ELECTRONIC STRUCTURE OF

ALCOHOLIC AND PHENOLIC

HYDROXYL GROUPS
In alcohols, both the oxygen
and the carbon attached to it
are sp3-hybridized.
Two of the four sp3-hybridized
orbitals of oxygen overlap
separately with 1s orbital of H
and an sp3-orbital of carbon of
the alkyl group to form O-H
and C-O sigma bonds
respectively while the
remaining two sp3-orbitals
contain lone pairs of electrons..
The C-O-H bond angle is
slightly less (108.9º) than the
tetrahedral angle (109º 28')
due to greater lone pair-lone
pair than lone pair-bond pair
repulsions.
The carbon-oxygen bond
length is 142 pm..
The O-H bond in phenols, like
the O-H bond in alcohols, is
formed by overlap of a sp3-
orbital of oxygen with 1s-
orbital of hydrogen while the
C-O bond is formed by the
overlap of a sp3-orbital of
oxygen with a sp2-orbital of
carbon of the benzene ring..
The C-O-H bond angle in
phenol is approx the same
(109º) as in methanol but the
carbon-oxygen bond length in
phenol is slightly less (136 pm)
than in methanol..
This is due to resonance as a
result of which carbon-oxygen
bond acquires some double
bond character because of
conjugation of the lone pair of
electrons of oxygen with the
benzene ring and sp2-
hybridised state of carbon..
Since the oxygen atom is more
electronegative than both
carbon and hydrogen, the
electrons of the C-O and the O-
H bonds are displaced towards
the oxygen atom.
As a result, the electron density
near the oxygen atom is
slightly higher than that near
carbon and hydrogen atoms..
An alcohol molecule is dipolar
in nature with the oxygen
carrying a partial negative
charge and carbon and
hydrogen each carrying a
partial positive charge.
This is supported by the fact
that methanol has a dipole
moment of 1.71 D..
Phenol, on the other hand, has
a smaller dipole moment (1.54
D) than methanol.
This is due to the reason that
the C-O bond in phenol is less
polar due to the electron-
withdrawing effect of the
benzene ring while in
methanol, C-O bond is more
polar due to electron-donating
effect of the CH3 group..
Due to this dipolar nature,
alcohols and phenols form
intermolecular hydrogen
bonds..
11.4.1. ELECTRONIC
STRUCTURE OF ETHERS
Ethers like water have a
tetrahedral geometry, i.e.,
oxygen is sp3-hybridized.
Two of the four sp3-orbitals of
the oxygen atom overlap with
sp3-orbitals of two alkyl
groups to form two sp3-sp3
sigma bonds..
The remaining two sp3-
orbitals of oxygen contain a
lone pair of electrons each.
The C-O-C bond angle in ethers
is slightly greater than the
tetrahedral angle due to
repulsive interactions between
the two bulky R groups..
The C-O-C bond angle in
methoxymethane (dimethyl
ether) has been found to be
111.7º while the C-O bond
length (141 pm) is almost the
same as in alcohols (142 pm)..
11.5. METHODS OF
PREPARATION OF ALCOHOLS
1. From Haloalkanes
When haloalkanes are heated
with aqueous sodium or
potassium hydroxide or moist
silver oxide, they undergo
hydrolysis to produce
alcohols..
R-X + KOH(aq) Δ → R-OH + KX
CH3CH2-Br + KOH(aq) Δ →
CH3CH2-OH + KBr
 C6H5CH2Cl + KOH(aq) Δ →
C6H5CH2-OH + KCl
CH3-I + AgOH → CH3-OH + AgI
2. From Alkenes
(i) Hydration of Alkenes
The term hydration means
addition of a molecule of
water.
The hydration of alkenes can
be carried out either indirectly
or directly..
In the indirect process, alkenes
are passed through conc.
H2SO4 to form alkyl hydrogen
sulphates.
These upon hydrolysis with
boiling water give alcohols..
CH2=CH2 + HOSO2OH →
CH3CH2-OSO2OH
CH3CH2-OSO2OH + H2O (Boil)
→ CH3CH2OH + H2SO4

Hydration of Unsymmetrical
Alkenes (Markovnikov’s Rule)
In case of unsymmetrical
alkenes, the addition of H2SO4
takes place in accordance with
the Markovnikov’s rule..
 CH3CH=CH2 + HOSO2OH →
CH3-CH(OSO2OH)-CH3 → CH3-
CH(OH)-CH3 + H2SO4
Reactive alkenes directly add a
molecule of water in presence
of mineral acids as catalyst to
form alcohols..
CH3-C=CH2 + H2O → CH3-
C(OH)-CH3
Mechanism of Hydration of
Alkenes
Step 1.
Electrophilic attack by
hydronium ion on alkene gives
a carbocation intermediate.
Addition of proton occurs on
carbon atom of double bond
yielding a more stable
carbocation..
CH3-CH=CH2 + H3O+ → CH3-
CH+-CH3 (2° carbocation)
Step 2.
Nucleophilic attack by water
on the carbocation gives
protonated alcohol..
CH3-CH+-CH3 + H2O → CH3-
CH(OH2+)-CH3
Step 3.
Deprotonation to form alcohol..
CH3-CH(OH2+)-CH3 + H2O →
CH3-CH(OH)-CH3 + H3O+
Hydroboration–Oxidation
Diborane (B2H6) is an electron
deficient molecule.
It reacts with alkenes to form
trialkylboranes which upon
subsequent oxidation with
alkaline H2O2 give alcohols..
3CH3CH=CH2 + B2H6 →
(CH3CH2CH2)3B
(CH3CH2CH2)3B + 3
H2O2/OH- → 3 CH3CH2CH2OH
+ H3BO3
The addition of borane to the
double bond occurs at the less
substituted carbon atom giving
anti-Markovnikov alcohols..
Oxymercuration–Reduction
Alkenes react with mercuric
acetate, (CH3COO)2Hg, to form
oxymercuration products
which upon reduction with
NaBH4 in basic medium give
alcohols.
This is called oxymercuration-
reduction and gives alcohols
corresponding to
Markovnikov’s addition of
water to alkenes without
rearrangement..
 CH3CH2CH=CH2 +
(CH3COO)2Hg →
oxymercuration product →
NaBH4/OH- → CH3CH2-
CH(OH)-CH3

Comparison of Hydration,
Hydroboration–Oxidation and
Oxymercuration–
Demercuration
Hydration of alkenes occurs
through carbocation
intermediates which may
rearrange to more stable
carbocations to give
rearranged alcohols..
3,3-Dimethyl-1-butene + H+ →
2° carbocation → 1,2-methyl
shift → 3° carbocation → 2,3-
Dimethyl-2-butanol
Hydroboration–oxidation and
oxymercuration–reduction do
not involve carbocation
intermediates and hence give
unrearranged alcohols..
3,3-Dimethyl-1-butene → (i)
B2H6 (ii) H2O2/OH- → 3,3-
Dimethyl-1-butanol
 3,3-Dimethyl-1-butene →
Hg(OCOCH3)2/NaBH4 → 3,3-
Dimethyl-2-butanol
 Q1.
Which of the following
carbocations is most likely to
undergo 1,2-hydride shift?
(a) CH₃–C⁺H–CH₃
(b) (CH₃)₃C⁺
(c) CH₃–CH₂–C⁺H₂
(d) CH₃–CH⁺–C(CH₃)₃
 Answer: (d)
Explanation:
In option (d), carbocation is
secondary next to a tertiary
carbon. A hydride shift
occurs to form a more stable
tertiary carbocation.
 Q2.
Rearrangement of 3°
carbocations is least likely in
which case?
(a) 2-Methyl-2-propyl
carbocation
(b) tert-Butyl
carbocation
(c) 2-Phenyl-2-propyl
carbocation
(d) 1,2-
Dimethylcyclopentyl
carbocation
 (b)
Answer: (b)
Explanation:
tert-Butyl carbocation is
already highly stabilized and
does not rearrange further.
 Q3.
During the hydration of 3,3-
dimethyl-1-butene, which
carbocation rearrangement
occurs?
(a) Hydride shift only
(b) Methyl shift only
(c) Both hydride and
methyl shift
(d) No rearrangement
 Answer: (b)
Explanation:
Initially a 2° carbocation forms,
which undergoes 1,2-methyl
shift to give a more stable 3°
carbocation. Final product =
2,3-dimethyl-2-butanol.
 Q4.
The major product of
hydration of 1-
methylcyclopentene is:
(a) 1-methylcyclopentanol
(b) 2-
methylcyclopentanol
(c) 3-
methylcyclopentanol
(d) 1,1-
dimethylcyclopentanol
 Answer: (b)
Explanation:
Initial carbocation forms at C-
1, then ring expansion (via
1,2-shift of ring bond)
produces a more stable 3°
carbocation at C-2, leading to
2-methylcyclopentanol.
 Q5.
Which carbocation will
undergo ring expansion most
readily?
(a) Cyclobutyl carbocation
(b) Cyclopentyl
carbocation
(c) Cyclohexyl
carbocation
(d) Cyclopropylmethyl
carbocation
 Answer: (a)
Explanation:
Cyclobutane is highly strained.
Ring expansion reduces strain
→ hence cyclobutyl
carbocation rearranges easily
to cyclopentyl carbocation.
 Q6.
1,2-hydride shift occurs during
the reaction of HBr with:
(a) 2-methylpropene
(b) 3,3-dimethyl-1-
butene
(c) 1-butene
(d) 2-butene
 Answer: (c)
Explanation:
1-butene forms a 1°
carbocation, which rearranges
by 1,2-hydride shift to a more
stable 2° carbocation, giving 2-
bromobutane.
 Q7.
During rearrangement of
carbocations, stability order is:
(a) 1° > 2° > 3° > benzyl
(b) benzyl > allyl > 3° >
2° > 1°
(c) 3° > benzyl > allyl > 2°
> 1°
(d) 3° > 2° > 1° > allyl >
benzyl
 Answer: (b)
Explanation:
Benzyl and allyl carbocations
are resonance-stabilized and
hence more stable than typical
alkyl carbocations.
 Q8.
Rearrangement during acid-
catalyzed hydration of 1,2-
dimethylcyclobutene gives:
(a) 1,2-dimethylcyclobutanol
(b) 1,1-
dimethylcyclobutanol
(c) 1,2-
dimethylcyclopentanol
(d) 2,2-
dimethylcyclopentanol
 Answer: (d)
Explanation:
Carbocation at cyclobutane
undergoes ring expansion to
cyclopentane carbocation,
stabilized further by methyl
substitution → product is 2,2-
dimethylcyclopentanol.
 Q9.
The rearrangement in 3-
methyl-2-butanol dehydration
follows which pathway?
(a) E1 with hydride shift
(b) E2 without
rearrangement
(c) E1 with methyl shift
(d) E1cb
 Answer: (a)
Explanation:
Carbocation intermediate
forms during E1 dehydration.
1,2-hydride shift stabilizes it,
then elimination gives major
alkene.
 Q10.
What is the major product
when 1,2-
dimethylcyclopentanol
undergoes acid dehydration?
(a) 1,2-
dimethylcyclopentene
(b) 1,1-
dimethylcyclopentene
(c) 1-methylcyclohexene
(d) 2-methylcyclohexene
 Answer: (c)
Explanation:
Carbocation forms, then ring
expansion occurs from 5-
membered to 6-membered
ring, giving 1-
methylcyclohexene as the
major product.
 Q11.
Carbocation rearrangement in
acid-catalyzed hydration of 3-
methyl-1-butene leads to:
(a) 3-methyl-1-butanol
(b) 2-methyl-2-butanol
(c) 3-methyl-2-butanol
(d) 2-methyl-1-butanol
 Answer: (b)
Explanation:
1° carbocation at C-1
undergoes methyl shift →
stable 3° carbocation → 2-
methyl-2-butanol.
 Q12.
Which reaction shows ring
expansion via carbocation?
(a) Nitration of benzene
(b) Dehydration of
cyclobutanol
(c) Friedel-Crafts
alkylation of toluene
(d) Bromination of
ethane
 Answer: (b)
Explanation:
Dehydration of cyclobutanol
forms cyclobutyl carbocation,
which undergoes ring
expansion to cyclopentyl
carbocation → gives
cyclopentene.
 Q13.
The intermediate carbocation
in hydration of 3,3-dimethyl-1-
butene is:
(a) Primary
(b) Secondary
(c) Tertiary after
rearrangement
(d) Allylic
 Answer: (c)
Explanation:
Initially secondary carbocation
forms, then 1,2-methyl shift
gives tertiary carbocation.
 Q14.
Which rearrangement is more
favorable?
(a) 1° → 2° hydride shift
(b) 2° → 3° methyl shift
(c) 2° → 3° hydride shift
(d) 3° → 2° hydride shift
 Answer: (b)
Explanation:
Both hydride and methyl shifts
occur to increase carbocation
stability, but 2° → 3° (methyl
shift) gives maximum
stabilization.
 Q15.
When cyclobutylmethyl
carbocation is formed, it
stabilizes by:
(a) Hydride shift
(b) Ring contraction
(c) Ring expansion
(d) Resonance
 Answer: (c)
Explanation:
Cyclobutylmethyl carbocation
undergoes ring expansion to
form cyclopentyl carbocation,
which is more stable.
 Q16.
Which compound upon acid-
catalyzed hydration gives
rearranged product?
(a) 2-methylpropene
(b) 3-methyl-1-butene
(c) Cyclohexene
(d) Ethene
 Answer: (b)
Explanation:
3-methyl-1-butene forms 1°
carbocation at first, which
undergoes rearrangement to
3° carbocation → rearranged
alcohol.
 Q17.
In acid-catalyzed hydration of
2,2-dimethyl-1-butene, the
major alcohol is:
(a) 2,2-dimethyl-1-butanol
(b) 2,2-dimethyl-2-
butanol
(c) 3,3-dimethyl-2-
butanol
(d) 2,2-dimethyl-3-
butanol
 Answer: (b)
Explanation:
Carbocation formed is tertiary
at C-2 → stable → product is
2,2-dimethyl-2-butanol (no
rearrangement needed).
 .

Q18.
The major product in
dehydration of 1-
methylcyclobutanol is:
(a) 1-methylcyclobutene
(b) 1-
methylcyclopentene
(c) 2-methylcyclopentene
(d) 1,2-
dimethylcyclobutene
 Answer: (b)
Explanation:
Carbocation forms at C-1, then
ring expansion from
cyclobutane to cyclopentane
occurs → final alkene = 1-
methylcyclopentene.