IIT-JEE ChEmistry by N.J.

sir organic chemistry

Alcohol and Phenol
Alcohol acid catalysed hydration
+

CH3 CH = CH2 + H CH3 + CH CH2 H
: :

O 1. Lewis Base
R H
O
2. Nucleophiles H H
3. Polar protic solvents
CH3CHCH3+H
+ CH CHCH 3
3
Difference between alcohol & phenol
OH O+
H H
OH CH2OH
O

IR
Phenol alcohol H+ H H
partial double bond character between C & O (a)

high boiling point & water solubility due to Hydrogen

bonding. H/H2O
(b)
Classification
O
OH H+ H H
(c)

.S
CH2 CH2 OH
1 alcohol
(primary alcohol)
CH3CHCH3
2 alcohol
(Secondary alcohol) Ans.
OH
OH
(a) (b) (c) OH
CH3 H

CHCOH
3 Oxymercuration Demercuration (O M D M)
CH3 O OH
1. Hg(OAC)2 H H
.J
3 alcohol CH3 CH = CH2 CH3CHCH3
(tertiary alcohol) 2. NaBH4
(n hexane or paraffin solvent)
CH2 = CH OH (vinylic alcohol)
Features:
CH2 = CH CH2 OH (allylic alcohol)
(1) Markownikoff addition
(2) No. Rearrangement
General Methods of preparation
(3) Non classical carbocation
N

O
(1) from alkanes 1. Hg(OAC)2 H H
(1) OH
Cl2 /h aq.KOH 2. NaBH4
CH4 CH3 Cl H
CH3 OH
Me Me O
1. Hg(OAC)2 R H
Br2 /h (2) OR
MeCH MeCBr 2. NaBD4 D
Me Me CH3
CH3 O
O 1. Hg(OAC)2 H H
(3) CH3CCH = CH2
H H CH3COH 2. NaBH4
CH3
CH3 CH3 OH
CH3C CH CH3
(2) from alkenes
OH CH3
+ O
H H H CH3CHCH3
(i) CH3 CH = CH2
1
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 CH3 OH
(5) Conversion of lower alcohol into higher alcohol
Ans. (3) CH3C CH CH3

CH3 HI CH3I CH3 MgBr CH3 CH3

CH3OH

Hydroboration oxidation SO2Cl2 /h CH CH KOH(aq.)CH CH OH

3 2 3 2
1. BH3 THF |
CH3 CH = CH2 Cl
OO CH3OH CH3CH2OH
2. H H OH
CH3 CH2 CH2 OH
(6) from epoxy compounds
Features
1. anti markownikoff addition 1. RMgX R
2. No. Rearrangement
1.
2.H /H2O
Ex: O
1. B2H6 THF OH
1. 1. RMgX
OO 2.

RCH2CH2O MgX

IR
2. H H OH
2.H /HOH
1. B2H6 THF O
2.
OO H RCH CH OH
2. H H OH 2 2

3. 1.BD3 / THF (7) from primary amines

H
2.HOOH/ OH
NaNO
R N: 2
R OH
1.B2H6 / THF HCl
4.

5.
.S
CH3 CH = CH2
2.CH3 COOD
1.B2D6 / THF
CH3 CH = CH2

H
H
NaNO2
R N:
HCl
R N2 Cl

(diazotisation)
2.CH3 COOD
H
1.B2H6 / THF
6. CH3 CH = CH2
2.CH3 COOH Mechanism:
Ans. 1.

OH H H
(1) H (2) H (3) D + + +
.J
:

RNH2 + NO RNN=O RNN=OH

:
OH OH
(4) CH 3CHCH 2 (5) CH3CHCH2 H
H D D D H
(6) CH3CHCH2 +H
RN = NO RN = NOH
D H H +
N

(3) from alkyl halides H +

:
:

aq.KOH R OH O + RN = N D RN N
RX H +
SN2 (8) from Carbonyl compounds
aq.KOH H
CH Cl R
2 H2 /Hi
C=O R C OH
O R Na/EtOH
H H R
CH2Cl
Sn/HCl

(4) from grignard reagent
Zn/ ACOH

2 R mg 1. O2
2 R OH
2.H /H2O Fe/H2O

Mechanism:
. . LiAlH4

R
:

R + O = O ROO
(9) MPV Reduction:

H /H2O Meerwain pondorf werley reduction)

R O + RO R OH + R OH

2
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ETOOS Academy Pvt. Ltd.
F-106, Road No. 2, Indraprastha Industrial Area, End of Evergreen Motors (Mahindra Showroom), BSNL Office Lane,
Jhalawar Road, Kota, Rajasthan (324005)
 CH3 O
1. CHO Al R
R CH3 3
CH3 (6) R H+ CH3MgBr CH4 + RO

MgBr
C=O CH OH + Al(OH)3 + 3 C = O
2. H3O+
R R CH3 (7)
O

: :
(10) Oppenaur Oxidation O
H H
CH2 = C = O CH2 = C O CH3 C OR
R (CH3 )3 COAl R
CH OH 3. C=O + OR
R R H
O
(11) from Carboxylic acid
C R'OH/H OR
LiAlH4 (8) R OH R CH (acetal)
R COOH R CH2OH
OR
O O
(12) from Carboxylic acid derivatives
O C R'OH C O
(9) R H R OR + H H
LiAlH4

IR
(a) R C Cl R CH2OH
O
LiAlH4 Reaction due to C O bond Cleavage
(b) R C OR R CH2OH
ROH
O O
C C LiAlH4 (1) HI
R OH RH
(c) R O R R CH2OH Red P
O
(d)
.S LiAlH4
R C NH 2 R CH2NH2 (2) R OH
1 2
HCl/ ZnCl
2 R Cl.(Lucas Test)
SN or SN
(13) from hydrolysis of ester.
SOCl2
O (3) R OH R Cl + HCl + SO2
O SN1
C H2SO4 (dil)
(a) R OR R C OH + ROH PCl3
(4) 3R OH 3 R Cl + H3PO3
O O SN2
dil H2SO4 18
(b) C CH3 C OH+ MeOH O PCl5
.J
Me OMe (5) R H R Cl + HCl +
18 SN1 & SN2
O
General Reaction of alcohols
(a) Reactions sue to O H bond Cleavage P
Cl Cl
ROH Cl
(6) Conc.H2SO4 CH CH = CH
CH3CH2 CH 3 2
N

O | 170C
Na RO Na+ + H
(1) R H 2 OH
1
(acidic nature) (E1CB) Conc. H2SO4(E )
OH
ThO2 170C
O
(2) R H + Blue litmus Red litmus
(Alcohols are weak acids)

O
(3) R H + NaOH

Oxidation of alcohol
O O
(4) R H + NaHCO3
Red hot
1. R1 CH R2 R1 C R2
Cu Tube
O O OH
(5) R H + CH2N2 R CH3

3
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ETOOS Academy Pvt. Ltd.
F-106, Road No. 2, Indraprastha Industrial Area, End of Evergreen Motors (Mahindra Showroom), BSNL Office Lane,
Jhalawar Road, Kota, Rajasthan (324005)
 O CH2OH
Red hot K MnO4
R CH OH RC Q.2
Cu Tube H H
H
(1 alcohol to aldehydes)
K MnO4 /H
O Q.3 OH
Red hot
R CH CH3 R C CH3
Cu Tube
OH O
(2 alcohol to ketones) O
CH3 CH
CH3 Ans. 1. 2. 3.
Red hot
R CH CH3 R C = CH2
Cu Tube
OH

:
(3 alcohol dehydration to alkenes)
N
/CrO3/HCl

IR
(3) P.C.C.
Ph CH OH Red hot Cu
Q.1
2 1: 2 : 3
OH 1 aldehyde

CH 2 ketone
CH3 Red hot Cu
Q.2 .S 3 no.effect)

Red hot Cu OH O
Q.3
1.
P.C.C.

OH
O O
Ans. 1. CH C
OH P.C.C. H
2.
O
.J

:
CCH3 N
2. 3.
4. Collins Reagent : CrO3 : CH2Cl2

Oxidation of alcohol OH O
+ +
(2) Oxidising agent KMnO4 / H or K2Cr2O7/H P.C.C.
O 1.
K MnO4 /H
N

1. R CH2 OH RC
H O
(1 alcohol acid)
C
K MnO4 /H OH P.C.C. H
2. R1 CH R2 R CR 2.
1 2

OH O 5. Johns Reagent (H2CrO4 in anhydrous acetone)

(2 alcohol ketone)
1 aldehydes 2 ketones
CH3 3 alkenes
CH3
K MnO4 /H R1 C = CH 2 6. MnO2 Weak oxidizing agent
3. R1 CH CH3
MnO2
OH CH2 = CH CH2 OH
(3 alcohol alkenes) O
OH CH2 = CH C
K MnO4 /H H
Q.1

4
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ETOOS Academy Pvt. Ltd.
F-106, Road No. 2, Indraprastha Industrial Area, End of Evergreen Motors (Mahindra Showroom), BSNL Office Lane,
Jhalawar Road, Kota, Rajasthan (324005)
 Ans.
MnO2 Ph
CH2 OH O
Q.1 Me C OH + Ph C OH
O
Ph
CH O
Q.2 H C OCH3
O Ph O
Me
Q.1
Me C O C Ph H

Q.3 Et C O CH
H2O Me
Ph O
Q.4 Me C O CH2 CH3
O
O
H

Q.2 H C OH + CH3 OH

IR
CH3OH CO
O Q.5
Me H
Q.3 Et C OH + CH OH CO
Me
O O
H O
Q.4 Me C OH + CH2 CH3
OH Q.6 R O C R

Q.5
.S O
COH
+
HO
H
Q.7
OH O
COMe
COH
HO
O OH O
O
C
Q.6 R OH + HOCR H
OPh
Q.8
OH O
.J
C Me O
OH H
Q.7 + Me OH
COMe
Q.9 H
(Methyl Salicylate)
OH Et
CH3
N

O
COOH O
Q.8 + Ph H H
Q.10 MeCO H

(Phenyl Salicylate ) Me
Me
MeOH
Q.9 H COOH +
H
Et
CH3
O
H
H
Q.10 Me C OH + HO

Et

5
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ETOOS Academy Pvt. Ltd.
F-106, Road No. 2, Indraprastha Industrial Area, End of Evergreen Motors (Mahindra Showroom), BSNL Office Lane,
Jhalawar Road, Kota, Rajasthan (324005)
 Cl

: :
Phenol:- OH NaOH
2.

OH OH
OH NO2
+ H O H
3. N2 Cl

Phenol 1-Napthol 2- Napthol (Benzene diazonium chloride)

-Napthol - Napthol OH
OH
COOH
OH

IR
OH NaOH/CaO
4.

OH
(Soda lime decarboxylation)

OH OH 5. Hydroperoxide Method:-
Catechol Resorchinol Quinol (hydroquinone)
CH3 H3PO4
+ CH2 = CH CH3 ------
CH3
.S
OH
CH3
O2/air

H /H2O
OH OH -------- + ------- ----------
O-cresol m-cresol p-cresol

H2SO4 /(conc.)
6. --------------
.J

Napthalene Anthracene 1. NaOH(molten)

-----------------------
2. H

Reaction of Phenol:-
(1) Electrophilic aromatic Substitution:-
N

OH

Phenanthrene
HNO3
(a) ----------- + -----------
Methods of preparation:- H2SO4
1. Dows Prcess:-
Cl OH

NaOH Br2
(b) ----------- + -------------
360C/320atm CS2

(Follows Benzyne Mechanism) OH

Br2
(c) ---------------------
H2O

6
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ETOOS Academy Pvt. Ltd.
F-106, Road No. 2, Indraprastha Industrial Area, End of Evergreen Motors (Mahindra Showroom), BSNL Office Lane,
Jhalawar Road, Kota, Rajasthan (324005)
 OH COOH O
CH3 C
OH
NaNO2 + O ----- + ------
(d) -------------------- CH3 C
HCl
O
OH
Phenol as Nucleophile:-

: :
Conc.H2SO4 OH
(e)

------- + ------------
O

: :
(f) Reimer Tiemern Reaction:- O
OH 1. Ph H + C6H5 C Cl
O
C6H5 C O Ph + HCl

IR
CHCl3
-------- + --------- O
KOH
CH3 C

: :
O
2. Ph H + O
(g) Kolbe Reaction
CH3 C
OH
O
O O
NaOH
.S
1. CO2 (high P)
--------------- Ph O C CH3 + CH3 C OH

---------------
2. H
(h) Fries Rearrangement:- Hydrogenation:-
O OH
OCCH3
H2 /Ni
.J
---------------
AlCl3
------ + ------------
Reduction:-
OH
(i) HO + N=N -----
+ Zn/dust ---------------

N

Coupling Reaction:-
(j) Leaderer marnase reaction:- Oxidation:-
OH OH
O
C
H H / H+ CrO3
---------------
---------------

OH OH (Quinone)

CH2 CH2 CH 2

CH2 CH2

B alkaline polymer

7
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F-106, Road No. 2, Indraprastha Industrial Area, End of Evergreen Motors (Mahindra Showroom), BSNL Office Lane,
Jhalawar Road, Kota, Rajasthan (324005)
 R
SI
J.
N.

8
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IIT-JEE ChEmistry by N.J. sir
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