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
CH3—CH—CH3+H
+  CH —CH—CH 3 
3
 Difference between alcohol & phenol
O–H O+
H H
O–H CH2–OH
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)
CH3—CH—CH3
2°– alcohol
(Secondary alcohol) Ans.
OH
OH
(a) (b) (c) OH
CH3 H

CH—C—OH
3 Oxymercuration – Demercuration (O M D M)
CH3 O OH
1. Hg(OAC)2 H H
.J
3°– alcohol CH3 — CH = CH2 CH3—CH—CH3
(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
Me—C—H   Me—C—Br 2. NaBD4 D
Me Me CH3
CH3 O
O 1. Hg(OAC)2 H H
(3) CH3—C—CH = CH2
H H CH3—C—OH 2. NaBH4
CH3
CH3 CH3 OH
CH3—C — CH — CH3
(2) from alkenes
OH CH3
+ O
H H H CH3—CH—CH3
(i) CH3 — CH = CH2
1
----------------------------------------------------------------------------------------------------
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 OH
(5) Conversion of lower alcohol into higher alcohol
Ans. (3) CH3—C — CH — CH3

CH3 HI  CH3–I CH3 –MgBr CH3 – CH3

CH3–OH  

Hydroboration – oxidation SO2Cl2 /h CH – CH KOH(aq.)CH –CH –OH

  3 2 3 2
1. BH3 THF |
CH3 — CH = CH2 Cl
O–O – CH3OH  CH3—CH2—OH
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 
O–O – 2. 
–
 R–CH2–CH2–O MgX

IR
2. H H OH 
2.H /HO–H
1. B2H6 THF O
2.
O–O – H  R–CH –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
:

R—NH2 + NO R—N—N=O R—N—N=O—H

:
OH OH
(4) CH 3—CH—CH 2 (5) CH3—CH—CH2 H
H D D D H
(6) CH3—CH—CH2 +H
R—N = N—O R—N = N—O—H
D H H +
N

(3) from alkyl halides H +

:
:

aq.KOH R — OH O + R—N = N D R—N N

R—X   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’
CH2—Cl
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  R—O—O 
 (9) MPV – Reduction:–

 — H /H2O Meerwain pondorf werley reduction)

R —O + RO   R— OH + R— OH

2
----------------------------------------------------------------------------------------------------
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. CH—O Al R 
R CH3 3
CH3 (6) R H+ CH3MgBr CH4 + R—O
—
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 COAl R
CH — OH  3. C=O + O—R
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— CH2—OH
O
LiAlH4 Reaction due to C — O bond Cleavage
(b) R — C — OR  R— CH2OH
R—O—H
O O
C C LiAlH4 (1) HI
R — OH  R—H
(c) R O R  R— CH2—OH Red P
O
(d)
.S LiAlH4
R — C — NH 2  R— CH2—NH2 (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 + R’OH 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
R—O—H Cl
(6) Conc.H2SO4 CH — CH = CH
CH3—CH2— CH   3 2
N

O | 170C
Na  R—O— Na+ + ½ H
(1) R H  2 OH
1
(acidic nature) (E1CB) Conc. H2SO4(E )
OH
ThO2 170°C
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
----------------------------------------------------------------------------------------------------
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 CH2–OH
Red hot K MnO4
R — CH — OH   R—C 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 —C—H
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. C—H C
OH P.C.C.  H
2. 
O
.J

:
—C—CH3 N
2. 3.
4. Collin’s 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  R—C

H O
(1° – alcohol  acid)
C
K MnO4 /H OH P.C.C.  H
2. R1 — CH — R2  R —C—R 2. 
1 2

OH O 5. John’s 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
----------------------------------------------------------------------------------------------------
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
—C—H 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 C—O
O Q.5
Me H 
Q.3 Et — C — OH + CH — OH  C—O
Me
O O
H  O
Q.4 Me — C — OH + CH2 — CH3 
OH Q.6 R — O — C — R’

Q.5
.S O
—C—OH
+
H—O
H 
 Q.7
OH O
—C—OMe
—C—OH
H—O
O OH O
O
C
Q.6 R — OH + H—O—C—R’ H 
 OPh
Q.8
OH O
.J
C Me O
OH H
Q.7 + Me — OH 
 C–O–Me
Q.9 H
(Methyl Salicylate)
OH Et
CH3
N

O
—COOH O
Q.8 + Ph H H 
 Q.10 Me–C–O H

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

Et

5
----------------------------------------------------------------------------------------------------
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:- O—H 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. Dow’s Prcess:-
Cl OH

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

(Follow’s Benzyne Mechanism) OH

Br2
(c)  ---------------------
H2O

6
----------------------------------------------------------------------------------------------------
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
—O—H
NaNO2 + O ----- + ------
(d)   -------------------- CH3 — C
HCl
O
OH
Phenol as Nucleophile:-

: :
Conc.H2SO4 O—H
(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) Kolb’e 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
O—C—CH3
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
----------------------------------------------------------------------------------------------------
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)
 R
SI
J.
N.

8
----------------------------------------------------------------------------------------------------
IIT-JEE ChEmistry by N.J. sir
A-833, Indra VIhar, near IL back door,
ContaCt: 9414969800, 9549908816
web : symmetryiitjee.com