CarooCauuon ( OiSadi

O uenyloutane

act both as
Rcept-Based.Queetlons
acids and bases.
Aleohols can Explain.
Alcohols can bases
act
asinacids in strongly basic medium by releasing H*
the acidic medium.
ion. Similarly, they can

act as
Lewis

R-0-H+OH R - ö + H;0;R- -H +H*R-ö-H

Acid (Base) Alkoxide ion Base (Acid) Protonated alcohol

Sodium metal can not be used for drying alcohols. Assign reason.
Sodium metal reacts with alcohol to evolve hydrogen gas. Moreover, it also catches fire in hatr.
Therefore, it can not be used for drying alcohol.
2CgH,OH + 2Na 2C2H,ONa +H2
Ethanol Sod. ethoxide
Ethyl alcohol and dimethyl ether are isomerlc but alcohol is a liquid at room temperature
whle ether is a gas. Explain.
Ethyl alcohol molecules are associated due to intermolecular hydrogen bonding but the same
s not present in the molecules of dimethyl ether. As a result of association, ethyl alcohol is a
ligquid at room temperature while dimethyl ether is a gas.
At room temperature tertiary alcohols form white turbidity very fast with Lucas reagent
wnle primary alcohols do not. Glve reason.
Acarbocation HC1(g)
intermediate is formed when with alcohol in the
reacts an presence of
antydrous ZnClh (dehydrating agent). Since tertiary carbocation is very stable while primary
is rather fast Lucas reagent to
Carbocation unstable therefore, alcohols react very with
tertiary
formWne turbidity immediately while the primary alcohols do not react at room temperature.
Slow Cl

R R-C
R-0-H+H-C1 R-0-H
Carbocation Alkyl chloride
Alcohol Protonated
alcohol
 Predict the product of the reaction between HBr and Dul-z-en-1-o1.
Q.5.
CH-CH-CH-CH2-OH CH-CH=CH-CH2-ÕH2 0
Ans.
But-2-en-1-0o CH-CHe
CH3-CH-CH=CH, <-H
HBr CH,
Br
3-Bromobut-1-ene Catbs at
Q.6.
Hydration of 3-phenylbut-1-ene in dilute H2S04 forms 2-phenylbuts.

3-phenylbutan-2-ol. Why?
The secondary carbocation initially formed as a result of hydration chanoes
phenylbutan-2-d
Ans.
carbocation
tertiary H* ion shift. Therefore, the final product is differenten
by from the en
product.

Hi ion
H,C-CH-CH =CH2 HC-¢-H-CH-CHin HC--C
CHs CgHs
2° Carbocation
CA
3-Phenylbut-1-ene 3 Carbocatin
(Less stabe) (More stable

HO
OH
-H
H3C-C-CH2-CH3 H3C-C-CH-
CgHs CgHs
2-Phenylbutan-2-ol
Q7. On
reacting tertiary butyl alcohol and normal butyl alcohol separately with a few
dilute KMn04, purple colour drop
disappears and a brown precipitate is formed only in u
Which of the two alcohols will
respond to the reaction '
Ans Only n-butyl alcohol is oxidised under the reaction
react.
conditions while tertiary butyl ai

CHCHCHCH,OH +KMnO4 CH^CH2CH,COOK+Mn0

n-butyl alcohol +KO
(Purple) Pot. salt of n-butyric acid Brown ppt.
 of water in the presence of concentrated sulphuric
a molecule
n-2-ol loses as the major product. Suggest a suitable mechanism.
reletramethyle one
CH3 CH
-H20
H
CH-C-CH-CH CH-C-CH-CH
-C Hs OH CH
2° Carbocation
:PaKnl)Ua7--o1
CH ion Shift

CH CH
-HT
CH3-CC-CHj -CHJ-C-CH-CH3

CH CH3
3° Carbocation
Tetramethylethylene
with Hg(OAc)/H20;
3-Ethylpent-2-ene is reacted
aigthe structure ofthe majorproductwhen
NuB4? oxymercuration-demercuration and proceeds as follows:
known as
Te Eaction is
Hg(OAc)2 /H20 CH3-CH2-C-CH-CH3
CH-CH-CCH-CH
OH HgOAc
3-Ethylpent-2-ene
NaBH4

CH-CH2-C-CH-CH
OH
3-Ethylpentan-3-ol
is a weaker acid. Discuss.
is a stronger acid than phenol while
p-cresol
P-trophenol the para position in the ring, it
electron withdrawing group. When present at
e-NO2 group is an
group aue to conjugation
and the release
the electron density on the oxygen atom or
ases On the other hand, -CH3group an electron releasing group.
is
1onbecomes easier than inphenol. atom and release of H* ion becomes difficult
BCreasesthe electron density on the oxygen the
p-nitrophenol 1s a strongeracid than phenol whilep-cresolis a weaker
ared phenol.
to Therefore,
properties of phenols).
section 12.10 (Cnemical
aCid. ror further details, consult
unlike phenol, 2,4-dinitrophenolis soluble in aqueous sodium
Ow do youaccount for the fact that
carbonate solution?
he presence oftwo electron withdrawing -NO2 groups in the ring at the ortho and para
dinitrophenol a stronger a d tnan pneno.. It therefore, reacts with aqueous
poSitionscarbonate
Sodium makes 2to form corresponding sodium salt which is soluble. But phenol being a weaker
not react with aqueous sodium carbonate. For more details, consut section 12.16.
does D
 |12.78 well as phoe
NESH
Acohols
react
with halogen
acids as

Explain. horus halldes

o. 1
haloarenes.

not form to
phenols do
the C-O
bond has a partial double bondd
character due t Torm
In phenois,
cleaved by the X halogen acids or
1on of or phosph O Tesonane bae
orus
n v casily
alcohols and cleavage is therefore, possible. Thu halides
singie
while
bond in

phens donot
reactivity of
form haloarenes.

alcohols in the esterification .

alconols eaiBully the y
The order of
Q.18 primary> secondary >>
tertiary. Justify.
of alcohol cleavee
difficult and cleaves.
reaction, 0-H bond
In the esterification The
As
I eftfet makes the cleavage of the bond the alco presence
of ak
csterification. Greater the number or aikyl groups present.
sent, becomes
lesser will
alcohol. The relative order of reactivity 1s, therefore, justified. For wil }
les
128
For more be the
a 14 Dehvdration of alcohol to form an alkene is always carried out- exails, tunod
not with concentrated HCl or HNO3. Explain.
As. Under the acidic conditions, alcohol is initially protonated and
carbocation. If HCl is used, then Cl" ion being a strong then loses HO
substitation to form alkyl chloride. However, HSO ionnucleophile will
nucleophile and cannot participate in the nucleophilic released by HTesult in tuc
and eliminate a proton to form alkene as the substitution. It will rather
product as follows
22 3
C R-CH-CH2-C
Alkyl chloride
R-CH-CH
Carbocation

Concentrated HNO, is a powerful

HSO4R-CH =CH2+ H2S04
Alkene
and then to acid.
Thus,
oxidising agent.
out of the mineral
It will cause
oxidation of alcohol to ae
H2S04. Even acids listed,
Q.15. Phenol is
phosphoric acid can be used. dehydration is carried by concera
acldic while
Ans. In cyclohexanol
phenol, the oxygen atom of 0-H
is neutral.
Justlfy.
due to the group becomes electron (A.LS&.X
of ring. conjugation of electron deficient
pairs on it with the pi electron
Therefore,
the electron
H* can be
released. However, in pairs :0-H
pairs on the oxygen atom
with the ring
since it has no are not
involved cyclohexanol,
in any
of H ion is
quite difficult.
pi electron pairs.
Therefore,
conjugation
the release
Q. 16. Phenol has a
smaller dipole
moment than
Ans. methanol. Discuss.
0-H (D.S.B.

(H effect)
HC 0-H
Pnenyl group has -I (+I effect)
atom. As a (inductive effect) and it tends to
which methylresult, the polarity or decrease the elecu
electron density on the 0
group has +I dipole moment of 0-H
effect. Dond
bond is1s less than in methyl alcon
 12,79

acidic than
a c i d
o-methoxyphenol. Explain.
ore
s
Oreithdrawing group. It tends to withdraw the electrons from the ring as
1elec Aom of 0-H bond. This facilitaes the release of proton. It is
ahenol

f r o n tn e o x V g e n

in
Od than o-methoxyphenol
aC
the methoy group is an electron. For
which
12.16 (chemical properties of phenols).
srosecion
on reaction of an alkane with H,SO/H,0 which is not
4..O produced
is
al isomers. Identify the compound. (CB.S.E. P.M.T. (Malns) 2007)
ble
dntoo p i

compound and the reaction conditions suggest that the compound is an

of the
alcohol.
Since it is not resolvable, it is symmetrical and is tertiary butyl
TmeOlacula
o r m

a
an ether.
ether.
follows
is isobutane. The alcohol has been formed
not as
nd
alkane

CHy H20 CH
HS04 /hestCH3-¢-S03H CH-¢-OH
CH--H
CH CH CH
Tert-butyl alcohol
Isobutane

most reactve towards attack by an electrophile?

the folowing is the
sbth of
CI CH,OH NO
OH

(I1) (AV)
in the ring. Both
to attack centres of high electron density
will always prefer In benzyl alcohol (I),
An electrophile are electron withdrawing
groups.
chloro (-C) groups activate it. Phenol ()
citro (-NO,) and and is not in a position to
attached to the ring attack both
the OH group is not directly activates the ring
towards electrophilic
because phenolic group
section 12.16 (Chemical
properties of
s the most reactive consult
For more details,
al the ortho and para positions.

pkenols).
dionnl Jmnartant-QuestiOns