Alcohols, Phenols and Ethers C HAP T ER :7

ALCOHOLS CLASSIFICATION OF ALCOHOLS

Alcohol contains one or more hydroxy (OH) group(s) • C2H5OH : Monohydric alcohol
directly attached to a carbon atom. • CH2OH-CH2OH : Dihydric alcohol
-H -H
CH4 CH OH R—H R—OH • HOH2C-CHOH-CH2OH : Trihydric alcohol
+OH 3 +OH alcohol
Methane Methyl alcohol

NOMENCLATURE OF ALCOHOLS
Common and IUPAC Names of Some Alcohols

Compound Common Names IUPAC Names

CH3–OH Methyl alcohol Methanol
CH3–CH2–OH Ethyl alcohol Ethanol
CH3–CH2–CH2–OH n-Propyl alcohol Propan-1-ol
CH3–CH–CH3 Isopropyl alcohol Propan-2-ol
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OH
CH3–CH2–CH2–CH2–OH n-Butyle alcohol Butan-1-ol
CH3–CH–CH2–CH3 sec-Butyl alcohol Butan-2-ol
|
OH
CH3–CH–CH2–CH3 Isobutyl alcohol 2-Methylpropan-1-ol
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OH
CH3 tert-Butyl alcohol 2-Methylpropan-2-ol
|
CH3–CH–OH
|
CH3
CH2–CH–CH2 Glycerol Propane-1,2,3-triol
| | |
OH OH OH

• Cyclic alcohols are named using the prefix cyclo and considering the -OH group attached to C-1

OH
OH

CH3
Cyclohexanol
2-Methyl Cyclopentanol
PREPARATION OF ALCOHOLS • Dehydration of Alcohol : Dehydration of
• By Hydrolysis of Haloalkanes : alcohols takes place in acidic medium. Intra-
R-X + aq.KOH → ROH + KX molecular dehydration leads to the formation of
• By Reduction of Carbonyl Compounds : alkene while inter molecular dehydration which
4RCOOH + 3LiAlH4 → 4RCH2OH (1°alcohol) forms ether. Ease of dehydration: 3° > 2° > 1°
• Hydroboration-Oxidation : • Satyzeff’s Rule : Elimination through b carbon
containing minimum b hydrogen.
B2H6/THF/H2O2
H3C H3C CH3
CH2 OH CH3—C—CH2—O—H + H+
Anti Markonikov’s Addition conc. H2SO4
CH3
• Hydroxylation of Alkenes : CH3
OH
Dil.KMnO4 or OsO4 CH3—C—CH2—O+—H

OH CH3 H
syn-Hydroxylation • Oxidation of Alcohol:
RCH2–OH + [O] → RCHO → RCOOH
OH RCH2 + OH + [O] + PCC → RCHO
RCO3 H/H-
• Haloform Reaction: Compound containing
OH CH3CO–group (or compound on oxidation gives
anti-Hydroxylation CH3CO–group) which is attached with a C or H, in
presence of halogen and mild alkali gives halo-
PHYSICAL PROPERTIES form. CH3-CH2-COCH2-CH3, CH3-CO-Cl. CH3COOH
will not respond to haloform reaction while
OF ALCOHOL CH3CH2OH will respond to haloform Reaction.
• Lower alcohols are liquid at room temperature H O
while higher ones are solid. Cl2
CH3—C—OH CH3—C—H
• High boiling point due to presence of O.A. -HCl
intermolecular hydrogen bonding. Order of H
Boiling Point : primary > secondary > tertiary Cl + NaOH
CH3CH2OH 2 CHCl3
• Solubility in water decreases with increase in
molecular mass due to decrease in extent of
intermolecular hydrogen bonding.
Test for Alcohols
CHEMICAL PROPERTIES
Lucas Test Victor Meyer test
OF ALCOHOL
• Alcohol’s Reaction with Metal :
ROH + Na→2RO+Na– + H2
USES OF ALCOHOL
• Formation of Halides : 3ROH + P+l2→3Rl + H3PO3
• Denatured alcohol : A toxic alcohol used as a fuel
• Reaction with HNO3: R-OH + HO-NO2→R-O-NO2 or solvent.
• Reaction with Carboxylic Acid (Esterification) • Rubbing alcohol : A denatured alcohol used in
: R-OH + R’-COOH + H+ ↔ R’ - COOR topical applications.
• Reaction with Grignard Reagent : • Propanol : Used to sterilize
R’OH + RMgX→RH + R’OMgX • Alcoholic beverages : Any drink containing
• Reduction of Alcohol: ethanol.
ROH + 2HI + Red P→RH + I2 + H2O • Alcohol fuel: An alternative fuel
PHENOLS • Aromatic Nucleophilic Substitution of Nitro
• A Phenol contains one or more hydroxyl group Aryl Halides
(OH) attached to a carbon atom (s) of the Cl ONa
benzene ring. NaOH
C6H5—H -H C6H5OH O2N O2N
+OH (Phenol)
• Distillation of phenolic acids with soda-lime
• The simplest hydroxy derivative of benzene is
produces phenols, e.g. sodium salicylate
phenol, it is its common name and also an
gives phenol.
accepted IUPAC name. As the structure of phenol
involves a benzene ring, in its substituted Cl ONa
NaOH
compounds the terms ortho (1,2-disubstituted), CaO
meta (1,3-disubstituted) and para (1,4-disubsti- CO2Na
tuted) are often used in the common names.
OH CH3 CH3 CH3
OH PHYSICAL PROPERTIES
OH
OF PHENOLS
• Phenol is a colourless, toxic, corrosive, needle
OH shaped solid.
Common
Name: Phenol o-Cresol m-Cresol p-Cresol • Phenol liquifies easily due to high hygroscopic
IUPAC nature.
Phenol 2-Methyl 3-Methyl 4-Methyl
Name: • Phenol is less soluble in water, but readily soluble
phenol phenol phenol
in organic solvents.
• Dihydroxy derivatives of benzene are known as 1, • Simplest phenols, because of hydrogen bonding
2-, 1, 3- and 1, 4-benzenediol. have quite high boiling points.
OH OH OH • o-nitrophenol is, steam volatile and also is less
OH soluble in water because of intramolecular
hydrogen bonding.
OH

Common
OH CHEMICAL PROPERTIES
Name: Catechol Resorcinol Quinol
OF PHENOLS
Hydroquinone
IUPAC • Formation of Esters : Phenyl esters (RCOOAr)
Benzene-1, Benzene-1, Benzene-1, are not formed directly from RCOOH. Instead,
Name:
2-diol 3-diol 4-diol acid chlorides or anhydrides are reacted with
ArOH in the presence of strong base.
PREPARATION OF PHENOL (CH3CO)2O + C6H5OH + NaOH CH3COOC6H5 +
CH3COONa + H2O
• Hydrolysis of chlorobenzene: (Dow’s process)
• Displacement ∆
of OH group :
Cl ONa OH ArOH + Zn ArH + ZnO (poor yields)
NaOH H+
360°C; 320 atm • Hydrogenation :
OH OH
• Alkali fusion of Sodium benzene sulphonate Ni, 175°C, 15 atm
+ 3H2
SO3Na ONa + OH
NaOH H Cyclohexanol
350°C
• Oxidation to Quionones:
OH O
USES OF PHENOLS
O2 • Several commercial compounds are synthesized
from a precursor containing phenol.
or CrO2
phenol • Phenol is included in the production of plywood,
O ear and nose drops and disinfectants.
benzo-1, 4-quinone
• Phenol are widely used as an antiseptic and disin-
• Electrophilic Substitution: The –OH and fectant in several mouthwash, deodorant, lotion
—O(phenoxide) are strongly and soap.
activating, i.e., ortho, para-directing.
OH OH OH • They also used in manufacturing of drugs like
H aspirin, salo, phenacetin, salicylic acid etc.
E- E
+ • Phenol used in manufacturing of resins like bakali-
te which used in manufacturing of electrical
phenol H E goods like plugs and switches etc.
Oxonium cations
O O O • The nitro derivatie of phenol like 2,4,6-trinitrophe-
H nol (picric acid) used to make explosives and
E- E dyeing wool and silk.
+
• Phenols are also used in preparation of other
phenoxide H E chemicals like; azo dyes, phenolphthalein and
anion Fairy stable
unsaturated ketones Cyclohexane.
Special mild conditions are needed to achieve
electrophilic monosubstitution in phenols because
their high reactivity favors both polysubstitution
and oxidation.

ETHERS
• An ether contains an alkoxy/aryloxy group (R-O/Ar-O)in place of the H atom of a hydrocarbon.
-H -H
R—H R—O—R Ar—H Ar—O—R
+RO- (aliphatic ether) +RO- (Aromatic ether)
• Common names of ethers are derived from the names of alkyl/aryl groups written as separate words in
alphabetical order and adding the word `ether’ at the end. For example, CH3OC2H5 is ethyle methyl ether. If
both the alkyl groups are the same, the prefix `di’ is added before the alkyl group. For example, C2H5OC2H5
is diethyl ether.
• Structures of Functional Group-In alcohols, the oxygen of the -OH group is attached by a sigma σ bond
formed by the overlap of an sp3 hybridised orbital of carbon with an sp3 hybridised orbital of oxygen.
• According to the IUPAC system of nomenclature, others are regarded as hydrocarbon derivatives in which
a hydrogen atom is replaced by an -OR or -OAr group, where, R and Ar represent alkyl and aryl groups,
respectively. The larger (R) group being chosen as the parent hydrocarbon. The names of a few ethers are
given as examples in the Table below :
Common and IUPAC Names of Some Ethers

Compound Common Names IUPAC Names

CH3OCH3 Dimethyl ether Methoxymethane
C2H5OC2H5 Diethyl ether Ethoxyethane
CH3OCH2CH2CH3 Methyl n-propyl ether 1-Methoxypropane
C6H5OCH3 Methylphenyl ether (Anisole) Methoxybenzene (Anisole)
C6H5OCH2CH3 Ethylphenyl ether (Phenetole) Ethoxybenzene
C6H5O(CH2)6–CH3 Heptylphenyl ether 1-Phenoxyheptane
CH3O–CH–CH3 Methyl isopropyl ether 2-Methoxypropane
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CH3
C2H5–O–CH2–CH2–CH–CH3 Phenylisopentyl ether 3-Methylbutoxybenzene
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CH3
CH3–O–CH2–CH2–OCH3 — 1,2-Dimethoxyethane
H3C CH3 2-Ethoxy-1,1
OC2H5 Dimethylcyclohexane

PREPARATION OF ETHERS
• From alcohols :
H SO
CH3CH2OH 2 4 CH3CH2–O–CH2CH3
140°C
Ether
• Williamson’s synthesis :
R-X + Na+ -O-R’ → R-O-R’ + Na+X-
In case of tertiary substrate, elimination occurs giving alkenes.
From alkenes :
CH3 CH3
H2SO4
CH3—C=CH2+ H—OCH3 CH3—C—OCH3
CH3
• From Grignard reagent : Treating α halo ethers with suitable Grignard reagents.
Dry Cl
CH3—O—CH2Cl + CH3Mgl ether CH3—O—CH2CH3 + Mg
l
On standing in contact with air, most aliphatic ethers are converted slowly into unstable peroxides. The
presence of peroxides is indicated by formation of a red colour when the ether is shaken with an aqueous
solution of ferrous ammonium sulphate and potassium thiocyanate.
CHEMICAL PROPERTIES OF ETHERS
• Halogenation of Ethers :
Cl Cl
CH3CH2–O–CH2CH3 2 CH3CH2–O–CHCH3 2 CH3CH–O–CHCH3
Cl Cl Cl
• Ethers as base : H
CH3CH2–O–CH2CH3+ H–Br → CH3CH2–O–CH2CH3Br–
+
• Reaction With cold conc. HI/HBr :
R—O—R’ + Cold HI R-OH + R’I (R’<R)

• Hot conc. HI/HBr :

R—O—R’ + Hot HI RI + R’I + H2O

• Electrophilic substitution reactions :

OCH3 OCH3 OCH3 OCH3 OCH3 OCH3
Br2/CS2 Br conc.HNO3 NO2
+ +
conc.H2SO4
Anisole o-bromoanisole Br Anisole o-Nitroanisole NO2
p-bromoanisole p-Nitroanisole

USES OF ETHERS
• In the past, ethers were commonly used as a general anaesthetic in surgery. They are no longer a common
anaesthetic due to their high flammability.
• Useful solvents for other organic compounds such as fats and oils.
• Ethers with higher molecular masses can be used as solvents for varnishes and lacquers.
• Dimethyl ether is used as a propellant for aerosol sprays.
• Produces excellent relaxation of the muscles, pulse rate and rate of respiration.