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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 =CHOH
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
Markonikovs 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 hydroborationoxidation: 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
Propan1ol
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
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 BOR
3 N
aO
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
5
R- CH
2
0H
1 alcohol
LiAlH / Na+C H OH
RCHR
|
OH
2 alcohol
Note :
(i) We cannot obtain 3 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
4
RCH
2
0H
||
O
+ 4H
LiAlH
4
R CH
2
0H + HX R C X
||
O
iAlH
R- C- 0R' + 4H
||
0
RCH 0H + R'0H
2
RC00C0R + 8H
L
iAlH
2 RCH
2
0H + H
2
0
6. From Grignard reagent (RMgx)
(i) Reaction withoxyrene:
o- +o o+ o+ +2
R : MgX + H
2
CCH
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 C0 Mg X
o- o+ o-
o+
+2
R C0 Mg X + H0 H R C0 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-
OH + Na 2R - 0 - Na + H
2
|
The acidic order of alcohols is
Me0H > 1 > 2 > 3
2. Esterification / Reaction with carboxylic : When reaction of alcohol with carboxylic acid in
presence of sulphuric acid to form ester.
conc.H SO
4
RCOR + H
2
O
||
O
ester
7
Alcohol
Mechanism :-
H
2
S0
4
----- H
+
+ HSO
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 OR
||
O
R OH+ R C O CR
||
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
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
CH
2
=
CH
2
H
+
+ HS0
4
-
H
2
S0
4
CH
3
- CH
2
- - H + H
+
CH
3
- CH
2
-
H
-H
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
3 amine
R
2
NH
2 amine
RNH
2
1 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. 3 > 2 > 1, 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 1 alcohol, acidic KMn0
4
is used as oxidant while for 2 alcohol acidic
K
2
Cr
2
0
7
(more strong than KMn0
4
) is used.
(e) For both (1 and 2 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
acid
ic K
2
C
r
2
O
o]
H
2
C
rO
4
+ dil. HNO
or KI +H
3
PO
4
or SOCl
2
or SO
2
Cl
2
(1) RX
(1) Alkene
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
(2) RX
3
1 , 2 , 3 amines
(3) R - O - R
(4) R - SH Thiol
il. H
2
S
Th0
2
(4) RCOOR
RCOOH
a
(5)
(6)
RONa
NO
2
(5) 1 amine
H
3
Mg
X
CH
Exception - Methyl amine gives
CH -O-CH or ether
4
R' OR
ald
.R'
CH
3 3
(7) C Acetal
N
Darzon reduction
dry HCl
(6) Aldehyde or ketone
H OR
(1 alc.) (2 alc.)
Na
/ EtO
R-OH
R' OR
(7) Acid or
Ket
one
'CO
'
dry HCl
Bouveault Blanc reduction
(8) C Ketal
Acidderivative
HCHO or Ald.or ketone
RM
X
H
2
O
R' OR
(8)
'C
Z
R'COOR ester (Z = OH,Cl, OCOCH ) (9)
(10)
(11)
(12)
(13)
(14)
3
(1 alc) (2alc) (3 alc.)
O
2
H
2
S
4
ROSO OH (Alkyl hydrogen sulphate)
2
RONO (Alkyl nitrate)
H
2
O
(9) RMgX
H
NO
hS
O
2
Cl
CH
2
CH
2
erm
en
tati
(15) RO- CH - CH - OH
2 2
Alkoxyalkanol
H
2
= C
O
ROCOCH (16)
(17)
Ester
3
D
eh
ydr
atio
n
Alkene
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 - 3 alc Alkene
Crystallization
Sucrose
(1) Cane sugar Molasses
1alc.
[
]
Aldehyde
O
]
Acid (same no. of C-atom)
[
(19)
(20)
(21)
2alc.
[
O ]
Ketone
[[O
Invertase
zymase
Fermentation
Invert sugar
hydrolysis
EtOH
3alc.
[
CrO
4
(22) 1 or 2alc. Aldehyde or ketone + Cr
+3
(green)
Diastase
HOH
(2) Grain Starch Maltose
(orange)
, H
CrO
Maltase Zymase
hydrolysis
EtOH
Fermentation
Glucose (23) 3 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 182C
while toluene (mol. wt 92) boils at 110C.
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. Kolbes 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
Libermanns Reaction: When phenol is treatedwith sodiumdissolvedin conc. Sulphuricacid, a red colouration
appears, which changes to blue on adding aqueous Na0H. This reaction is called Libermanns 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. Williamsons 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
140C
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 2 and 3 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 (180) but they are at an angle of about 110, 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 (105). 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
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), ocresol (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 78Ccontains 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. 78C. 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 OHandbgmCH 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
441.2
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
. PhO
2. H
+
(d)
Ph
O
H
+
(catalyst )
PhOH (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)
. PhL
(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
2 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
1
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
-NC(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) Kolbes 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
(Elbs oxidation)
H
c.
H
2
S
4
140
(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 240C. 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 Kolbes 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
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)
290C
138C
(C) H
2
C-CH -CH
2
(R) 102C
| |
OH OH
|
OH
CH
3
|
H
3
C C CH
2
CH
3
|
OH
(D) (S) 82.4C
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