ALCOHOL

 Alcohols :-

 Alcohols are the hydroxy derivatives of aliphatic hydrocarbons.

ex :- CH3  OH



aliphatic + hydroxy = Alcohol

part part
CH3


ex :- CH3  CH  OH
2
, CH3  CH  CH  OH 2
etc.

–H
 R H + OH
R  OH
alkane alcohol
[Aliphatic hydro carbon]

 NOTE :-

 Hydrogen displaced or replaced from the aliphatic hydrocarbon must be of two different
carbon atom not from the same carbon atom.
 This is due to the reason that presence of two or more hydroxyl groups on the same
carbon atom makes the molecule unstable & hence immediately loses a molecule of
water to form an aldehyde, ketone or a carboxylic acid.

 C OH C
 OH O


 + H2O.


aldehyde or ketone.

OH O
 

  C  OH  C  OH + H2O.
carboxylic acid.
OH

 Classification of Alcohols on the basis of no. of —OH group attached to carbon.

ex :- CH3  CH  OH
2
, CH2 OH , CH2 OH
 


[monohydric] CH  OH
2
CH  OH

[Dihydric] CH  OH
2

[trihydric]

Page - 01
 Alcohols



Primary alcohol [1o] Secondary alcohol [2o] Tertiary alcohol [3o]
CH3 CH3


CH3  CH  OH
2
CH3  CH  OH CH3  C  OH
(1o) (2o) (3o)

 Allylic Alcohol :-

 If the OH group is attached to allylic carbon.

allylic carbon. CH3

 
ex :- CH2  CH  CH  OH 2
, CH2  CH  CH  OH , CH2  CH  C  OH


(1o) (2o) CH3 (3o) CH3

 Benzylic Alcohol :-

 If the OH group is attached to benzylic carbon.

CH3 CH3

 
 

ex :- CH  OH 2
C  OH C  OH
(1o) H CH3
(2o) (3o)
 NOTE :-

 In alkyl alcohol, allylic alcohol & Benzylic alcohol, OH group is attached to
sp3-hybridised c-atom.
sp2

 Vinylic alcohol : CH2  CH  OH

OH sp2


 Phenol :

 Nomenclature of Alcohols :-
–C
 IUPAC System :- Alkane Alkanol
+ ol

 Common System :- Alkyl alcohol

Page - 02
 CH3


ex :- CH3  OH , CH3  CH  OH
C.N. = methyl alcohol C.N. = Isopropyl alcohol
IUPAC = Propan-2-ol.

CH3
 
 CH3  C  OH C.N. = tertiary butyl alcohol
IUPAC = 2-methyl propanol
CH3
1 2 3 4
 CH3   CH CH2  CH3 C.N. = secondary butyl alcohol


OH IUPAC = Butan-2-ol.


OH C.N. = Cyclohexyl alcohol.
IUPAC = Cyclohexanol

OH




CH
 2
3 C.N. = methyl cyclopentyl alcohol
IUPAC = 2-methyl cyclohexanol.

(Q). Write the IUPAC name of following alcohols :-

 OH CH2


(i). CH  CH  CH  CH  CH  CH
3 2 2 3


CH  Cl CH 2 3

CH  OH 2


(ii). CH  CH  CH  CH  CH  CH
3 2 3



CH3 OH

OH


(iii). Br (iv). H2C  CH  CH  CH  CH  CH

2 2 3


OH
Br


(v). CH3  C  C  CH  OH 2


CH3

Page - 03
 Electronic structure of the functional group :- [Alcohol]

H 1s
~ sp 3 l.p. present in sp3 hybrid orbital.

:
3
1s ~ sp
H 3 C O :
p sp3 ~ sp3
~s 1s
1s ~ sp 3
H [methanol] H

Bond Angle :-
C  O
108.9o
H

Bond length :-
C  O
142 Pm
& O  H
96 Pm

 The C  O  H bond angle is slightly less than the tetrahedral angle (109 28`) due to o

greater l.p.-l.p. repulsion than l.p.-l.p. repulsion.

 Lower alcohol are polar in nature.

 Methods of Preperation of Alcohols :-

(1). From Haloalkanes :-

 Reaction of haloalkanes with aq. NaOH, aq. KOH, aq. Na2CO3 moist Ag2O gives alcohol.

R X + KOH (aq.) R  OH + KX.

Mech :-
 
R X R  OH + KX.



2
+ –
1 K OH

ex :- CH3  CH  Br 2
+ KOH (aq.) CH3  CH  OH2
+ KBr..

(2). From Alkenes :-



From hydration of alkene we can formed alcohol.



Hydration means addition of water (H2O) to alkene.



addition of water means addition of H+ & OH–.

 Hydration of alkene can be done by three processes :

Page - 04
 (a). By Acid catalysed process Mechanism in syllabus.

(b). By Oxymercuration - Demercuration

(c). By Hydrobaration - Oxidation Mechanism not in syllabus.

(a). By Acid catalysed hydration process :-

H
C 


H2SO4
 C  C

+ H2O C





alkene water OH alcohol

 Mechanism :-

Step-1 : Protonation of alkene to form carbocation by electrophilic attack of H3O+.

H2SO4 (aq.) 2H+ + SO42 –.

H2O + H+ H3O+ = hydronium ion.

H
 C



 C  O+  H  +
 C



C + H + H2O.





H carbocation.

 During this step, addition of proton occurs on that c-atom of the double bond which
yields a more stable carbocation.

Step-2 : Nucleophilic attack of water on carbocation.

H H


 C



 

+ .. +
 C  C  OH


C + H2O 2


Step-3 : Deprotonation to form alcohol.

H H OH


 C


 


 

..
C  C  O+  H + H2O  C  H O+ 3


H
 Observation :-

 It is an electrophilic addition rexn.

 Intermediate is carbocation. so rearrangement can take place.
 Also follow Markonikaff’s rule for addition of E+.
i.e. H+ is added to that carbon which contains more no. of H-atoms.

Page - 05
 H2SO4, H3PO4 is generally used as acid catalyst but HX is not used as acid catalyst
because then X – act as nu – not H2O.
 In overall rexn addition of H+, OH– exist.

H2SO4
ex.1 :- CH3  CH  CH 2
+ H2O

H3PO4
ex.2 :- CH3  C  CH 2
+ H2O

CH3

CH2  CH  CH 2


ex.3 :- H2SO4
+ H2O

ex.4 :- CH 2
H2SO4
+ H2O

CH3


ex.5 :- H2SO4
+ H2O

(c). By Hydroboration - Oxidation :-

1. BH3, T.H.F
CH3  CH  CH 2
2. H2O2, – OH
CH3  CH  CH  OH
2 2

 T.H.F. = tetrahydro furan =

: :

 Syn addition occur.

 Overall rexn is addition of water [H+ & OH–] to an alkene.
 Here, Antimarkonikaff’s rule is followed for the addition of E+ (H+).
i.e. H+ is added to that carbon which bears less no. of H-atoms.
 One step pathway. so no intermediate & so no rearrangement.

CH2  CH  CH 2


ex.1 :- 1. B2H6 , T.H.F.

2. H2O2, – OH

ex.2 :-
CH 2
1. B2H6 , T.H.F.
2. H2O2, – OH

Page - 06
 CH3


1. B2H6 , T.H.F.
ex.3 :-
 CH 2. H2O2, – OH
3


(3). From Carbonyl [— C —] compounds :-

(a). By redn of Aldehyde & Ketones :-

 Aldehyde & ketones are reduced to the corresponding alcohols by addition of hydrogen in
the presence of catalyst.
 Catalyst used are finely divided metal such as Pt, Pd or Ni.
O H O


 
Pd
R CH + H2 RCH

H
O


Pd
ex :- CH3 CH + H2 CH3  CH  OH
2

 Sodium borohydride (NaBH4) or Lithium aluminium hydride (LiAlH4) used as Reducing

agent to reduce aldehyde & ketone.
 Both LiAlH4 & NaBH4 act as hydride (H–) donar.

H Al H – HB H –
H H


+ +
Li Na


H H  shifted with its b.p.

 shifted with its b.p.

 ‘Al’ give its H– more easily than ‘B’ to become stable because Al is more electro +ve
than B.

Mechanism :-
–
O

O Li +  H  from solvent.
O
 


 

H2O
C  C C


H
– H H  from R.A. [alcohol]

 ‘H’ linked with ‘O’ in product comes from solvent (H2O) & ‘H’ linked with ‘C’ comes
from R.A.
O H O
 


1. NaBH4
ex.1 :- H CH 2. H2O
HCH = CH3  OH
Formaldehyde
H

Page - 07
 O


1. NaBH4
ex.2 :- CH3 CH 2. H2O
CH3  CH  OH2

(1o)
O


 C H CH2  OH


1. LiAlH4
ex.3 :-
2. H2O (1o)

O

1. NaBH4
ex.4 :- CH3  CH  C  H 2. H2O


CH3

O OH



1. LiAlH4
ex.5 :- CH3  C  CH 3
2. H2O
CH3  CH  CH 3
ketone (2 ) o

O


1. LiAlH4
ex.6 :-
2. H2O

O


C  CH 3


1. LiAlH4
ex.7 :-
2. H2O

 Except formaldehyde all aldehyde on redn form 1o-alcohol.

 All ketone on redn form 2o-alcohol.
O


1. LiAlH4
 CH3  C  CH 3
2. H2O

(b). By redn of Carboxylic acids & Esters :-

 Redn of Esters :-

O


1. LiAlH4
R  C  OR` 2. H2O
R  CH  OH2
+ R`OH

Page - 08
 Mechanism :-
 –
O +m O 1 O

 


 
2 – +
 C  O  R`  C  O  R` C

:
R R R + R`O Li


2
– H
H H
H2O
LiAlH4

R  CH  OH2
+ R`OH
[always 1o] [may be 1o,
2o or 3o]

 Reducing ability of esters is less than Aldehyde & Ketone due to presence of +m group
in esters which decreases +ve character of carbonylic carbon due to this attack of Nu–
becomes slow on ester than aldehyde & ketone.
 One-molecule of ester gives 2-molecule of alcohol (same or different.)

O


R  C  OR`  alkoxy part



acyl part

 Acyl part of ester gives 1o-alcohol or methyl alcohol.

But alkoxy part of ester can give CH3  OH, 1 , 2 or 3 alcohol depending on
o o o

structure of R` linked with alkoxy oxygen.

O


1. LiAlH4
ex.1 :- H COC H 2 5
2. H2O
CH3  OH + C2H5  OH
O


1. LiAlH4
ex.2 :- CH3 COC H 2 5
2. H2O

O CH3


 

1. LiAlH4
C  O  C  CH 3


ex.3 :- 2. H2O
CH3

O


O 1. LiAlH4
ex.4 :-
2. H2O

Page - 09
 Redn of Carboxylic acid :-

 LiAlH4 is the only effective Reducing agent.

O


1. LiAlH4
R  C  OH 2. H2O
R  CH  OH
2

Mech :-
– 
O O H O


 

 


.....
H2O
R COH R COH RCOH unstable


 
– H H
H
–H2O
[From LiAlH4]
O

 
R C aldehyde

H
–
O O OH
 


 
H2O
R CH R CH R CH


– H H
H
=
[From LiAlH4]
R  CH  OH
2

O


1. LiAlH4
ex.1 :- CH3  C  OH 2. H2O
CH3  CH  OH
2

O


1. LiAlH4
C  OH


ex.2 :- 2. H2O

(Q). :- Convert :- CH3  OH CH3  CH  OH

2

 LiAlH4 is an expensive reagent & therefore used for preparing special chemicals only.
 Commercially, acids are reduced to alcohols by converting them to esters followed by
their redn using hydrogen in the presence of catalyst.
O O


R`O H / H+ H2
R COH –H2O
R  C  O  R` Catalyst
R  CH  OH + R`OH
2

Page - 10
(4). From Grignard reagents :-

 alkyl magnesium halide or Aryl magnesium halides are called grignard reagent.

Ph  Mg  X or R  Mg  X


– +
R Mg X


–
act as Nu & attack on electron deficient species.

 Reaction of aldehyde & ketones with G.R. followed by acidification gives alcohol.

Mech :-
– +
O O MgX OH


 

 
2 H3O+ or HCl (aq.)
C C C


or NH4Cl (aq.)
1
R  MgX R R

O


1. PhMgBr
ex.1 :- H CH 2. H3O+
Ph  CH  OH
2

1o-alcohol
O


1. CH3MgBr
ex.2 :- H CH 2. H3O+

O


1. (CH3)2CHMgBr
ex.3 :- H CH 2. H3O+

O


1. CH3MgBr
ex.4 :- CH3 CH 2. H3O+

O


1. CH3 CH2 MgBr

ex.5 :- CH3  CH  C  H


2. H3O+
CH3
O


1. CH3 CH2 MgBr

ex.6 :- CH3  C  CH 3
2. H3O+
Ketone

Page - 11