides, instead of substitution, elimination takes place, resulting in alkenes. Phenols are converted into ethers.

Physical properties of ethers Boiling points:

The boiling points of ethers are lower than those of alcohols of comparable molecular masses due to the presence of H-bonding in alcohols. Chemical reactions of ethers: Cleavage of C O bond Least reactive; under drastic conditions with excess of hydrogen halides, the C O bond is cleaved

The order of increasing reactivity of hydrogen halides is HCl < HBr < HI Electrophilic substitution Halogenation

Friedel Crafts alkylation

Friedel Crafts acylation

 Nitration

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