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ALCOHOL

1. INTRODUCTION 2
2. METHOD OF FORMATION 3
3. PHYSICALPROPERTIES OFALCOHOL 7
4. CHEMICAL PROPERTIES OFALCOHOL 7
5. DISTINCTION BETWEEN PRIMARY, SECONDARY
AND TERTIARYALCOHOLS 12
PHENOL
1. INTRODUCTION 16
2. METHOD OF PREPARATION OF PHENOL 16
3. PHYSICAL PROPERTIES OF PHENOL 17
4. CHEMICAL PROPERTIES OF PHENOL 19
5. DISTINCTION BETWEEN ALCOHOLAND PHENOL 22
ETHERS
METHOD OF PREPARATION OF ETHERS
1. 23
2. PHYSICAL PROPERTIES OF ETHERS 24
3. CHEMICAL PROPERTIES OF ETHERS 24
1
CONTENTS
S.NO. TOPIC PAGE NO
Alcohol
1. INTRODUCTION :
(i) These are the organic compounds in which –OH group is directly attached with carbon.
(ii) These are hydroxy derivatives of alkanes and mono alkyl derivatives of water.
(iii) Their general formula is C
n
H
2n+1
OH or C
n
H
2n+2
O.
ClassificationofAlcohols
Mono, Di, Tri orPolyhydric Compounds
Alcohols and phenols may be classified as mono–, di–, tri- or polyhydric compounds depending on
whether theycontain one, two, three or manyhydroxyl groups respectivelyin their structures as given
below:
(i) Compounds containing C ÷ OH bond: In this class of alcohols, the –OHgroup is attached to an
sp3
sp
3
hybridised carbon atomof an alkyl group. They are further classified as follows
(a) Primary, secondary and tertiary alcohols: In these three types of alcohols, the –OH group is
attached primary, secondaryand tertiary carbon atom, respectivelyas depicted below:
(b) Allylic alcohols: In these alcohols, the —OHgroup is attached to a sp
3
hybridised carbon next to
the carbon-carbon double bond, that is to an allylic carbon. For example
(c) Benzylic alcohols: In these alcohols, the —OH group is attached to a sp
3
—hybridised carbon
atomnext to an aromatic ring. For example
Allylic and benzylic alcohols maybe primary, secondaryor tertiary.
2
ALCOHOL
Alcohol
(ii) Compounds containing C ÷ OHbond: These alcohols contain —OHgroup bonded to a car-
sp
2
bon-carbon double bond i.e., to a vinylic carbon or to an aryl carbon. These alcohols are also
known as vinylic alcohols.
Vinylic alcohol: CH =CH–OH
2
Phenols :
2. METHOD OF FORMATION :
From alkenes
(1) By acidcatalyzed hydration: Alkenes react with water in the presence of acid as catalyst to form
alcohol. In case of unsymmetrical alkenes, the addition reaction takes place in accordance with
Markonikov’s rule
Mechanism: The mechanismof the reaction involves the following three steps:
Step 1:
H O + H
+
÷ H O
+
3 3
Step 2:
Step 3:
(2) By hydroboration–oxidation: Diborane (BH ) reacts with alkenes to give trialkyl boranes as
3 2
addition product. This is oxidized to alcohol byhydrogen peroxide in the presence of aqueous sodium
hydroxide.
H BH
2
CH
3
– CH= CH
2
CH
3
–CH = CH
2
(CH
3
– CH
2
– CH
2
)
3
B (CH
3
– CH
2
– CH
2
)
2
BH

2H
2
O
2
, OH H
2
O
CH
3
– CH
2
– CH
2
–OH + B(OH)
3
Propan–1–ol
Note : In this reaction addition of water at double bond according to Anti Markonikov Rule
3
Alcohol
Mechanism of Hydroborations-deboration
B2H6 ÷THF/H 2O2 /OH
÷
e.g., CH
3
—CH = CH
2
CH
3
—CH
2
— CH
2
—OH
÷÷÷÷÷÷÷÷÷÷
©
H

transfer
+ CH
3
– CH = CH
2
÷÷ CH – CH – CH
2
÷÷÷÷÷ CH
3
—CH
2
– CH
2
. .
©
O
.
.
BH
2 BH
3
BH
3
These steps are repeated twice to form (CH
3
– CH
2
– CH
2
)
2
B and then :
R R
R
. . . .
– H
©
©
. . . .
H –
.
O
.

.
O
.
– H
R —B ÷÷÷÷÷÷÷ R —B —O —O —H ÷÷÷÷ R —B —O
. .

.
O
.
—H
R R H R
–OH
R —B —OR
R
OR
|
RO —B —OR
With H
2
O
2
, finally is formed by above mentioned method
OR
|
RO —B—OR ÷÷
3 N
÷
aO
÷
H
÷÷
3. Oxymercuration
Na BO + 3ROH
3 3
Involves an electrophilic attack on the double bond by the positively charged mercury species. Theproduct
is a mercuriniumion, an organometallic cation containing a three-membered ring.
With mercuric acetate, the product is 3-methyl-2-butanol (Markonikov addition with no rearrangement,
Oxymercuration demercuration reaction).
NaBH
4
(CH
3
)
2
CHCH– CH
2
Hg(OCOCH
3
)
2
(CH ) CHCHCH
(CH
3
)
3
CHCH = CH
2
3-Methylbutene-1
3 3 3
HgOCOCH
3
OH
OH
3-Methyl-1butanol
not-isolated
OAc
Hg
+
+
Hg(OAc)
C = C —C —C —
mercurinium ion
Mercuration commonly takes place in a solution containing water and an organic solvent to dissolve the
alkene. Attack on the mercurinium ion by water gives (after deprotonation) an organomercurial alcohol.
+
Hg(OAc)
Hg(OAc) Hg(OAc)
–H
+
—C —C — —C —C — —C —C —
. .
H
2
O:
+
:
.
O
.
H
organomercurial alcohol
H —
.
O:
.
H O:
H
2
4
Alcohol
Hg(0Ac)
|
H
| |
4 —C —C —+NaB(0H)
4
+ 4Hg+ + 4
-
0Ac
| |
H0
alcohol
|
+ NaBH
4
+ 4
-
0H ÷÷ 4 —C —C —
|
0H
|
organomercurial alcohol
The second step is demercuration, to form the alcohol. Sodium borohydride (NaBH
4
, a reducing agent)
replaces the mercuric acetate rearrangement with hydrogen.
4. By Reduction of Carbonyl compounds :
LiAlH / Na+C H OH
RCH+ 2H
||
O
RCR+ 2H
||
O
÷÷÷
4
÷÷÷
2
÷
5
÷÷÷ R- CH
2
0H
1º alcohol
LiAlH / Na+C H OH
÷÷÷
4
÷÷÷
2
÷
5
÷÷÷
RCHR
|
OH
2º alcohol
Note :
(i) We cannot obtain 3º alcohol from this method
(ii) If we use NaH as reductant then the process is called as 'Darzen's process'.
5. By Reduction of Acid & its derivatives
R÷ C ÷ OH + 4H ÷
L
÷
iAl
÷
H
÷
4
÷ RCH
2
0H
||
O
+ 4H ÷
LiAlH
÷
4
÷ R CH
2
0H + HX R ÷ C ÷ X
||
O
÷
L
÷
iAlH
÷
4
÷
R- C- 0R' + 4H
||
0
RCH 0H + R'0H
2
RC00C0R + 8H ÷
L
÷
iAlH
÷
4
÷
2 RCH
2
0H + H
2
0
6. From Grignard reagent (RMgx)
(i) Reaction withoxyrene:
o- +o o+ o+ +2
R : MgX + H
2
C—CH
2
÷÷÷R —CH
2
— CH
2
—0 MgX
0
o- +
H
3
0
R —CH
2
— CH
2
—0H
primary alco.
5
Alcohol
(ii) Reaction withCarbonyl compounds:
÷÷
i)
÷
ether
÷÷÷
R: Mg — X + C = 0
R —C —0 —H + MgX
2
ii ) H 0
+
, X
-
3
+2
R: MgX + C = 0 ÷÷÷R —C—0 Mg X
÷
o- o+ o-
o+
+2 ÷
R —C—0 Mg X + H—0 —H ÷÷÷R —C—0 —H + 0 —H + MgX
2
+X
÷
H H
(iii) Reaction withacetaldehyde:
CH
3
CH
3
H
3
C ÷÷÷÷
CH
3
—CH
2
— MgBr + H
0
Et20
0MgBr
H
+
H
3
0
CH
3
H
3
C 0H
butan-2-ol
(iv) Reaction with ketone :
CH
3
CH
3
H
3
C
÷÷÷÷
H
3
C 0
CH
3
—CH
2
—CH
2
—MgBr + Et
2
0
0MgBr
H
3
C
+
H
3
0
CH
3 H
3
C
0H
CH
3
2-methylpentan-2-ol
7. By Fermentation
Fermentation is a slow decomposition of complex organic compounds into simpler compounds in the
presence of suitable micro-organisms which are the source of biochemical catalyst known as enzymes.
(C
6
H
10
0
5
)
n
Starch
CH
3
.CH
2
.CH
2
.CH
2
0H + CH
3
.C0.CH
3
n-Butyl alcohol
6
Alcohol
3. PHYSICALPROPERTIES OFALCOHOL:
(1) The lower alcohols are liquids while higher having more than 12 carbon atoms are solids. They are colorless
neutral substances with characteristic sweet alcoholic odour and burning taste.
The lower alcohols are readily soluble in water and the solubility decreases with the increase in molecular
weight.
The solubility of alcohols in water can be explained due to the formation of hydrogen bond between the
highly polarized -0H groups present both in alcohol and water.
(2)
o + o ÷
H - 0
o + o ÷
H - 0
o + o ÷
H - 0
H R H
Hydrogen bonding between alcohol and water molecules
However, in higher alcohols the hydrocarbon character (alkyl chain) of the molecule increases and thus
alcohols tend to resemble hydrocarbon (which are insoluble in water) and hence the solubility in water
decreases. When the ratio of C to 0H is more than 4, alcohols have little solubility in water.
Boiling points of alcohols are much higher than those of the corresponding alkanes. It is again due to the
formation of hydrogen bonding between the hydroxyl groups of the two molecules of an alcohols with the
result several molecules are associated to form a large molecule.
(3)
o + o ÷
H - 0
o + o ÷
H - 0
o + o ÷
H - 0
R R R
Hydrogen bonding in alcohol molecules
Among the isomeric alcohols, b.p. and m.p. show the following trend.
Primary > Secondary > Tertiary
This is because of the fact that in secondary and tertiary alcohols, the alkyl part (hydrogen character)
outweighs the -0H group due to branching.
Lower alcohols form solid addition compounds with anhydrous metallic salts like CaCl
2
and MgCl
2
,
viz., CaCl
2
.4C
2
H
5
0H and MgCl
2
.6C
2
H
5
0H
By analogy towater of crystallization, these alcohol molecules arereferred to as alcohol of crystallization.
For this reason, alcohols cannot be dried over anhydrous calciumchloride.
(4)
4. CHEMICAL PROPERTIES OFALCOHOL
1. Reaction with Na:
2R-
O–H + Na ––––––÷ 2R - 0 - Na + H
2
|
The acidic order of alcohols is
Me0H > 1º > 2º > 3º
2. Esterification / Reaction with carboxylic : When reaction of alcohol with carboxylic acid in
presence of sulphuric acid to form ester.
conc.H SO
÷÷÷÷÷
2
÷÷
4
÷ R–C–O–R + H
2
O
||
O
ester
7
Alcohol
Mechanism :-
H
2
S0
4
-----÷ H
+
+ HSO
÷
4
©
R÷ ÷
. .
RCO
H
+
R ÷ C
+
||
O
ROH
RC
||
O
OR
H+ ---÷ O C ÷R
. . H
2
O H
||
O
| ||
H O
Note :- The above reaction is laboratory method of ester preparation.
3. Reaction withAcid derivatives :-
R-0-H + X ÷ C ÷ R
||
O
C
÷
on
÷
c.H
2
÷
SO
÷
4
+ HX R÷ O÷ C ÷R
||
O
Conc.H
2
SO
4
÷÷÷ ÷ R÷ C ÷ O÷R
||
O
R ÷ O÷H+ R ÷ C÷ O÷ C÷R
||
O
||
O
4. Reaction with IsocyanicdAcid :-
?
?
R O H
o
+
C
||
O
o ÷
+ H - N = H - N = H - NH - C O
||
O
R
÷÷÷ ÷÷÷ C ÷ O ÷R
|
OH
amino ester (urethane)
Reaction with ethylene oxide :- 5.
0
o-
H
o+ ROH
H
2
O
R - - + ÷÷÷
1,2-dialkoxy ethane
Reaction with Diazomethane :- 6.
R- 0 - H + CH
2
N
2
÷÷÷ R- 0 - CH
3
(ether)
7. Reaction with H
2
SO
4
:-
..
(i) CH
3
- CH
2
- 0H + H
2
S0
4
(excess) ÷÷
140
÷
º
÷
C
÷ CH
3
- CH
2
- O - CH - CH
2 3 ..
Mechanism :-
H
2
S0
4
÷÷÷ + HS0
4
¯
CH
3
- CH
2
- O

: + H
+
÷÷÷ CH
3
- CH
2
÷÷
|
H
H
+
O
 +
- H
|
H
CH
3
–CH
2
–OH
CH
3
- CH
2
÷÷÷÷÷÷
(protonated ether)
. .
CH
3
÷ CH
2
÷ O÷ CH
2
÷ CH
3
. .
8
÷÷÷
+
Alcohol
(ii) CH
3
- CH
2
- 0H + H
2
S0
4
(excess)
Mechanism :-
÷÷
160
÷
º
÷
C
÷
CH
2
=
CH
2
H
+
+ HS0
4
-
H
2
S0
4
÷÷÷
©
CH
3
- CH
2
- - H + H
+
÷÷÷ CH
3
- CH
2
-
H
-H
÷
÷
÷
H
÷
O
÷
CH
3
-
CH
2
= CH
2
CH
2 2
Note : In the above reaction excess of ethanol is present so, intermediate carbocation satisfies itself by
elimination.
8. Action of halogen acids
anhy. ZnCl
2
C
2
H
5
0H + HCl C
2
H
5
Cl + H
2
0
The reactivity of halogen is in the order : HI > HBr > HCl.
S
N
1 reaction with the Lucas reagent (fast)
CH
3
CH
3
H —C —0
+
CH
3
H —C —Cl
-
ZnCl
2
H
CH
3
CH
3
. . ZnCl2
-
Cl
H — C
+
H —C —0
. .
— H
CH
3
CH
3
CH
3
. .
-
H 0
. .
—ZnCl
2
S
N
2 reaction with the Lucas reagent (slow)
9. Action of thionyl chloride : When alcohol react with thionyl cloride to form alkyl hylide and reaction is
called darzen process.
C
2
H
5
0H + S0Cl
2
Mechanism
. . Cl
C
2
H
5
Cl + HCl + S0
2
Cl
0 0
. . . . . . . .
R —0
. .
—S
-
R —0 — S —0
. .
: R — 0: S = 0 R —0 —S + HCl
+ +
Cl
Cl¯
Cl
Cl
H H Cl H
thionyl chloride chlorosulfite ester
. .
0
. .
0 ¯ 0
(fast)
R
+
R S = 0 S = 0 R S = 0
Cl Cl Cl
chlorosulfite ester ion pair
9
.

.
.

.
.

.
.

.
.

.
.

.
.

.
Alcohol
This mechanism resembles the S
N
1, except that the nucleophile is delivered to the carbocation by the
leavinggroup, giving retentionof configurationas shown inthefollowingexample. (Under different conditions,
retention of configuration may not be observed.)
H H
0H Cl
S0Cl
2
C
CH
3
(CH
2
)
4
CH
2
CH
3
(R) 2-octanol
C
CH
3
(CH
2
)
4
CH
2
(R)-2-chlorooctane
(84%)
CH
3
di ne oxa
(solvent)
10. Action of phosphorus halides (PX
5
and PX
3
). For example,
(i) C
2
H
5
0H + PCl
5
C
2
H
5
Cl + HCl + P0Cl
3
Ethyl chloride
Mechanism
3 R - 0H + PCl
5
÷÷÷ P(0R)
3
Cl
2
+ 3HCl
P (0R)
3
Cl
2
+ R0H ÷÷÷ P(0R)
4
Cl + HCl
Cl
(0R)
3
P
. .
.
0
.
÷÷÷ (R0) P = 0 + RCl 3
R
÷÷÷
(R0)
3
P = 0 + 3HCl + 3R0H
11. Action of ammonia
Al
2
0
3 R0H
Al
2
0
3
R0H
Al
2
0
3
R0H + NH
3
R
3
N
3º amine
R
2
NH
2º amine
RNH
2
1º amine
The ease of dehydration of alcohols is in the order :
Tertiary > Secondary > Primary
12. Dehydration: Alcohols undergo dehydration (removal of a molecule of water) to formalkenes on
treating with acid e.g., concentrated H S0 or H P0 , or catalysts such as anhydrous zinc chloride or
2 4 3 4
alumina
10
d
u
Alcohol
Mechanismof dehydration
Step 1:
Step 2:
Step 3:
The acid used in step 1 is released in step 3. To drive the equilibriumto the right, ethene is removed as
it is formed. The relative ease of dehydration, i.e. 3º > 2º > 1º, of alcohols follows the order of stability of
carboniumions.
Oxidation
(a) Primary alcohol initially forms aldehyde on oxidation and on further oxidation forms respective
acid.
(b) Secondary alcohol initially forms respective ketone on oxidation which on further oxidation
forms acid of less carbon. 0xidation of ketone is slightly difficult than aldehyde due to stability so,
we use strong oxidizing agent for oxidation.
(c) Tertiary alcohols are resistant to oxidation in normal conditions but on taking strongest oxidizing
agent like chromic acid in dilute nitric acid then they form less carbon ketone.
(d) For oxidation of 1º alcohol, acidic KMn0
4
is used as oxidant while for 2º alcohol acidic
K
2
Cr
2
0
7
(more strong than KMn0
4
) is used.
(e) For both (1º and 2º alcohol) we can use common oxidizing agent also, like chromic acid in
dil ute H
2
S0
4
. Colour of this solution is orange and it turns into green colour due to Cr
+3
.
(f) Reacting species of solution is HCr0
4
¯.
13.
÷÷
[
÷
o]
÷
÷
acid
÷
ic K
÷
Mn
÷
O
÷
4
÷
÷
acid
÷
ic K
÷
2
C
÷
r
2
O
÷
7
÷
÷÷
[
÷
o]
÷
÷
H
2
C
÷
rO
÷
4
+ dil. HNO
÷
3
÷
(ketone of lesser carbon)
11
Alcohol
14. Dehydrogenation / Catalytic Oxidation
Cu / ZnO
300º
1º alcohol
aldehyde
Cu / ZnO
300º
secondary alcohol
ketone
Cu / ZnO
300º
tert. alcohol alkene
(Note : – This is dehydration process.)
5. DISTINCTION BETWEEN PRIMARY, SECONDARY AND TERTIARY
ALCOHOLS :
(1) Lucas test : This test is based on the difference in the three types of alcohols (having 6 or less carbon)
towards Lucas reagent (a mixture of conc. hydrochloric acid and anhydrous zinc chloride)
ZnCl
2
RCl + H
2
0 ROH + HCl
Since alkyl halides are insoluble, their formation is indicated by the appearance of a turbidity in the reaction
mixture. The order of reactivity is tertiary > secondary > primary, the teritary alcohols produce turbidity
immediately, the secondary alcohols give turbidity within 5 - 10 minutes, and the primary alcohols do not
give turbidity at all, at roomtemperature.
Catalytic dehydrogenation (action of reduced copper at 300ºC). Discussed ealier.
(i) Primary alcohols form aldehydes
(ii) Secondary alcohols form ketones.
(iii) Tertiary alcohols formolefins.
Victor Meyer test : This test is based on the different behaviour of primary, secondary and tertiary
nitroalkanes towards nitrous acid. The test involves the following steps.
(i) Alcohol is treated with concentrated hydriodic acid or red phosphorus and iodine to form the
correspondingalkyl iodide.
(ii) Alkyl iodide is reacted with silver nitrite to formthe corresponding nitroalkane.
(iii) The nitroalkane is treated with nitrous acid (NaN0
2
+ H
2
S0
4
) followed by treatment with alkali
(Na0H or K0H). Upon such treatment different alcohols give different colours.
(a) Primary alcohols produce a blood red colour
(b) Secondary alcohols produce a blue colour.
(c) Tertiay alcohols produce no colour.
(2)
(3)
12
Alcohol
Primary
CH
3
CH
2
0H
P + I
2
CH
3
CH
2
I
AgN0
2
Secondary
(CH
3
)
2
CH0H
P + I
2
Tertiary
(CH
3
)
3
C0H
P + I
2

(CH
3
)
2
CHI
AgN0
2
(CH
3
)
3
Cl
AgN0
2

CH
3
CH
2
N0
2
(CH
3
)
2
CHN0
2
(CH
3
)
3
CN0
2
HONO HONO H0N0

CH
3
CN0
2
| |
N0H
Nitrolic acid
+ Na0H
CH
3
CN0
2
| |
N0Na
Sod. salt of nitrolic acid
(Red colour)
(CH
3
)
2
.CN0
2
|
N0
(Pseudonitril)
+ Na0H
No reaction
(Blue colour)
No reaction
(Colourless)
Ex.1 Give the structure of
Hg(0A
C
)
2 / H
2
0
; NaBH
4
.
CH
2
CH
3
the major organic product when 3-ethylpent-2-ene is treated with
CH
2
CH
3
Hg(0A
C
)
2
/ H
2
0
(Mark addition)
CH
3
CH
2
—C — CH —CH
3
Sol. CH
3
CH
2
—C = CH —CH
3
3-Ethylpent-2-ene Hg0A
C
0H
CH
2
CH
3
CH
3
CH
2
—C — CH
2
CH
3 NaBH
4
Reduction
0H
3-Ethylpentan-3-ol
13
Alcohol
WASH - ABSOLUTE ALCOHOL
Wash[10-15%EtOH]
Distillation
Rawspirit [90%EtOH]
Fractional distillation
20-21ºC 78ºC
Mainly CH CHO Rectified spirit [95.5% EtOH] Fuel oil
3
Excess benzene Azeotropic distillation
65ºC
[Glycerol + CH COCH
3
+ Higher alcohol]
3
C H + C H OH+ H O
6 6 2 5 2
(74.1%) (18.5%) (7.4%) (Ternary mixture)
68
0
C
C H + EtOH
6 6
(80%) (20%) (Binary mixture)
78.3
0
C
Absolute alcohol
[100% EtOH]
14
Alcohol
ALCOHOL
GR GMP
HX or PX or PX
÷÷÷÷÷÷
3
÷÷
5
÷÷÷
or KI +H
3
PO
4
or SOCl
2
or SO
2
Cl
2
(1) RX
÷
H
÷
2
÷
O
÷
(1) Alkene
÷
R
÷
e d
÷
P/
÷
HI
÷ (2)
(3)
RH aq. NaOH or aq. KOH
÷÷÷÷÷÷÷÷÷
or aq. K
2
CO
3
or moist Ag
2
O
d
÷
il. H
÷
2
S
÷
O
÷
4
÷
(2) RX
÷
N
÷
H
÷
3
÷ 1º , 2º , 3º amines
(3) R - O - R
÷
H
÷
2
÷
S
÷
(4) R - SH Thiol
÷
d
÷
il. H
÷
2
S
÷
O
÷
4
÷
Th0
2
(4) RCOOR
÷RCOOH
÷
N
÷
a
÷ (5)
(6)
RONa
÷
H
÷
NO
÷
2
÷ (5) 1º amine
÷
C
÷
H
3
÷
Mg
÷
X
÷CH
Exception - Methyl amine gives
CH -O-CH or ether
4
R' OR
÷÷
ald
÷
.R'÷
÷
CH
÷÷
O
÷
3 3
(7) C Acetal
N
÷
a
÷
H
÷
Darzon reduction
dry HCl
(6) Aldehyde or ketone
H OR
(1º alc.) (2º alc.)
÷÷÷
Na
÷
/ EtO
÷
H
÷÷÷÷
R-OH
R' OR
(7) Acid or
÷
Ket
÷
one
÷
R
÷
'CO
÷
R
÷
'
÷
dry HCl
Bouveault ÷Blanc reduction
(8) C Ketal
Acidderivative
HCHO or Ald.or ketone ÷
R÷M
÷
g
÷
X
÷
H
2
O
R' OR
(8)
÷
R
÷
'C
÷
O
÷
Z
÷ R'COOR ester (Z = OH,Cl, OCOCH ) (9)
(10)
(11)
(12)
(13)
(14)
3
(1º alc) (2ºalc) (3º alc.)
O
2
÷
H
÷
2
S
÷
O
÷
4
÷ROSO OH (Alkyl hydrogen sulphate)
2
RONO (Alkyl nitrate)
÷ ÷÷
H
2
O
(9) RMgX
÷
H
÷
NO
÷
3
÷
2
÷
P
÷
hS
÷
O
2
÷
Cl
÷
CH
2
÷CH
2
÷÷÷
O
÷÷÷
RSO Ph (Alkyl benzene sulphonate)
2
H C - CH (OR) Acetal
3 2
(10) CH MgBr
CH÷ CH
÷÷÷÷÷ 3
+
H
3
O
CH
2
N
2
÷÷÷÷÷ R - O - CH Ether
3
O
CH
2
÷ CH
2
(11) Sugar ÷
F
÷
erm
÷
en
÷
tati
÷
o
÷
n
÷
(15) ÷÷ ÷÷÷÷ RO- CH - CH - OH
2 2
Alkoxyalkanol
÷
C
÷
H
2
÷
= C
÷
=
÷
O
÷ROCOCH (16)
(17)
Ester
3
D
÷
eh
÷
ydr
÷
atio
÷
n
÷
Alkene
÷÷
C
÷
atalytic dehydrogenatio
÷
n
÷
(18) Aldehyde or ketone
1
0
or alcohol , Cu or ZnO , 300
0
C
2
0
Formation of EtOH by fermention -
Exception - 3º alc ÷Alkene
Crystallization
÷÷÷÷÷÷
Sucrose
(1) Cane sugar Molasses
1ºalc. ÷
[
÷
O
÷
]
÷Aldehyde
O
÷
]
÷Acid (same no. of C-atom)
[
÷
(19)
(20)
(21)
2ºalc. ÷
[
÷
O ]
÷Ketone ÷
[[O
÷
]
÷
Invertase
÷
zymase
÷
Fermentation
÷÷÷÷÷
Invert sugar
hydrolysis
EtOH
3ºalc. ÷
[
÷
O
÷
]
÷
÷
÷
O
÷
H
÷
CrO
÷ ÷
4
(22) 1º or 2ºalc. Aldehyde or ketone + Cr
+3
(green)
Diastase
÷÷÷÷÷
HOH
(2) Grain ÷Starch Maltose
(orange)
÷
÷
O
÷
, H
÷
CrO
÷
Maltase Zymase
÷
4
÷÷÷÷÷
hydrolysis
EtOH
÷÷÷÷÷
Fermentation
Glucose (23) 3º alc No reaction (No. green colour)
(orange)
15
Alcohol
PHENOL
1. INTRODUCTION :
When0Hgroup attached at benzine ring is known as phenol.
Nomenclature of Phenols
0H 0H 0H 0H
CH
3
H
3
C CH
3
CH
3
CH
3
4-methyl phenol
(p-cresol)
2-methyl phenol
(o-cresol)
3-methyl phenol
(m-cresol)
2-6 dimethyl phenol
Some dihydric and trihydric phenols are given below:
0H 0H 0H
0H
0H
1-2-Benzenediol
(Catechol)
1-3-Benzenediol
(Resorchinol) 0H
1-4 Benzenediol
(Qunol)
0H 0H 0H
0H
0H 0H H0 0H
0H
1-2-4 Benzenetriol
(Hydroxyqionol)
1-2-3 Benzenetriol
(pyrogallol
1-3-5 Benzene-triol
(Phloroglucinol)
2. METHOD OF PREPARATION OF PHENOL:
(a) Fromhaloarenes
16
Alcohol
2. Frombenzenesulphonic acid
3. Fromdiazoniumsalts
When diazoniumsalts react with water vapour gives phenol.
4. Fromcumene
When Cumene (isopropylbenzene) is oxidised inthe presence of air and acid gives phenol and acetone.
3. PHYSICALPROPERTIES OF PHENOL:
(i) Pure phenols are generally colourless solids or liquids. The light colour usually associated with phenols
is due to its oxidation by air in presence of light.
(ii) Phenols, in general, are insoluble in water; but phenol itself, and polyhydric phenols are fairly solublein
water which is believed to be due to the formation of hydrogen bonds with water.
(iii) Due to intermolecular hydrogen bonding, phenols usually have relatively high boiling points than the
corresponding hydrocarbons, aryl halides and alcohols. For example, phenol (mol. wt. 94) boils at 182ºC
while toluene (mol. wt 92) boils at 110ºC.
Higher b.p. than alcohols is dueto higher polarityof the0 -Hbond and consequentlystronger intermolecular
hydrogen bonding in phenols than in alcohols. Appreciable solubilities of the phenol and polyhydric phenols
in water is also due to strong hydrogen bonding between phenols and water molecules.
0
Ar
0 Ar
H
0
0
0
H
Ar 0 H
H
H H
N
0
o-Nitrophenol (Intramolecular
H-bonding possible due to
closeness of -N0
2
and -0H groups)
Hydrogen bonding between
phenols and water molecules
Intermolecular hydrogen
bonding in phenols
17
Alcohol
Phenols containing groups like -N0
2
or -C00H in the ortho position to the -0H group can also form
intramolecular hydrogen bonds (e.g. o-nitrophenol) which is responsible for their lower boiling points and
less solubility in water than the corresponding meta or para isomer.
Due to possibility of intramolecular hydrogen bonding (also known as chelation) in the ortho isomer,
intermolecular hydrogen bonding is not possible and hence the ortho isomer can neither get associated nor
can formhydrogen bonding with water with the result it has a low b.p. and less solubility in water than the
meta and para isomers which can associate (union of two or more molecules of the same species) as well
as can form hydrogen bonding with water.
0 — H 0
0
H
H
0 0H
N
N
N
0 0
0 — H
0 H H 0
0
Hydrogen bonding between p-nitrophenol and water
p-Nitrophenol (2 molecules) (Intramolecular H-bonding is
not possible due to large distance between -N0
2
and -0H
groups; hence intermolecular H-bonding is possible)
(iv) They possess characteristic colour. They are highly toxic in nature and possess antiseptic properties. They
may produce wounds on skin.
Note :
(i) Phenol exists as a resonance hybrid of the following structures.
..
:
0H
..
:
0H
+
: 0H
+
: 0H
+
: 0H
:–
– :
..
IV V
I III
II
Due to resonance, oxygen atom of the -0H group acquires a positive charge (see structures III
to V) and hence attracts electron pair of the 0 - H bond leading to the release of hydrogen atom as
proton.
..
:
0 - H
..
:
0
:
H
+
+
Phenol
Phenoxide ion
Since resonance is not possible in alcohols (due to absence of conjugation of the lone pair of electron of
oxygen with a double bond), the hydrogen atom is more firmly linked to the oxygen atom and hence
alcohols are neutral in nature.
18
Alcohol
(ii) 0nce the phenoxide ion is formed, it stablises itself by resonance, actuallyphenoxide ion is more stable
than the parent phenol.
.. –
:
0
:
.. –
:
0
:
..
:
0
..
:
0
..
:
0
: –
– :
..
IX X VI VIII
VII
3. Comparison of acidity of phenols and carbonic acid.
Relative acidity of the various common compounds.
> R0H
Alcohols
RC00H
Carboxylic acid
> H
2
C0
3
> C
6
H
5
0H
Phenol
> H0H
Water Carbonic acid
4. CHEMICAL PROPERTIES OF PHENOL:
1. Nitration:
(a) Whenphenol react with dilute nitric acid at lowtemperature (298K), gives a mixture of ortho and
para nitrophenols.
(b) Whenphenol is react with concentrated nitric acid, gives 2,4,6-trinitrophenol.
2. Halogenation:
(a) When the reaction is carried out in solvents of low polarity such as CHCl or CS and at low
3 2
temperature, monobromophenols are formed.
19
Alcohol
(b) When phenol is treated withbromine water, 2,4,6-tribromophenol is formed as white precipitate.
3. Kolbe’s reaction :
Mechanismof Reaction
O
0
Na 0
C
H
0
tautomerisation
O
Na
+
0
H H
0 0
0H
0
0 0
Na
+
+
÷÷
H
3
0
÷÷
Salicyclic acid
Sodium salicylate
4. Reimer-Tiemann reaction : 0n treating phenol with chloroform in the presence of sodium
hydroxide, a -CH0 group is introduced at ortho position of benzene ring. This reaction is known as
Reimer - Tiemann reaction.The intermediate substituted benzal chloride is hydrolysed in the presence
of alkali to produce salicylaldehyde.
The mechanismofthe Reimer-Tiemann reaction is believed to involve the formation of
dichlormethylene.
Na0H+CHCl ÷ :CCl +NaCl+H 0
3 2 2
20
Alcohol
Phenols with blocked p-positions give cyclohexadienones containing the dichromethyl group.
0H
0H 0
0
÷
Na0
÷
H
÷ +
CHCl
3
H
3
C CH
3 CH
3 CH
3
In the Reimer-Tiemann reaction, the o-isomer predominates, but if one of the o-positions is occupied,
the aldehyde group tends to go the p-positions; e.g., guaiacol forms vanillin
0H
0H
0
0
CH
3 CH
3
÷÷
Na0H
÷
CHCl3
0
Libermann’s Reaction: When phenol is treatedwith sodiumdissolvedin conc. Sulphuricacid, a red colouration
appears, which changes to blue on adding aqueous Na0H. This reaction is called Libermann’s reaction
2NaN0
2
+ H
2
S0
4
Na
2
S0
4
+ 2HN0
2
Nitrous acid
N - 0H 0 H0 — —H + H - 0 - N = 0 H0 — —N = 0
- H
2
0
p-Nitrosophenol
H -
- 0H
-
Na0H +
N — — 0H N — 0 0 — 0Na
- H
2
0 - H
2
0
Blue
Indophenol (Red)
5. Reactionof phenol withzinc dust : Whenphenol is heated with zinc dust gives benzene.
6. Oxidation:0xidation of phenol with chromic acid produces a conjugated diketone known as
benzoquinone. In the presence of air, phenols are slowlyoxidised to dark coloured mixtures containing
quinones.
21
Alcohol
5. DISTINCTION BETWEEN ALCOHOLAND PHENOL:
(i)
(ii)
Phenols turns blue litmus red but alcohols do not.
Phenols neutralize base, while alcohols do not.
0H
0Na
+ Na0H
+ H
2
0
No reaction R-0H + Na0H
(iii) Phenols give violet colour with FeCl
3
, while alcohols do not.
0
0H
Fe + 3HCl
3 + FeCl
3
3
Violet
No reaction R - 0H + FeCl
3
Identify the major products in the following reactions
0H
Ex.1
N0
2
CH
3
B
÷
romine
÷÷
(i) (ii) ÷÷
HN0
÷
3
÷A
Water
B
H2S04
0
CH
3
Br
CH
3
0 0H
Sol. A= B =
0
2
N
Br CH
3
N0
2
22
Alcohol
ETHERS
1. METHOD OF PREPARATION OF ETHERS :
1. Williamson’s Synthesis: Heating of alkyl halide withsodiumor potassiumalkoxide
gives ether. This is a good method for preparation of simple as well as mixed ethers.
R-X + Na-O-
R'
R-O-
R'
+ NaX
÷÷÷
This method is not applicable to tert. alkyl halides because the alkoxide ions beingbothpowerful nucleo-
philes and bases could being dehydrogenation of the tertiary alkyl halides to formalkenes.
R -ONa ÷÷÷ R -O
÷
+ Na
+
R' -O-Na
Ar -O-Na
R -O-R
R -O -Ar
Aryl Ether
R -X + ÷÷÷
aq. NaOH
-OH + CH
3
-CH
2
-Br ÷÷÷÷÷ -O -CH
2
-CH
3
The reactivity of primary (1°) alkyl halide is in the order CH > CH -CH > CH -CH -CH and
3 3 2 3 2 2
the tendencyof the alkyl halide to undergo elimination is 3° > 2° >1°. Hence for better yield thealkyl
halide should be primary of the alkoxide should be secondaryor tertiary.
C
2
H
5
Br + NaO-C - ÷÷÷C
2
H
5
-O -C -+ NaBr
2. By heating excess of alcohols with conc. H
2
SO
4
, e.g.,
conc.H
2
SO
4
140ºC
C
2
H
5
- O - C
2
H
5
+ H
2
O
Diethyl ether
C
2
H
5
- OH + HO - C
2
H
5
Ethanol (2 molecules)
Recall that 2º and 3º alcohols under the above conditions give alkenes as the main product. Moreover,
this method is limited only for the preparation of simple ethers.
By heating alkyl halide with dry silver oxide (only for simple ethers) 3.
C
2
H
5
I + Ag
2
O + IC
2
H
5
C
2
H
5
.O.C
2
H
5
+ 2 AgI
Remember that reaction of alkyl halides with moist silver oxide (Ag
2
O + H
2
O = AgOH) gives alcohols.
By the use of diazomethane to form methyl ethers.
BF
3
4.
n-C
7
H
15
OH + CH
2
N
2
n-C
7
H
15
OCH
3
+ N
2
Methyl n-heptyl ether
BF
3
C
6
H
5
OCH
3
Anisole
C H OH + CH N
6 5 2 2
23
Alcohol
2. PHYSICALPROPERTIES OF ETHERS :
1. Their boiling points are much lower than the isomeric alcohols. This is because of absence of -OH group in
ethers and hence they are incapable of forming intermolecular hydrogen bonds.
2. Since the two C - O bonds in ethers are not linear (180º) but they are at an angle of about 110º, i.e., the
molecule is bent, the dipole moment of the two C - O bonds do not cancel each other. Consequently, ethers
are slightly polar and have a small net dipole moment (e.g. 1.18 D for diethyl ether).
Note that the bond angle in ether is somewhat greater than water (105º). It is due to the repulsion between
bulky alkyl groups.
3. CHEMICAL PROPERTIES OF ETHERS :
Ethers are much less reactive than compounds containing other functional group. They do not react with
active metals like Na, strong base like NaOH, reducing or oxidising agents.
1. Formation of peroxides : On standing in contact with air, ethers are converted into unstable peroxides (R
2
O
÷O) which are highly explosive even in lowconcentrations. Hence ether is always purified before distillation.
Purification (removal of peroxide) can be done by washing ether with a solution of ferrous salt (which reduces
peroxide to alcohols) or by distillation with conc. H
2
SO
4
(which oxidises peroxides).
The presence of peroxides in ether is indicated by formation of red colour when ether is shaken with an
aqueous solution of ferrous ammonium sulphate and potassium thiocyanate. The peroxide oxidises
Fe
2+
to Fe
3+
which reacts with thiocyanate ion to give red colour of ferric thiocyanate.
CNS
-
Peroxide + Fe
2+
Fe
3+
Fe(CNS)
3
Red
However, the formation of peroxide is prevented by adding a little Cu
2
O to it.
Basic nature : Owing to the presence of unshared electron pairs on oxygen, ethers are basic. Hence they
dissolve in strong acids (e.g., HCl, conc. H
2
SO
4
) at low temperature to formoxonium salts.
2.
[(C
2
H
5
)
2
OH]
+
HSO
4
-
]
Diethyloxonium
hydrogen sulphate
(C
2
H
5
)
2
O + H
2
SO
4
Diethyl ether
On account of this property, ether is removed from ethyl bromide by shaking with conc. H
2
SO
4
.
The oxonium salts are stable only at low temperature and in a strongly acidic medium. On dilution,
they decompose to give back the original ether and acid.
Ethers also form coordination complexes with Lewis acids like BF
3
, AlCl
3
RMgX, etc.
R
R
2
O
..
R
2
O: + BF
3
Mg
R
2
O BF
3
(b) 2R
2
O + RMgX
(a)
R
2
O
X
It is for this reason that ethers are used as solvent for Grignard reagents.
Action of dilute H
2
SO
4
(hydrolysis).
dil. H
2
SO
4
, heat
3.
C
2
H
5
-O-C
2
H
5
2 C
2
H
5
-OH
Pressure
4. Action of concentrated H
2
SO
4
.
C
2
H
5
-O-C
2
H
5
+ H
2
SO
4
(conc.)
heat
C
2
H
5
OH + C
2
H
5
HSO
4
24
Alcohol
5. Action of conc. HI or HBr.
(i) C
2
H
5
- O-C
2
H
5
+ HI (cold)
(ii) C
6
H
5
-O-C
2
H
5
+ HI
C
2
H
5
OH + C
2
H
5
I
C
6
H
5
OH + C
2
H
5
I
Mechanismof reaction : S 2 and S 1 mechanisms for the cleavage of ethers with HI. S 2cleavage
N N N
occurs at a faster rate with HI thanwith HCl?
H
+
Step 1:
R ÷ O÷ R' + HI ÷÷÷
R
+ I
-
O
R'
base
2 acid
2
acid
1
base
1
H
+
O
Step 2 for S
N
2 I
÷
÷
s
÷
low
÷÷RI + HOR' (R is 1°) + R R'
Step 3 for S 1 R
+
+ I
-
÷÷RI (R be 3°)
N
(b) The transfer of H
+
to ROR' instep 1 is greater with HI, which is a stronger acid, than with HCl.
Furthermore, in step 2, I
-
, being a better nucleophile than Cl
-
, reacts at a faster rate.
25
Alcohol
SOLVEDEXAMPLES
Ex.1 Place the following groups of compounds indecreasing order of acidity and justifyyour answers.
(a) Phenol (A), o-nitrophenol (B), m-nitrophenol (C), p-nitrophenol (D);
(b) Phenol (A), o-chlorophenol (E), m-chlorophenol (F), p-chloroophenol (G); and
(c) (A), o÷cresol (H), m-cresol, (I), p-cresol (J).
(a) NO is electron -withdrawing and acid -strengthening byboth induction and resonance. Its reso- Sol.
2
nance effect is effective fromonlythe ortho and para positions to about an equal extent. It predominates
over the inductive effect whichoperates fromall positions but at decreasing effectiveness with increasing
separation of NO and OH. Hence all the nitrophenols are more acidic thanphenol withm-nitrophenol
2
being the weakest of the three. Since the inductive effective fromthe closer o positions is the strongest,
one might expect o-nitrophenol to be stronger than p-nitrophenol. However, the intramolecular H-bond
in o-nitrophenol must be broken and this requires some energy. The decreasing order is D>B>C>A.
(b) Although Cl is electron - donating by resonance, its electron - withdrawing inductive effect that
decreases with increasing separation of Cl and OHpredominates, making all the chlorophenols more
acidic than phenol. The decreasing order is E > F > G>A.
(c) Me is electron - donatinginductive fromall positions and hyperconjugativelyfromthe ortho andpara
positions. The three isomers are weaker acids than phenol. m-Cresol is the strongest because its acidity
is not weakened by hyperconjugation. The decreasing order isA> I > J >H.
Hydrolysis ofcompound (A) of molecular formula C
9
H
10
Cl Br yields (B) of molecular formula C
9
H
10
O.
(B) gives the haloform reaction. Strong oxidation of (B) yields a dibasic acid which forms only one
mononitro derivative. What isA?
Ex.2
Cl Br
C -CH
3
COONa
O = C -CH
3
H
2
O I
2
Sol. + CHI +
3
NaOH
CH
3
(A)
CH
3
CH
3
(B)
C
9
H
10
O
O = C -CH
3
COOH
COOH
NO
2
HNO
3 [O]
H
2
SO
4
COOH
(One mononitroderivative)
CH
3
(B)
COOH
Ex.3 When Bromobenzene is monochlorinated two isomeric compounds (A) and (B) are obtained.
Monobromination of (A) gives several isomeric products of molecular formula C
6
H
3
Cl Br
2
, while
monobrominationof (B) yields onlytwo isomers (C) and(D). Compound (C) is identical withoneof the
compounds obtained fromthe bromination of (A). Give the structures of (A), (B), (C) and (D) and also
structures of four isomeric monobrominated products of (A). Support your answer with reasoning.
26
Alcohol
Br Br Br
Cl
Cl
2
/FeCl
3
-HCl
Cl
2
/FeCl
3
-HCl
Sol.
Bromobenzene
o-Bromochlorobenzene
(A)
Cl
p-Bromochlorobenzene
(B)
Br
Br
Br
Cl
Cl Cl
Br
2
+
Br
(B)
2-Bromochlorobenzene
(A)
Br
2-Chloro-1,4-dibromobenzene
(ii)
2-Chloro-1,3-dibromobenzene
(i)
Br
Br
Cl
Br Cl
+
Br
4-Chloro-1,3-dibromobenzene
(C
6
H
3
ClBr)
(iii)
3-Chloro-1,2-dibromobenzene
(iv)
Br
Br
Br
Br
Br
2
+
Br
Cl
4-Chloro-1,3-dibromobenzene
(C)
Cl
4-Chloro-1,2-dibromobenzene
(D)
Cl
4-Bromochlorobenzene
(B)
(C) is identical with(iii).
Ex.4 Anorganic liquid with sweet smell and b.pt 78°Ccontains C, Hand O. Onheating with conc. HSO
2 4
gives a gaseous product (B) of empirical formula (CH)n. Compound (B) decolourises bromine water
2
and alk. KMnO . (B) also reacts with one mole of H in presence of Ni. What are (A) and (B)?
4 2
Sol. Compound (empirical formula CH ) decolourizes Br water, reacts with alk. KMnO and adds one
2 2 4
mole of H and so (B) is alkene.
2
Compound (B) is obtained from(A) by the action of H SO and so (A) is alcohol.
2 4
Ahas b.pt. 78°C. So (A) is ethanol
C
2
H
5
OH ÷÷÷÷÷÷÷C
2
H
4
Conc.H
2
SO
4
Reactions: (i)
Ethanol Ethylene
C
2
H
4
+ Br
2
(B)
water ÷decolourises (C H Br ) (ii)
2 4 2
C
2
H
4
+ KMnO
4
÷decolourises (HCOOK) Pot. formate
(B)
(iii) C H + H ÷C H
2 4 2 2 6
27
Alcohol
Ex.5 Two isomeric compounds (A) and (B), have same formula C
11
H
13
OCl. Both are unsaturated, and
yield
the same compound (C) oncatalytic hydrogenation and produce 4-Chloro-3-ethoxybenzoic acid on
vigorous oxidation.(A) exists ingeometrical isomers, (D) and (E), but not (B). Give structures of (A) to
(E) withproper reasoning.
As oxidation of (A) and (B) gives 4-Chloro-3-ethoxybenzoicacid, the structures of (A) and (B) can be
writtenas
Sol.
COOH
R
OC
2
H
5
OC
2
H
5
vigorous
oxidation
Cl
Cl
4-Chloro-3-ethoxybenzoic acid
(C)
(A) and (B)
Since the molecular formula ofAand B is C
11
H
13
OCl, therefore Rmust be C
3
H
5
. As (A) and (B)
are
unsaturated compounds, both give the same compound (C) oncatalytic hydrogenation. Therefore R
must be -CH = CH-CH
3
or -CH
2
-CH = CH
2
. Thus structures of (A) and (B) can be
CH = CH -CH
3
CH
2
-CH = CH
2
CH
2
-CH
2
-CH
3
OC
2
H
5
OC
2
H
5
OC
2
H
5
and
H
2
/Ni
Cl
(A)
Cl
(B)
Cl
(C)
Only(A) can exist as geometrical isomers and not B. Thus structures of (D) and (E) are
H
H H
CH
3
CH
3
H
C = C
C = C
OC
2
H
5
OC
2
H
5
Cl
(D)
Cl
(E)
Ex.6 An alkyl halide, X, of formula C
6
H
13
Cl on treatment with potassium tert. butoxide gives two
isomeric
alkenes Yand Z (C
6
H
12
). Both alkenes on hydrogenation give 2,3-Dimethyl butane. Predict
structures of X, Yand Z.
H
3
C -CH -CH -CH
3
- +
H
2
/Pt.
C
6
H
13
Cl
(X)
[(CH
3
)
3
CO] K
C
6
H
12
(Y and Z)
Sol.
CH
3
CH
3
2,3-Dimethylbutane
Pot. tert. butoxide
-KCl, -(CH
3
)
3
COH
Product, 2, 3-dimethyl butane suggest that (Y) and (Z) must be and Xmust be
CH
2
CH
3
CH
3
CH
3
CH
3
CH
3
H
3
C
CH
3
H
3
C
H
3
C
H
3
C
H
3
C
C = C CH -C CH -C
Cl
(Y)
C
6
H
12
(Z)
C
6
H
12
(X)
(C
6
H
13
Cl)
28
Alcohol
This series of reactions are
|
CH
3
CH
3
H
3
C
H
3
C
CH
2
CH
3
CH
3
CH
3
H
3
C
H
3
C
o
H C
|
C = C
3
H
3
C
CH -C C - C
Cl
+
[(CH
3
)
3
CO]
-
K
+
2,3-Dimethylbut-1-ene
(Z)
2,3-Dimethylbut-2-ene
(Y)
2-Chloro-2,3-dimethylbutane
(X)
H
2
/Ni
H /Ni
2
CH
2
CH
3
H
3
C
H
3
C
CH -CH
2,3-Dimethylbutane
Ex.7 Amixture of ethyl alcohol and n-propyl alcohol on treatment with H
2
SO
4
gives a mixture of three ethers.
On the other hand, a mixture of tert. butyl alcohol and ethyl alcohol gives the good yieldof a single ether.
Identify the ether and account for its good yield.
H
2
SO
4
-H O
H
3
C - CH
2
- CH
2
- OH
n-Propyl alcohol
H
3
C - CH
2
- O - CH
2
- CH
3
Diethyl ether
H
3
C - CH
2
- OH
Ethanol
Sol. (a) +
2
+
H
3
C - CH
2
- CH
2
- O - CH
2
- CH
2
- CH
3
H
3
C - CH
2
- CH
2
- O - CH
2
- CH
3
+
Ethyl n-propyl ether
Di-n-propyl ether
CH
3
CH
3
H
2
SO
4
-H O
H
3
C - C - O - CH
2
- CH
3 (b)
H
3
C - CH
2
- OH
Ethyl alcohol
+
H
3
C - C - O - H
2
CH
3 CH
3
tert. butyl alcohol
The mixture of ethyl alcohol and tert. butyl alcohol on treatment with H
2
SO
4
gives tert. butyl ethyl
ether
in good yield, because tert. butyl alcohol gives stable tert. butyl carbocation which rapidly undergoes
nucleophilic attack byethyl alcohol to give tert. butyl ethyl ether.
CH
3
CH
3
CH
3 ..
C
2
H
5
-O
..
-H
H
+
-H O
+
H
3
C - C + H
3
C - C -OH H
3
C - C -O - C
2
H
5
2
CH
3
tert. butyl carbocation
CH
3
CH
3
H
CH
3
..
H
3
C - C -O
..
-CH
2
- CH
3 -H
+
CH
3
Ethyl tert. butylether
On the other hand, in first case, both ethyl alcohol and n-propyl alcohol yield almost equally stable
carbocations, each one of which can be attacked either by ethyl or n-propyl alcohol giving a mixture
of three ethers.
29
Alcohol
Ex.8 0.535gmethanol and acetaldehyde mixture when heated with Fehling solution gave 1.2 gmof a red
precipitate. What is the percentage of acetaldehyde in the mixture? [Atomic weight. of Cu= 63.8].
C H OH + CH CHO = 0.535 Sol.
2 5 3
Let ‘a’ gmC H OHand‘b’gmCH CHObe present in mixture
2 5
a + b = 0.535
3
Nowmixture reacts with Fehling solution to give a red precipitate, which suggests a characteristic
reaction for aldehyde, is
CH CHO + 2CuO ® CH COOH + Cu O
3
Fehling solution
3 2
red ppt.
Q143.6 gmCu Ois given by 44gmCH CHO
2 3
44×1.2
1.2 gmCu Ois given by = 0.368 gmCH CHO
2
So, b = 0.368 gm
143.6
3
0.368
% CH CHO =
×100
= 68.73%
3
0.535
Ex.9 Howwill you prepare (a) carbitol (water soluble organic solvent) and (b) 18-crown-6 (a crown-ether)
fromethylene oxide.
+
H
Sol. (a)
C H - OH + CH - CH C H O - CH CH - OH
2 5 2 2
O
2 5 2 2
CH
2
-CH
2
O
C
2
H
5
- O - CH
2
- CH
2
- O - CH
2
- CH
2
- OH
Carbitol
HCl
(b) 3 CH - CH
HO - CH - CH - O - CH - CH - O - CH - CH OH
2 2
O
2 2 2 2
(A) Triethyl glycol
HCl
2 2
ClCH
2
CH
2
OCH
2
CH
2
- OCH
2
- CH
2
Cl
(B)
O
O
O
NowA+ B
aq. KOH
O O
O
18-Crown-6
Ex.10 Predict the product(s) of each reaction below. Be sure to specify the stereochemistry where appropri-
ate. (Ph, phenyl; *, isotope label)
(a) Ph-O-CH -Ph
÷
excess HI
÷÷
2
(b) (H C) CH-O-C(CH )
3 2 3 3
(c)
÷
1
÷
equiv HI
÷
30
Alcohol
O
÷
÷
1
÷
. PhO
÷
2. H

(d)
Ph
O
H
+
(catalyst )
÷÷÷÷÷
Ph÷OH (e)
Ph
O
(f)
+
H
CH
2
CH
3
÷
H
÷
(c
÷
ataly
÷
st )
÷
H
H
H
2
O
O
(g)
H
CH
2
CH
3
÷
1. OH
÷÷
+
÷÷
H
H
2. H
*
A
-O -CH
2
-CH = CH
2
÷÷÷
(h)
+ ÷
(i) CH
3
- S -CH
3
+ (CH
3
CH
2
)
3
O BF
4
÷÷÷
H
O
CH
3
H
O
CH
3
÷
HCl
÷
(j)
÷
1
÷
. PhL
÷
i
÷
(k)
2. H
+
Sol. (a) Ph -OH + I-CH -Ph S 1 cleavage at the benzyl carbon of the protonated ether
2 N
(b) (H
3
C)
2
CH -OH + Br -C(CH
3
)
3
S
N
1 cleavage at the more substituted carbon of the proto-
nated ether
OH
(c) S 2cleavage at the less hindered carbonofthe protonated ether
+ CH
3
I H
N
(d) S 2 attack at the less hindered carbon of the oxirane
N
Ph -CH -CH
2
-O -Ph
OH
Ph -CH -CH
2
-OH
L
(e)
OPh
31
Alcohol
H
CH
2
CH
3
(f) HO -CH
2
- Like S 1 attack by water on the more substituted carbon of the
proto-
N
OH
nated oxirane
CH
3
(g) HO -CH
2
-
S 2 attack at the less hindered carbon of the oxirane, with retention of
N
H
CH
2
CH
3
configuration at the other carbon
OH
CH
2
(h) Claisen rearrangement
CH
3
+
÷
(i)
H
3
C
S
BF
4
+ (Ch
3
CH
2
)
2
O
S 2 attack by the sulfide onthe trialkyloxonium ion
N
CH
2
CH
3
H
OH
CH
3
(j)
Like S 1 attack byCl onthe more substituted carbon of the protonated oxirane
N
-
Cl
(some Zisomer may also be formed)
Ph
H
(k) S 2 attack by “Ph
-
” at the less substituted carbon of the oxirane
OH N
CH
3
Ex.11 3,3-Dimethylbutane-2-ol loses a molecule of water in the presence of concentrated sulphuric acid to
give tetramethylethylene as a major product, suggest a suitable mechanism.
CH
3
CH
3
+
H
Sol.
CH
3
- C CH -CH
3
CH
3
-C -CH -CH
3 -H O
2
H
3
C
+
OH
2
CH
3
OH
CH
3
CH
3
CH
3
+
1,2-Methyl shift
CH
3
-C -CH -CH
3
CH
3
2º Carbocation
Less stable
C = C
-H
+
CH
3
CH
3
Tetramethylethylene
0.037 g of an alcohol, ROH was added to CH
3
MgI and the gas evolved measured 11.2 cm
3
at S.T.P.
What is the molecular mass of ROH? On dehydration ROHgives an alkene which on ozonolysis gives
acetone as one of the products. ROHon oxidation easily gives an acid containing the same number of
carbon atoms. Give structrue of ROHandthe acid with proper reasoning.
Ex.12
Sol. CH
4
+ ROMgI ROH + CH
3
MgI
Alcohol
11.2 cm
3
methane = 0.037 g alcohol 
32
Alcohol
0.037 × 22,400
22,400 cm
3
methane =
= 74 g alcohol
11.2
Molar mass of alcohol (C
n
H
2n+1
.OH) is 74 g mol
-1
12n + 2n + 1 + 17 = 74 or 14n + 18 = 74
56

14n = 56 or n = = 4
14
Molecular formula of alcohol is C
4
H
9
OH. Since the alcohol can be easily oxidised to acid, it must be

alcohol. Ondehydration alcohol gives alkene which onozonolysis gives acetone as one of the proudcts.
Thus alcohol must consist of the fragment (CH
3
)
2
CH- and hence the alcohol is isobutyl alcohol. The
concerned reactions are as follows :
CH
3
CH
3
-CH -
CH
2
OH
Isobutyl alcohol
CH
3
CH
3
-C = CH
2
+ H
2
O
Isobutylene
Conc.H
2
SO
4
A
O
CH
3
CH
3
-C = CH
2
+ O
3
CH
3
CH
CCl
4
Low temp.
C CH
H
2
O/Zn
2
3
O O
Ozonide
CH
3
C = O + HCHO + H
2
O
2
CH
3
Acetone
CH
3
CH
3
CH
3
[O]
-H O
[O]
CH
3
-CH -CH
2
OH
2-Methylpropan-1-ol
CH
3
-CH -COOH
2-Methylpropanoicacid
CH
3
-CH -CHO
2-Methylpropana1
2
Ex.13 Amixture of two aromatic compoundsAand Bwas separated by dissolving inchloroformfollowed by
extraction with aqueous KOHsolution. The organic layer containing compound A, when heated with
alcoholic solution of KOHproduced a compound C(C
7
H
5
N) associated with an unpleasant odour. The
alkaline aqueous layer on the other hand, when heated with chloroformand then acidified gave a mixture
of two isomeric compounds Dand Eof molecular formula C
7
H
6
O
2
. Identify the compoundA, B, C, D,
Eandwrite their structures.
KOH
(alc.)
Organic layer
(A)
C
7
H
5
N
(C)
|
mixture of
|
CHCl /H
+
|
3
Sol. A and B
|
C H O
\ .
7 6 2
(D)
CHCl
3
/H
+
Aqueous layer
(B)
C
7
H
6
O
2
(E)
Since the compound C having the molecular formula C
7
H
5
Nhas an unpleasant smell, it must be an
isocyanide corresponding to the structure C
6
H
5
-N÷C(C).
Consequently, (A) must be an amine corresponding to the structure C
6
H
5
NH
2
(A) (Aniline)
Since (B) gives positive Reimer-Teimann reaction, it must be a phenol corresponding to the
structure C
6
H
5
OH.
CHCl
3
/H
+
Thus,
OH
+
OHC OH
OH
(E)
(B)
CHO
(D)
33
Alcohol
Q.1
Q.2
Drawthe structures of all isomeric alcohols of molecular formula CH Oand give their IUPACnames.
5 12
While separating a mixture ofortho and para nitrophenols bysteamdistillation, name the isomer which
will be steamvolatile. Give reason.
Showhowwill you synthesis:
(i) 1-phenylethanol froma suitable alkene.
(ii) cyclohexylmethanol using analkyl halide by anSN reaction.
Q.3
2
(iii) pentan-1-ol usinga suitable alkyl halide?
Q.4
Q.5
Q.6
Give two reactions that showthe acidic nature of phenol. Compareacidityof phenol withthat of ethanol.
Explain why is ortho nitrophenol more acidic than orthomethoxyphenol ?
Explain howdoes the -OHgroup attached to a carbonof benzene ring activate it towards electrophilic
substitution?
Give reasonfor the higher boiling point of ethanol in comparison to methoxymethane.
Howis 1-propoxypropane synthesized frompropan-1-ol ?Write mechanism of this reaction.
Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable method.
Give reason.
Write the equationof the reaction of hydrogen iodide with:
(i) 1-propoxypropane (ii) methoxybenzene and (iii) benzyl ethyl ether.
Explain the fact that in aryl alkyl ethers (i) the alkoxy group activates the benzene ring towards
electrophilic substitution and (ii) it directs the incoming substituents to ortho and para positions in
benzene ring.
Write the mechanismof the reaction of HI with methoxymethane.
Describe the mechanismof alcohols reacting bothas nucleophiles and as electrophiles in their reactions.
Write one chemical reaction each to illustrate the following :
(i) Reimer -Tiemann reaction
(ii) Williamson's synthesis
Howwouldyou account for the following :
(i) Phenols are much more acidic than alcohols.
(ii) The boiling points of ethers are much lower than those of the alcohols of comparable molar masses ?
Write the reactionand the conditions involved inthe conversions of
Q.7
Q.8
Q.9
Q.10
Q.11
Q.12
Q.13
Q.14
Q.15
Q.16
(i) Propene to 1-propanol (ii) Phenol to Salicylic acid
Q.17 Howare the following conversions carried out ? (Write the reactions and conditions ineach case)
i) Ethanol to 2-propanol
(ii) Phenol toAcetophenone.
Q.18
Howare the following conversions carried out ?
(i) Phenol toToluene
(ii) Ethanol to 1, 1-dichloroethane.
34
EXERCISE-I
Alcohol
Q.19 Howare the following conversions carried out ? (Write reactions withconditions).
(i) 1-propanol to 1-chloro-2-propanol (ii) Phenol to salicylic acid
Write reactions and conditions for the following conversions
(i) 2-Propanone into 2-methyl-2-propanol (ii) n-Propyl alcohol into hexane.
Explain hydration of alkene ?
Write the method of formation of alcohol fromacid derivatives ?
Howwill you distinguish between the following pairs bychemical reactions ?
Q.20
Q.21
Q.22
Q.23
(i) 1-Propanol and 2-Propanol (ii) Ethanol and phenol
Q.24
Q.25
Give reasons for the fact that methanol is miscible with water while iodomethane is not.
Howwill you carryout following conversions
(i) EthylAlcohol to ethylene glycol (ii) 2-Propanol to 1-bromopropane
Q.26 Explain the mechanismof following reactions
2C
2
H
2
OH ÷÷÷
2
÷÷
4
÷C
2
H
5
OC
2
H
5
+ H
2
O
conc.H SO
413K
Give equations ofthe following reactions:
(i) Oxidation of propan-1-ol with alkaline KMnO solution.
Q.27
4
(ii) Bromine in CS withphenol.
2
(iii) Dilute HNO withphenol.
3
(iv) Treating phenol with chloroformin presence of aqueous NaOH.
Explain the following withanexample.
(i) Kolbe’s reaction.
(ii) Reimer-Tiemann reaction.
(iii) Williamsonether synthesis.
(iv) Unsymmetrical ether.
Write the mechanismof Reimer-Tiemann reaction ?
Exmplain estrification reactionwithmechanism?
Q.28
Q.29
Q.30
35
Alcohol
Q.1 Arrange the following as mentioned.
(1) C
6
H
5
CH
2
CH
2
Br,
(I)
C
6
H
5
CH(Br)CH
3
and
(II)
C
6
H
5
CH= CH-Br (Reactivity withAgNO
3
)
(III)
Cl
Cl
Cl
NO
2
(Reactivitywith NaOct) (2)
NO
2
NO
2
NO
2
(I)
H
2
O,
(I)
(II)
CH
3
O
-
and
(III)
(III)
CH
3
COO
-
(IV)
OH
-
(II)
(3) (Nucleophillicityrate
SN
2
reaction)
CH
3
COO
-
,
(I)
OH
C
6
H
5
O
-
(II)
C
6
H
5
SO
3
-
(III)
(4) (Leaving group ability)
(5) , C
2
H
5
OH, HCOOH, CH
3
COOH (Acidic strength)
(I) (II) (III) (IV)
CH
2
-OH
CH
2
-OH
(6) C
6
H
5
CH
2
OH, (C
6
H
5
)
2
CHOH, (C
6
H
5
)
3
COH,
NO
2
(IV)
Cl
(I) (II) (III) (V)
(Reactivity withHBr decreasing order)
(7) Phenol,
(I)
o-chlorophenol
(II)
m-chlorophenol,
(III)
p-chlorophenol
(IV)
(Decreasing acidic character)
(8) CH
3
CH
2
CH
2
CH
2
-OH,
(I)
CH
3
CH(OH)CH
3
.
(II)
(CH
3
)
2
C(OH)C
2
H
5
(III)
(decreasing order of reactivityfor esterification)
[Classifies SN
1
, SN
2
, E
1
or E
2
]
[Classify as SN
1
, SN
2
, E
1
, E
2
]
[Classify as SN
1
, SN
2
, E
1
or E
2
]
(9)
(10)
CH
3
CH
2
CH
2
Cl + I-
(CH
3
)
3
CBr + CN
-
(alc)
CH
3
CH(Br)CH
3
+ OH
-
(11)
(12) t-Butyl chloride, sec-butyl chloride and CCl
4
with alc silver nitrate.
36
EXERCISE-II
Alcohol
Q.2 Identity the productsA, B, C, Detc.
Me
dil. KMnO
4
HIO
4
OH
A
C A B
(1)
Me
CHCl
2
C
6
H
6
C
H
2
O/H
+
(A)
(2) CH
4
B CH
3
Br
D
AlCl
3
(anhyd)
OH
G
(3) H
A
+ H
B
(Elb’s oxidation)
H
©
(4) X(with intermediate)
OH
HI (excess)
Heat
(5) (CH
3
)
2
CHOCH
3
OH
CH
3
(CH
2
)
4
COOH
ZnCl
2
Zn-Hg
A B
(6)
HCl
OH
NO
2
(C
2
H
5
)
2
SO
4
OH
-
Zn/HCl NaNO
2
/HCl C
6
H
5
OH
5ºC
C A B D
(7)
OH
PBr
5
alcohol Br
2
B C
(8)
A
CH
3
CH
2
CH
2
Br
KOH
alcohol followed by NaNH
2
dil. H
2
SO
4
Hg
2+
NH
2
OH
E D F
Q.3 Explain the following giving reasons (equations wherever necessary)
(1)
(2)
Sodiummetal can be used for drying diethyl ether and benzene but not ethanol.
The boiling point of the three alcohols lie in the order : n-Butyl alcohol >sec-Butyl alcohol >ter
Butyl alcohol.
No esterification takes place between ethyl alcohol and excess of sulphuric acid at 170ºC.
Sodiumchloride solution in water is added to decrease the solubility of organic compounds in
water.
Acid catalysed dehydration of t-butanol is faster thanthat of n-butanol.
Alcohols cannot be used as solvent with Grignard reagents or with LiAlH
4
.
Phenols are more acidic than alcohols.
(3)
(4)
(5)
(6)
(7)
37
Alcohol
Alkylation of PhO
-
withan active alkyl halide such as CH
2
= CHCH
2
Cl gives phenylallyl ether (8)
and also some o-allyl phenol.
Although phenoxide ion has more number of resonating structures thanbenzoate ion, benzoic
acid is a stronger acid thanphenol.
Although n-alcohol and acetic acid both have the same molecular mass (60), the former boils at
a lower temperature (97º) than the latter (118ºC).
Drygaseous hydrohalic acids and not their aqueous solutions are used to prepare alkyl halides
fromalkenes.
Isobutane gas dissolves in63%H
2
SO
4
to forma deliquescent white solid. If the H
2
SO
4
solution
is diluted with water and heated, the organic compound obtained is a liquid boiling at 83ºC.
tert-Butyl iodide undergoes following reactions.
(CH
3
)
3
Cl + H
2
O ÷ (CH
3
)
3
COH+ HI
(CH
3
)
3
Cl + OH
-
÷ (CH
3
)
2
C = CH
2
+ H
2
O + I
-
CH
3
CH
2
I undergoes loss of HI with strong base faster than CD
3
CH
2
I for loss of DI
The carbocation is F
3
C-C
+
is destabilized while the carbocation Me
3
C
+
is stabilized.
p-Dihalobenzenes have higher melting points and lower solubilities than that of their o- and
m-isomers.
Iodoformgives precipitate with silver nitrate onheating, while chloroformdoes not.
Ethyl iodide becomes violet on standing inpresence of light.
When 2-chloro-3-methylbutane is treated with alcoholic potash, 2-methyl-2-butene is the
main product.
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
Q.4 What happens when(Give equations also)
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
Ethylidene bromide is hydrolysed with aq. potassiumhydroxide.
Chloral is treated with aqueous sodiumhydroxide.
Chloroformis boiled withaqueous potassiumhydroxide.
Phenol is treated with carbon tetrachloride inpresence of excess of alkali.
Propene is heated with chlorine at about 400ºCunder a pressure of 70 atmosphere.
Silver acetate is treated with bromine.
Carbon tetrachloride is treated with hydrogen fluoride inpresence of antimony fluoride.
2-Butanol is treated with acidified potassiumdichromate.
Diethyl ether is heated with sulphuric acid under pressure.
Excess of ethanol is heated with concentrated sulphuric acid at 140ºC.
Diethyl ether is heated with concentrated sulphuric acid.
Diethyl ether is treated with concentrated sulphuric acid at 0ºC.
Phenol is treated with excess of bromine water.
Tert. butyl iodide forms tert. butyl alcohol with water but with OH
-
yields Isobutylene. Explain.
WhyS
N
reaction proceeds faster in methanol than in C
6
H
6
?
Whydoes aqueous sodiumbicarbonate solution dissolve carboxylic acids but not phenols though they
are also acidic ?
What is the function of ZnCl
2
inLucas reagent employed inthe reaction of alcohols ?
Q.5
Q.6
Q.7
1
Q.8
38
Alcohol
Q.9 Dehydration of alcohols to alkenes is always carried out in the presence of conc. H
2
SO
4
and not with
conc. HCl or HNO
3
.
Give structures of (W), (X), (Y) and (Z) inthe following reactions :
CrO
3
Q.10
H
2
C = CH - CH
2
OH (W) ;
(CH Cl )
2 2
+ -
H
3
O CH
3
OH,H
+
KMnO
4
.OH
(W) (X) C H O (Y) C H O (Z) C H O .
5 10 2 5 12 4 3 6 3
(cold, dilute) H
2
O
Q.11 Anorganic compound (A), C
9
H
12
Owas subjected to a series of tests inthe laboratory.
It was found that this compound :
(i)
(ii)
(iii)
(iv)
(v)
Rotates the plane polarized light.
Evolves hydrogen gas with sodium.
Reacts with I
2
and NaOHto produce a pale yellow solid compound.
Does not react with Br
2
/CCl
4
.
Reacts withhot KMnO
4
to formcompound (B), C
7
H
6
O
2
whichcan also be synthesized by the
reaction of benzene and carbonyl chloride followed by hydrolysis.
Loses optical activityas a result of formation of compound (C) onbeing heated withHI and P.
Reacts with Lucas reagent in about 5 minutes.
(vi)
(vii)
Give structures ofAto Cwithproper reasoning and drawFischer projection for (A). Give reactionsfor
the steps wherever possible.
Compound (A), C
4
H
8
O, on catalytic hydrogenation gave (B) C
4
H
10
O. Compound (A) decolorized
Br
2
inCCl
4
and cold aqueous KMnO
4
solution. On refluxing, (B) withHBr, compound (C) is formed.
(C), on treatment with Mg in dry ether followed by hydrolysis, gave a hydrocarbon gas weighing1.5 g
per 1.12 litres at S.T.P. Give a structure for (A).
Explain brieflythe formation of products giving the structure of the intermediates.
Q.12
Q.13
(a)
NaNH
2
NH
3
(b)
OCH
3
OCH
3
Br
H
2
N
O
H
3
C C-OC
2
H
5
CH
O
O
C-OC
2
H
5
(i) OH
-
(ii) H
+
NaOEt Br
(c)
H
2
C
H C-CH-C-OH
3
C-OC
2
H
5
CH
2
-C-OH
O
O
39
Alcohol
Q.14 (a) An organic compound C
8
H
18
on monochlorination gives a single monochloride. Write the
structure
of the hydrocarbon.
Write the structures of possible major monosubstituted products formed whenBr
+
attacks the
following molecules.
(b)
, OCH
3
,
COO
HO
3
S NHCOCH
3
Q.15 Cyclobutyl bromide on treatment with magnesium in dry ether forms an organometallic A. The
organometallic reacts with ethanal to give an alcohol B after mild acidification. Prolonged treatment
of alcohol B with an equivalent amount of HBr gives 1-Bromo-1-Methylcyclopentane (C). Write
the structures ofA, Band explain howCis obtained fromB.
Write the products inthe following reactions Q.16
Peroxide
(i) H
3
C-CH = CH
2
+ BrCCl
3
H
3
C-CH=C(CH
3
)
2
+ HCl
Peroxide
(ii)
Q.17 Write down the structures for A, B, C, Dand F.
NaNH
2
Mel
Na/NH
3
(l)
PhC÷ CH A B
H
+ .
-
.
+ KNH
2
Ph
(i) C
C = C
Ph Br
(ii) D Me
I + Cu + Heat
Me
CH
3
+ H
3
C- C- CH
2
-Br + Anhy. AlCl
3
Heat
H
(iii) E
Q.18 Dehydrobromination of compounds (A) and (B) yield the same alkene (C).Alkene (C) can regenerate
(A) and (B) byaddition of HBr in the presence and absence of peroxide respectively. Hydrolysis of (A)
and (B) give isomeric products (D) and (E) respectively, 1, 1-Diphenylethane is obtained on the reaction
of (C) with benzene in the presence of H
+
. Give structures of (A) to (E) with reasons.
CompoundA, C
8
H
8
Ocan beoxidised with KMnO
4
to Bhaving molecular formula C
8
H
6
O
4
. Compound
B is dicarboxylic acid, but does not form anhydride on heating. B When treated with bromine in
presence of iron, gives only one monoderivative C, C
8
H
5
BrO
4
. Give the structural formula of A, B
and C.
Howare the following conversions carried out?
(i) Propene ÷ Propan-2-ol.
(ii) Benzyl chloride ÷ Benzyl alcohol.
(iii) Ethyl magnesiumchloride ÷ Propan-1-ol.
(iv) Methyl magnesiumbromide ÷ 2-Methylpropan-2-ol.
Q.19
Q.20
40
Alcohol
Q.21 Write the name the reagents and complete equation in following conversion reactions ?
(i) Oxidation of a primary alcohol to carboxylic acid.
(ii) Oxidationof a primaryalcohol to aldehyde.
(iii) Bromination of phenol to 2,4,6-tribromophenol.
(iv) Benzyl alcohol to benzoic acid.
(v) Dehydration of propan-2-ol to propene.
(vi) Butan-2-one to butan-2-ol.
Write the names of reagents and equations for the preparation of the following ethers byWilliamson’s
synthesis:
Q.22
(i) 1-Propoxypropane
(iii) 2-Methoxy-2-methylpropane
(ii) Ethoxybenzene
(iv) 1-Methoxyethane
Q.23 Illustrate with examples the limitations of Williamson synthesis for the preparation of certain types of
ethers.
Write equations ofthe following reactions: Q.24
(i) Friedel-Crafts reaction-alkylation of anisole.
(iii) Bromination of anisole inethanoic acid medium.
(ii) Nitrationof anisole.
(iv) Friedel-Craft’s acetylation of anisole.
Q.25 When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place:
Give a mechanismfor this reaction.
(Hint : The secondary carbocation formed instepII rearranges to a more stable tertiarycarbocationby
a hydride ion shift from3rd carbon atom.
Give equations onlyto distinguish between primary, secondary and tertiaryalcohols byLucas Test.
(i) Name the reagents and write the chemical equations for the preparation of the following compounds
byWillamson's synthesis
(a) Ethoxybenzene
(b) 2-Methyl-2-methoxypropane
(ii) Whydophenols not give protonationreaction readily ?
The following is not anappropriate reaction for the preparationof t-butylethyl ether.
Q.26
Q.27
Q.28
(i) What would be the major product of this reaction ?
(ii) Write a suitable reaction for the preparationof tert-butylethyl ether.
Give the structures and IUPACname of the products expected fromthe following reactions :
(i) Catalytic reduction of butanal.
(ii) Hydration of propene inthe presence of dilute sulphuric acid.
(iii) Reaction of propanone with methylmagnesium bromide followed byhydrolysis.
Write the chemical properties of ehter ?
Q.29
Q.30
41
Alcohol
Q.1 Hydrogen bonding is possible in-
(A) Ethers (B) Hydrocarbons (C) Alkanes (D) Alcohols
Q.2 The increasing order of boiling points of 1º, 2º, 3º alcohol is -
(A) 1º > 2º > 3º (B) 3º > 2º > 1º (C) 2º > 1º > 3º (D) None
Q.3 The solubility of lower alcohols in water is due to -
(A) Formation of hydrogen bond between alcohol and water molecules
(B) Hydrophobic nature of alcohol
(C) Increases in boiling points
(D) None of these
Conversion of CH
3
OH to CH
3
COOH can suitably be carried out with the reagent (under high
pressure condition) :
Q.4
(A) CO
2
/H
2
SO
4
(B) CO/BF
3
(C) CO
2
/BF
3
(D) CO/H
2
SO
4
Q.5 Which of the following reactions of an alcohol does not involve O - H bond breaking :
(A) Reaction with alkali metals
(C) Reaction with sulphonyl chloride
(B) Reaction with an acyl chloride
(D) Reaction with conc. sulphuric acid.
Q.6 Alkyl chloride is formed when alcohol is treated with HCl in presence of anhydrous ZnCl
2
. The
order of reactivity with respect to alcohol is :
(A) 3º > 2º > 1º (B) 1º > 2º > 3º (C) 2º > 1º > 3º (D) 1º > 3º > 2º
Q.7 When ethyl alcohol reacts with acetic acid, the products formed are-
(A) Sodium ethoxide + hydrogen
(C) Ethyl acetate + soap
(B) Ethyl acetate + water
(D) Ethyl alcohol + water
Q.8 Methyl alcohol reacts with phosphorus trichloride to form-
(A) Methane (B) Methyl chloride (C) Acetyl chloride (D) Dimethyl ether
Q.9 The -OH group of methyl alcohol cannot be replaced by chlorine by the action of-
(A) Chlorine
(C) Phosphorus trichloride
(B) Hydrogen chloride
(D) Phosphorus pentachloride
Q.10 Reaction of alcohol does not show cleavage of R-O linkage-
(A) ROH + PCl
5
(B) ROH + SOCl
2
(C) ROH + HCl (D) ROH + Na
Q.11 Replacement of -OH group in alcohol by -Cl cannot be carried out with-
(A) PCl
5
(B) SO
2
Cl
2
(C) PCl
3
(D) SOCl
2
Q.12 Which alcohol does not give a ketone on oxidation-
(A) Isopropyl alcohol
(C) Ethylmethylcarbinol
(B) Allyl alcohol
(D) Methylphenylcarbinol
Q.13 A compound X with molecular formula C
3
H
8
O can be oxidised to a compound Y with the
molecular formula C
3
H
6
O
2
, X is most likely to be-
(A) Primary alcohol
(C) Aldehyde
(B) Secondary alcohol
(D) Ketone
42
EXERCISE-III
Alcohol
Q.14 Tertiary alcohols are resistant to oxidation because :
(A) They do not have o hydrogen atom
(B) Of large +I effect of alkyl groups
(C) Of greater steric hindrance
(D) All the above
Ether in contact with air for a long time form peroxides. The presence of peroxide in ether can be
tested by adding Fe
2+
ion in it and then adding -
Q.15
(A) KCNS (B) SnCl
2
(C) HgCl
2
(D) KI
Q.16 Match list I with list II and then select the correct answer from the codes given below the lists -
List I
(A) (CH
3
)
3
C -OH
(B) CH
3
-O -C (CH
3
)
3
(C) C
2
H
5
-O -C
2
H
5
(D) CH
3
-O -CH (CH
3
)
2
Codes :
List II
(a) Sulphuric ether
(b) Chain isomer of 1-butanol
(c) Mixed ether
(d) Has one secondary carbon
A
b
b
b
c
B
d
c
c
b
C
a
a
d
a
D
c
d
a
d
(A)
(B)
(C)
(D)
Q.17 Ether reacts with chlorine in the dark to form-
(A) CH
2
Cl -CH
2
-O -CH
2
-CH
3
(B) CH
2
Cl -CH
2
-O -CH
2
-CH
2
Cl
(C) CH
3
-CH (Cl) -O -CH(Cl)-CH
3
(D) CCl
3
-CH
2
-O -CH
2
-CCl
3
Ether does not form oxonium salt on reaction with
-
Q.18
(A) Cold conc. H
2
SO
4
(C) Conc. HI
(B) Cold conc. HCl
(D) None of the above
Q.19 The ordinary alkyl ethers are cleaved by -
(A) Ethanol (B) Ethyl halide (C) BF
3
(D) Hydrogen iodide
Q.20 The decomposition of ethers by HI or HBr is called -
(A) Zerewitinoff's reaction
(C) Williamson's method
Ether is not formed in this reaction
(B) Ziesel's method
(D) Hell-Volhard-Zelinsky reaction
Q.21
Con
÷
c.
H
÷
2
S
÷
O
÷
4
140º
÷
(A) 2C
2
H
5
OH
(B) (CH
3
)
3
C-Cl + C
2
H
5
ONa ÷÷
(C) C
2
H
5
Cl + (CH
3
)
3
C-ONa ÷÷
(D) Oxygen of ether can be replaced by chlorine when treated with PCl
5
Unsymmetrical ethers are best prepared by -
(A) Willamson's continuous etherification process
(B) Reacting Grignard reagent with alkyl halide
(C) Treating sodium alkoxides with alkyl bromides
(D) Heating an alkanol with conc. H
2
SO
4
Which of the following is used as an additive by fire departments under the name Rapid-Water -
Q.22
Q.23
(A) Ethylene glycol
(C) Epichlorohydrin
(B) Polyethylene oxide
(D) Epoxy oxide
43
Alcohol
Q.24 In the Williamson's synthesis for diethyl ether, which species works as a nucleophile -
(A) Halide ion (B) Ethoxide ion (C) Ethyde ion (D) Hydride ion
Q.25 The structure of the compounds formed by the reaction of diethyl ether with oxygen of air is -
(A) CH
3
CH
2
- O - O - CH
2
CH
3
CH
3
|
(B) CH
3
CH
2
- O - CH÷ O - O - H
(C) CH
3
CH
2
- O - O - CH
2
- O - CH
3
(D) CH
2
(OCH
3
) - CH
2
- O - C
2
H
5
Ether bottles should not be kept open in air because - Q.26
(A) Ether is an anaesthetic
(C) Ether is costly
(B) Ether forms an explosive peroxide
(D) Ether gets oxidised to ethanol
Q.27 Isopropyl alcohol vapour is passed over alumina heated at about at about 240ºC. The product
formed is -
(A) diisopropyl ether
(B) propene
(C) a mixture of diisopropyl ether and propene
(D) 3-hexene
Q.28 Which of the following
methoxide -
(A) CH
3
CH
2
CH
2
Cl
(C) PhCH
2
Cl
is not expect ed t o give et her on react ion with sodium
(B) CH
2
= CHCH
2
Cl
(D) CH
2
= CHCl
Q.29 Consider the following reaction,
1.(CH
3
COO)
2
Hg,CH
3
OH
CH
3
CH = CH
2
÷÷÷÷÷÷÷÷÷÷÷
2.NaBH
4
The product formed in the reaction is -
(A) (B)
(C) (D)
Q.30 When phenol is reacted with CHCl
3
& NaOH followed by acidification, salicyladehyde is
obtained.
Which of the following species are involved in the above mentioned reaction as intermediates -
O
H
CHCl
2 (A) (B) (C) (D) Both (A) and (B)
Q.31 The presence of -OH on adjacent carbon atoms can be detected by the reaction of the compound
with -
(A) Conc. H
2
SO
4
(B) Conc. HNO
3
(C) HIO
4
(D) Acidic KMnO
4
44
Alcohol
Q.32 In phenols -
(A) - OH group is attached in side chain
(B) - OH group is directly attached to benzene nucleus
(C) Both (A) & (B)
(D) None
The compound containing hydrogen bond is- Q.33
(A) Toluene (B) Phenol (C) Chlorobenzene (D) Nitrobenzene
Q.34 Phenol on treatment with ammonia gives -
(A) Benzene (B) Benzoic acid (C) Aniline (D) None
Q.35 Salicylic acid, aspirin, nylon, plastics and picric acid have a common raw material, namely -
(A) Methane (B) Formic acid (C) Phenol (D) Alcohol
Q.36 Which of the following will not be soluble in sodium carbonate solution -
(A) (B) (C) (D)
Q.37 Under suitable conditions C
6
H
5
CH
2
OH (A) C
6
H
5
OH (B), and C
6
H
5
COOH (C) can act as acids.
The increasing order of their acidic strength is -
(A) A < B < C (B) A < C < B (C) B < A < C (D) C < B < A
Q.38 Kolbe’s reaction consists in obtaining -
(A) Anisol from phenol
(B) Salicylaldehyde from phenol and CHI
3
(C) Salicylic acid from sodium phenate and CO
2
(D) Salicylic acid from phenol and CO
2
The most suitable method of separation of a 1 : 1 mixture of o- and p- nitrophenol is - Q.39
(A) Sublimation (B) Chromatography (C) Crystallisation (D) Distillation
Q.40 p-Nitrophenol is stronger acid than phenol because nitro group is -
(A) Electron withdrawing
(C) Basic
(B) Electron donating
(D) Acidic
Q.41 Which derivative of phenol gives effervescence with NaHCO
3
-
(A) o-Cresol
(C) 2,4,6- Trinitrophenol
(B) Catechol
(D) 2,4,6- Tribromophenol
Q.42 The product obtained by the reaction of phenol with benzene diazonium chloride is -
(A) Phenyl hydroxylamine
(C) Phenyl hydrazine
(B) Para amino azobenzene
(D) Para hydroxy azobenzene
Q.43 Phenol and benzoic acid can be distinguished by -
(A) Aqueous NaHCO
3
(C) Aqueous NaOH
Phenol is converted into salicylaldehyde by-
(A) Etard reaction
(B) Aqueous NaNO
3
(D) Conc. H
2
SO
4
Q.44
(B) Kolbe reaction
(C) Reimer- Tiemann reaction
(D) Cannizzaro reaction
45
Alcohol
Q.45 Alcohols which can give white turbidityimmediately onreaction withLucas reagent are
CH
3
|
H
3
C÷ C ÷ OH
|
H
(A) (B) Ph
3
C-OH (C) H
3
C-OH (D)
OH
Q.46 Correct method to prepare Me
3
C-O-Me in good yield is / are
(i) Hg( OAc)
2
+MeOH
÷÷÷÷÷÷÷÷
(ii)SBH
(A) Me
3
C-Cl + MeONa ÷÷ (B) Me
2
C = CH
2
H
©
÷÷÷
MeOH
(C) Me
3
C - ONa + MeCl ÷÷
Which is not cleaved by HIO
4
?
(D) Me
2
C = CH
2
Q.47
(A) glycerol (B) glycol (C) 1,3-propandiol (D) 1-methoxy-2-propanol
Ph
÷
.conc
÷
HI
÷
product(s) of this reaction is / are? Q.48
O
Ph Ph
I
OH
(A) (B) (C) (D)
I I
Q.49 In whichof the following reactions 3°alcohol will be obtained as a product.
O
||
MgBr (excess) + H÷ C÷ Cl ÷÷ ÷÷
+
÷ (A)
H
O
||
(B) PhMgBr (excess) + CH
3
÷ C÷ Cl ÷÷÷÷
+
÷
H
O O
|| ||
(C) CH
3
MgBr (excess) + CH
3
÷ C÷ O÷ C÷ CH
3
÷÷ ÷÷
+
÷
H
O
||
(D) CH
3
MgBr (excess) + Cl ÷ C÷ O÷ Et ÷÷÷÷
+
÷
H
Which of the following reagents or process are suitable to distinguish MeOH&EtOH?
OH
Q.50
+
& H COOH
(A) NaOI (B)
(C) anhydrous ZnCl
2
+ conc. HCl (D) Victor Mayor's process
46
Alcohol
Matrix MatchType Question
Q.51 Matchthe column:
Column-I and column-II contains fourentries each. Entryof column-I are to be uniquelymatched with
onlyone entryof column-II.
ColumnI
(Compound)
H
3
C-CH
2
-CH
2
-CH
2
-CH
2
-OH
H
3
C÷ CH÷ CH
3
|
OH
Column II
(Boiling point in °C)
(A)
(B)
(P)
(Q)
290°C
138°C
(C) H
2
C-CH -CH
2
(R) 102°C
| |
OH OH
|
OH
CH
3
|
H
3
C÷ C÷ CH
2
÷ CH
3
|
OH
(D) (S) 82.4°C
Q.52 ColumnI
(Compound)
ColumnII
(A) (P) Gives orange colour with Brady's reagent (2,4-DNP)
O
(B) (Q) Gives haloformreaction
Cl
O
(C) (R) Gives positive Beilstein's test
Cl
(D) (S) Can give aldol reaction with dil. NaOH
(T) Gives white ppt. with alcoholic
AgNO
3
47
Alcohol
ANSWERKEY
EXERCISE - I
Q.1 1.
4.
7.
10.
II > I > III
III > I > II
II > III > IV> I
E
1
Me
2.
5.
8.
11.
II > III > I
III > IV > I > II
I > II > III
E
1
O
3.
6.
9.
12.
III > II > IV> I
III > II > I > V> IV
SN-2
(t- > S- > CCl
4
)
Me Me OH
Me
Q.2 1. A= B = C =
OH O
O
O
OH
CHO
CH
3
2. A= Br
2
/hv B = C = 2 Cl
2
/hv D =
OH
OH
©
OH
3. + 4.
O
OH
OH
OH OH
OH
5. 6. A= B=
CH - CH - CH + CH OH
3 3 3
OH OH
C - (CH
2
)
4
- CH
3
CH
2
- (CH
2
)
4
- CH
3
O
NO
2
©
N
2
Cl
÷
NH
2
7. A= B = C =
OC
2
H
5
OC H OC H
2 5 2 5
D =
C
2
H
5
O N = N OH
8. A= CH
3
CH
2
CH
2
- OH B = CH
3
- CH = CH
2
C = CH
3
- CH - CH
2
Br Br
CH
3
3
D = CH
3
- C ÷ CH E = CH
3
- C - CH
2
F =
CH
C = N - OH
O
OH
OCH
3
Br
Br
Q.11 A= B = m-Cresol C= Methyl iodide D= Phenol E =
CH
3
Br
OH Br
Q.12 A= B = C =
48
Alcohol
Q.14 a = 2, 2, 3, 3-tetramethylbutane
Br
-NH - C - CH
3
-C - O - -Br
SO
3
H -
b =
O
O
OH
Me
Br
MgBr
CH - CH
3
Q.15 A= B = C =
CH
3
Q.16 CH
3
- CH
2
- C - CH
3
CH
3
- CH - CH
2
- CCl
3
Br Cl
Ph
H
H
Me
Me
Q.17 A= Ph - C ÷ C Me B = C = Ph - C ÷ C - Ph
C = C
D = Me - E =
Me - -C - Me
- -Me
Me
Ph - CH - CH
3 Q.18 A= Ph - CH
2
- CH
2
- Br B =
Br
D = Ph - CH
2
- CH
2
- OH C =
E =
Ph - CH = CH
2
Ph - CH - CH
3
OH
CHO COOH COOH
-Br
Q.19
Me COOH COOH
EXERCISE - III
Q.1
Q.8
Q.15
Q.22
Q.29
Q.36
Q.43
Q.50
D
B
A
C
B
C
A
A,B
Q.2
Q.9
Q.16
Q.23
Q.30
Q.37
Q.44
Q.51
A
A
B
B
D
A
C
Q.3
Q.10
Q.17
Q.24
Q.31
Q.38
Q.45
A
D
C
B
C
C
A,B
Q.4
Q.11
Q.18
Q.25
Q.32
Q.39
Q.46
B
B
C
B
B
D
B,C,D
Q.52
Q.5
Q.12
Q.19
Q.26
Q.33
Q.40
Q.47
D
C
D
B
B
A
C,D
Q.6
Q.13
Q.20
Q.27
Q.34
Q.41
Q.48
A
A
B
C
C
C
A,B,C
Q.7
Q.14
Q.21
Q.28
Q.35
Q.42
B
A
B
D
C
D
Q.49 B,C,D
(A) Q; (B) S; (C) P; (D) R (A) P,Q,S(B) Q,R,T(C) P,S(D) R,T
49