Chapter Five

ALCOHOLS AND PHENOLS

 Introduction
 Alcohols and phenols can be thought of as organic derivatives
of water in which one of the water’s hydrogen's is replaced by
an organic group.
 The group name alcohol is restricted to compounds that have
their -OH group bonded to a saturated, SP3-hybridized carbon
atom.
 Compounds with their -OH group bonded to a vinylic, SP2-
hybridized carbon are called enols.
 Phenol is sometimes called hydroxybenzene.
 Naming Alcohols and Phenols
 Alcohols are classified as primary (1°), secondary (2°), or
tertiary (3°), depending on the number of organic groups
bonded to the hydroxyl-bearing carbon.

 Alcohols are named by the IUPAC system as derivatives of

the parent alkane, using the suffix –ol.
 Rule 1: Select the longest carbon chain containing the
hydroxyl group (OH).
 Rule 2: Number the alkane chain beginning at the end nearer
the hydroxyl group (OH).
 Cont.…..
 Rule3: Number the substituents according to their position
on the chain, and write the name, listing the substituents in
alphabetical order and identifying the position to which the -
OH is bonded.
 Properties of Alcohols and Phenols
 Alcohols and phenols have nearly the same geometry around
the oxygen atom as water.
 The R-OH bond angle has an approximately tetrahedral value
(108.5° in methanol) and the oxygen atom is sp3-hybridized.
 Also like water, alcohols and phenols have higher boiling
points than might be expected because of hydrogen-bonding.
 A positively polarized -OH hydrogen atom from one molecule
is attracted to a lone pair of electrons on the electronegative
oxygen atom of another molecule, resulting in a weak force
that holds the molecules together.
 Cont.…..
 Another similarity with water is that alcohols and phenols are
both weakly basic and weakly acidic.
 As weak bases, they are reversibly protonated by strong acids
to yield oxonium ions, RO+H2.

 As weak acids, they dissociate slightly in dilute aqueous

solution by donating a proton to water, generating H3O+ and an
alkoxide ion, RO-, or a phenoxide ion, ArO-.
 Cont.…..
 Example:

 The effect of alkyl substitution on alcohol acidity is due

primarily to solvation of the alkoxide ion formed on acid
dissociation.
 The more readily the alkoxide ion is solvated by water, the
more stable it is, and the greater the acidity of the parent
alcohol.
 Cont.…..
 For example, the oxygen atom of an unhindered alkoxide ion,
such as that from methanol, is sterically accessible and is
easily solvated by water.
 The oxygen atom of a hindered alkoxide ion, however, such
as that from tert-butyl alcohol, is less easily solvated and is
therefore less stabilized.
 Cont.…..
 Phenols are more acidic than alcohols because the phenoxide
anion is resonance-stabilized.
 Delocalization of the negative charge over the ortho and para
positions of the aromatic ring results in increased stability of
the phenoxide anion relative to un-dissociated phenol.
 Substituted phenols can be either more acidic or less acidic
than phenol itself, depending on whether the substituent is
electron-withdrawing or electron-donating.
 Phenols with an electron-withdrawing substituent are more
acidic because these substituents delocalize the negative
charge.
 Phenols with an electron-donating substituent are less acidic
because these substituents concentrate the charge.
 Cont.…..
 The acidifying effect of an electron-withdrawing substituent
is particularly noticeable in phenols with a nitro group at the
ortho or para position.
 Preparation of Alcohols and phenols
 Alcohols are prepared by the following methods:
1. From alkenes
(i) By acid catalyzed hydration: Alkenes react with water in the
presence of acid as catalyst to form alcohols.
 In case of unsymmetrical alkenes, the addition reaction takes
place in accordance with Markovnikov’s rule.
 Cont.…..
ii) By hydroboration–oxidation: Borane (BH3) reacts with
alkenes to give alkyl boranes as addition product.
 This is oxidized to alcohol by hydrogen peroxide in the
presence of aqueous sodium hydroxide.
 Addition to being regioselective for formation of anti-
Markovnikov alcohols.
 Cont.…..
Cont..
 Cont.…..
Cont.…
 Cont.…
2. From carbonyl compounds.
i) By reduction of aldehydes and ketones.
 Aldehydes and ketones are reduced to the corresponding
alcohols by addition of hydride ion.
 It is prepared by treating aldehydes and ketones with sodium
borohydride (NaBH4) or lithium aluminum hydride (LiAlH4).
 Aldehydes yield primary alcohols whereas ketones give
secondary alcohols.
 The principle behind the hydride reducing agents is the
presence of a polar covalent bond between a metal and
hydrogen.
 Because of higher electronegativity, the hydrogen bears
higher electron density which eventually makes it react as a
hydride ion.
 Cont.…
Cont.….
 Cont.…
 Phenol can be prepared by the following methods.
1. From halo-arenes:
 Chloro-benzene is fused with NaOH at 623K and 320 atm.
 Phenol is obtained by acidification of sodium phenoxide so
produced .
 Cont.…
[Link] benzene-sulfonic acid:
 Benzene is sulphonated with oleum (H2SO4) and benzene
sulfonic acid so formed is converted to sodium phenoxide on
heating with molten sodium hydroxide.
 Acidification of the sodium salt gives phenol.
 Cont.…
3. From diazonium salts:
 A diazonium salt is formed by treating an aromatic primary
amine with nitrous acid (NaNO2 + HCl) at 273-278 K.
 Diazonium salts are hydrolyzed to phenols by warming with
water or by treating with dilute acids.
 Cont.…
Cont.….
 Reactions of Alcohols and Phenol
1. Conversion of Alcohols into Alkyl Halides.
 Tertiary alcohols react with either HCl or HBr at 0 °C by an
SN1 mechanism through a carbocation intermediate.
 The reaction of a tertiary alcohol with HX takes place by an
SN1 mechanism when acid protonates the hydroxyl oxygen
atom, water is expelled to generate a carbocation, and the
cations reacts with nucleophilic halide ion to give the alkyl
halide product.
 Cont.….
 Primary and secondary alcohols are much more resistant to
acid, however, and are best converted into halides by treatment
with either SOCl2 or PBr3 through an SN2 mechanism.
 Hydroxide ion itself is too poor a leaving group to be
displaced by nucleophiles in SN2 reactions, but reaction of an
alcohol with SOCl2 or PBr3 converts the -OH into a much
better leaving group.
 Cont.….
2. Dehydration of Alcohols to yield Alkenes:
 Acid-catalyzed dehydrations usually follow Zaitsev’s and
yield the more stable alkene as the major product.

 Alcohol dehydrations carried out also with Phosphorus

oxychloride (POCl3) in pyridine take place by an E2
mechanism.
 Pyridine is both the reaction solvent and the base that
removes a neighboring proton in the E2 elimination step.
 Cont.….
Mechanism of the reaction
 Cont.….
3. Oxidation of alcohol
 Perhaps the most valuable reaction of alcohols is their
oxidation to give carbonyl compounds the opposite of the
reduction of carbonyl compounds to give alcohols.
 Primary alcohols yield aldehydes or carboxylic acids.
 Secondary alcohols yield ketones, but tertiary alcohols don’t
normally react with most oxidizing agents.
 Cont.….
 Primary alcohols are oxidized to either aldehydes or
carboxylic acids, depending on the reagents chosen and the
conditions used.
 Older methods were often based on Cr(VI) reagents such as
CrO3 or Na2Cr2O7.
 But a more common current choice for preparing an aldehyde
from a primary alcohol in the laboratory is to use the I(V)-
containing Dess–Martin periodinane (DMP) in
dichloromethane solvent.
 Cont.….
Mechanism of the reaction
 Cont.….
 Most other commonly used oxidizing agents, such as
chromium trioxide (CrO3) in aqueous acid, oxidize primary
alcohols directly to carboxylic acids.
 An aldehyde is involved as an intermediate in this reaction
but can’t usually be isolated because it is further oxidized too
rapidly.
 Cont.….
 Following reactions are shown by phenols only.
1. Electrophilic aromatic substitution.
 In phenols, the reactions that take place on the aromatic ring
are electrophilic substitution reactions.
 The –OH group attached to the benzene ring activates it
towards electrophilic substitution.
 Also, it directs the incoming group to ortho and para
positions in the ring as these positions become electron rich
due to the resonance effect caused by –OH group.
i) Nitration of phenol
 Cont.….
ii) Halogenation: On treating phenol with bromine, different
reaction products are formed under different experimental
conditions.

 The usual halogenation of benzene takes place in the

presence of a Lewis acid, such as FeBr3 which polarizes the
halogen molecule.
 In case of phenol, the polarisation of bromine molecule takes
place even in the absence of Lewis acid.
 It is due to the highly activating effect of –OH group attached
to the benzene ring.
 Cont.….
2. Kolbe’s reaction
 Phenoxide ion generated by treating phenol with sodium
hydroxide is even more reactive than phenol towards
electrophilic aromatic substitution.
 Hence, it undergoes electrophilic substitution with carbon
dioxide, a weak electrophile.
 Ortho hydroxybenzoic acid is formed as the main reaction
product.
 Cont.….
3. Reimer-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.
 The intermediate substituted benzyl chloride is hydrolyzed in
the presence of alkali to produce salicylaldehyde.

End