Alcohols Phenols Ethers PDF

Vidyamandir Classes Oxygen Containing Organic Compounds - I
Oxygen Containing Organic Compounds - I

(Alcohols, Phenols, Ethers, Glycols & Glycerol)
Alcohols Section - 1
The compounds in which hydroxyl group (OH) is attached to a saturated carbon atom are called as
Alcohols. The compounds in which a hydroxyl group is attached to an unsaturated carbon atom of a double
bond are called as Enols. The saturated carbon may be that of an alkyl, alkenyl, alkynyl, cycloalkyl or
benzyl group. However if a hydroxyl group is attached to a benzene ring, the compounds are called as
Phenols.
The alcohols are further classified as : Monohydric (containing one OH group), Dihydric (containing two
OH groups) and Trihydric (containing three OH groups).
Some important Monohydric alcohols are :

CH3OH (Methanol), CH3CH2OH (Ethanol), (CH3)2CHOH (Propan-2-ol / Isopropyl alcohol), (CH3)3C
OH (2-Methylpropan-2-ol / Tert. butyl alcohol), CH2 = CHCH2OH (Prop-2-en-1-ol / Allyl alcohol),
HC  CCH2OH (Prop-2-yn-1-ol), C6H11OH (Phenol),
Monohydric alcohols are further classified as: Primary (1) RCH2OH, Secondary (2) R2CHOH, Tertiary
(3) R3COH.
Preparations of Alcohols
1. Hydrolysis of alkyl halides : Alkyl halides undergo hydrolysis when heated with aqueous alkalies or
moist silver oxide. The hydrolysis occurs by a nucleophillic substitution reaction.
H O
2  R  OH  NaX
R  X  NaOH 
C2 H5  Br  KOH  aq  
 C2 H5  OH  KBr
Sometimes this method is not satisfactory as Olefins (alkenes) are also formed as side products
specially if halide is tertiary. If R is 3, then alkyl halides mainly give alkenes, when NaOH is concen
-trated (–OH as base).
 CH3 3 C  Br  NaOH  conc. 

  CH 3  2 C  CH 2   CH 3 3 C  OH
Major product Minor product
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Oxygen Containing Organic Compounds - I Vidyamandir Classes
However satisfactory results are obtained by using moist Silver oxide (AgOH) or aqueous K2CO3.
RI  AgOH 
 R  OH  Ag  I
2. From alkenes :
(a) By acid-catalysed hydration of alkenes : Alkenes react with cold concentrated H2SO4
to give alkyl hydrogen sulphates following Markonikov’s addition.
2  CH  C H  CH H O
CH 3  CH  CH 2  H  OSO3H 
 CH 3  C H  CH 3  3 3
Propene Cold |  |
OSO3H OH
Isopropylhydrogensulphate
Note : Alkyl hydrogen sulphate when boiled with water give alcohols.
(b) Hydroboration - Oxidation of alkenes : Alkenes react with diborane in presence of THF as sol
vent to form alkyl boranes (Hydroboration). Alkyl boranes are then oxidised and hydrolysed by the
addition of hydrogen peroxide in aqueous base.
2 6 1.B H /THF
CH 3CH  CH 2  CH 3 C H C H 2
| |
2.H 2 O 2 /OH  ,H  OH
H OH
Here the net addition (syn) of H – OH to alkenes is in accordance with Anti-Markonikov’s rule and
free from any rearrangement. It is an important method for preparing 1 alcohols.
Note : In the above reaction, ‘H’ comes from B2 H6 and ‘OH’ comes from H 2O molecule.
(c) Oxymercuration and demercuration : Mercuric acetate (Hg(OAc)2 ) in presence of water -

tetrahy drofuran solution reacts with alkene to form alkyl mercury compound. The mercury com
pound is reduced with NaBH4 when alcohol is formed.
H
1. Hg  OAc  2 / THF, H  OH
|
R  CH  CH 2  
 R  C H  C H2
2. NaBH 4 , OH |
OH
(2 Alcohol)
The above reaction (anti) occurs in accordance with Markonikov’s addition (unlike Hydroboration
reaction). The ‘H’ becomes attached to the carbon atom of the double bond with greater number of
hydrogen atoms. It too does not involve rearrangement.
Note : In the above reaction, ‘OH’ comes from H 2O and ‘H’ comes from NaBH 4 .
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3. Reduction of Aldehydes and Ketones : Aldehydes and Ketones on reduction yield alcohols. A
number of reducing agents like H2/Ni, Pt, Pd or Na/C2H5OH or Zn/HCl or LiAlH4 in ether or
NaBH4 in alkali can be used for this purpose.
(a) Bouveault - Blanc reduction : The reducing agent used is sodium and ethanol. The aldehyde
and ketones are reduced by nascent hydrogen into corresponding alcohols.
Na
RCHO  2  H   RCH 2OH (1° alcohol)
EtOH
(b) Reduction with LiAlH4 : It is better reducing agent for the conversion of carbonyl com-
pounds into alcohols. LiAlH4 is soluble in ether, the common solvent and it does not reduce
the carbon - carbon double bond.
LiAlH
4  CH CH  CHCH OH
CH 3  CH  CH  CHO  2  H   3 2
ether
Note : (i) NaBH4 also does not reduce carbon - carbon double bond. Also, NaBH 4 is a mild reducing agent.
(ii) Catalytic hydrogenation reduces carbon – carbon double bond as well as carbonyl group.
Ni
CH 2  CHCHO  4  H  
 CH 3CH 2CH 2OH
Catalyst
(iii) Ketones are reduced to secondary alcohols by Aluminium isopoxide in Isopropyl alcohol. The reduc
-tion by this method is known as Meerwin-Pondorrf-Verley (MPV) reduction and is considered as
an important method for the formation of secondary alcohols.
 CH3  CH  O  Al
 2 3
R 2C  O  R 2CH  OH
in Isopropyl alcohol
(iv) As a special case, LiAlH 4 also reduces double bond if conjugated with a phenyl group, in  ,  
unsatured carbonyl compound along with carbonyl group.
4 LiAlH
Ph  CH = CH  CHO  Ph  CH 2  CH 2  CH 2OH
ether
(v) NaBH 4 can reduce aldehydes, ketones and acyl chlorides to alcohols.
LiAlH 4 can reduce carboxylic acids, esters (to alcohols) and amides (to amines) also.

4. Hydrolysis of Ester : (Base or Acid catalysed)

Esters on hydrolysis by mineral acids or alkalies form alcohols and carboxylic acids. Hydrolysis of
ester takes place by acyl-o-cleavage reaction mechanism.
* H
 or OH  *
R  CO  O R '  H  OH  R 'O H  RCOOH

Alcohols being more volatile than acids can be easily separated by distillation.
5. From Ethers :
(a) Hydrolysis : Ethers when heated with dil. sulphuric acid under pressure are hydrolysed to the
corresponding alcohols.
H SO
2 4  ROH  R 'OH
R  OR '  H 2O  (Separated by fractional distillations)
dil.
(b) With concentrated HI :

HI
(i) If symmetric : R  O  R   ROH  RI
HI
(ii) If mixed : R  O  R '  (Iodide contains smaller alkyl group
 ROH  R ' I
except when R is 3)
HI
C2 H5  O  CH3  C 2 H5OH  CH 3I
Note : (i) The details of this reaction are given in Section - 3 (Ethers)
(ii) In this reaction, refluxing the products with KI(aq) gives only alcohols.
HI KI/ H 
C 2 H 5OCH 3  C 2 H 5OH  CH 3I 
 C 2 H 5OH  CH 3OH
HI (aq)/ H 
6. Action of Nitrous acid on primary amines : Primary alcohols are formed when primary amines
(only) are treated with nitrous acid (HNO2).
RNH 2  HONO 
 ROH  N 2  H 2O
C2 H5 NH 2  HNO2 
 C2 H5OH  N 2  H 2O
Note : Under similarly conditions, Methylamine does not yield Methanol. The product formed is Methylnitrite or
Dimethyl ether.
CH3 NH 2  2 HNO 2 
 CH3  O  N  O  2H 2O  N 2
or 2CH3 NH 2  2HNO 2 
 CH 3  O  CH 3  3H 2O  2 N 2

7. Reduction of Carboxylic acid and its derivatives :

(a) Catalytic Hydrogenation : It follows the order : RCOCl > RCOOR > RCOOH.
However, catalytic hydrogenation is used in industries because extremely high pressures and
temperatures are required.
(b) Bouveault – Blanc reduction :
Na
RCOOC 2H 5  RCH 2OH  C 2 H 5OH
EtOH
(c) Reduction by LiAlH4 : The acids can be reduced to primary alcohols by LiAlH4
(not by NaBH4).
1. LiAlH in ether
4
RCOOH   RCH 2OH
2. H O 2
Esters are more easily reduced than carboxylic acids by LiAlH4. Two alcohols are formed
from each ester molecule; one is derived form the acyl part and other from the alcoholic part.
O
|| 1. LiAlH 4
R  C  OR '   R  CH 2OH  R 'OH
2. H O 2
8. From Grignard Reagent : All the three types of monohydric alcohols can be prepared by the use
of Grignard reagents.
(a) Primary alcohols : Primary alcohols are obtained when Grignard reagent is reacted with
oxygen or Formaldehyde or Ethylene oxide.
(i)
The alcohol has same number of carbon atoms as present in the alkyl group of the
Grignard reagent.
(ii)
The alcohol has one carbon atom more than the alkyl group of the Grignard reagent.
(iii)
The alcohol has two carbon atoms more than the alkyl group of the Grignard reagent.

(b) Secondary alcohols : Secondary alcohols are obtained when Grignard reagent is reacted
with an aldehyde other than formaldehyde.
(i) 2 alcohols are obtained when Grignard reagent is reacted with an aldehyde other
than formaldehyde.
(ii) Formate esters on treatment with Grignard reagent first forms aldehyde which then
reacts with second molecule of Grignard reagent and forms secondary alcohols.
(c) Tertiary alcohols :

(i) Tertiary alcohols are obtained when Grignard reagent is reacted with ketones.
(ii) Esters on treatment with Grignard reagent first forms ketone which then reacts with
second molecule of Grignard reagent and forms tertiary alcohols.
9. Industrial Methods :
(a) Methanol : [CH3OH : Also known Carbinol or wood spirit]
(i) Destructive distillation of wood 
 Methanol (Natural method)
(ii) From Water gas (Synthetic method) :


C  H 2O  CO  H 2
Red hot coke Steam Water gas
300 C
CO  2H 2   CH 3OH
200 atm
A mixture of CuO, ZnO, Cr2O3 is used as catalyst for this reaction.

(iii) Oxidation of Methane :

Cu tube
CH 4  O 2 

 CH 3OH
100 C /200 atm
(b) Ethanol : [C2H5OH]

(i) Fermentation of Molasses (C12H22O11) :
Invertase Zymase
C12 H 22O11  C 6 H12O 6  C 6 H12O 6 
 2 C 2 H 5OH  2 CO 
H O 2
Molasses Glucose Fructose
From molasses, both glucose and fructose are formed, which are converted to ethyl alcohol
by zymase.
(ii) From Starch (C6H10O5)n :
2 nH O Maltase
2  C6 H10O5  n  n  C12 H 22O11   n  C6 H12O 6   n  C6H12O 6 
Diastase H 2O
Starch Maltose Glucose Fructose
From starch, both glucose and fructose are formed, which are converted to ethyl alcohol by
zymase.
(c) For 1° alcohols (OXO - Process) :

high temp. pressure
2 H / Ni
CH 2  CH 2  CO  H 2  CH 3CH 2CHO  CH 3CH 2CH 2OH
 CoH (CO)   4
high temp. pressure

CH 3CH  CH 2  CO  H 2  CH 3CH 2CH 2CHO  CH 3  C H  CHO
 Co (CO) 4  2 |
CH 3
 These can be reduced to give corresponding 1 and 2 alcohols.
Note : Absolute alcohol (100% pure ethyl alcohol). Rectified spirit (containing 95.87 % C2H5OH + 4.13 % H2O)
cannot be converted into absolute alcohol simply by distillation because the mixture of ethanol and water in
the ratio of 95.87 : 4.13 (a ratio present in rectified spirit) is a constant boiling mixture (azeotropic mixture)
having b.p. 78.13C.
Methylated spirit (Denaturated alcohol) It is rectified spirit (industrial alcohol) mixed with poisonous sub-
stances like CH3OH, pyridine, acetone, etc. to make it unfit for drinking purposes. The usual composition
of denatured alcohol is 8590% rectified spirit + 1015% methanol.
Power alcohol. Alcohol used for the generation of power is called power alcohol. It is a mixture of petrol
and alcohol in the ratio of 4 : 1 in presence of benzene or ether.

Physical Properties
1. The lower alcohols are readily soluble in water and the solubility decreases with the increase in molecu-
lar weight. The solubility of alcohols in water can be explained due to the formation of hydrogen bond
between the highly polarised –OH groups present both in alcohol and water.
     
H  O.........H  O.........H  O
| | |
H H H
Relative solubility of isomeric alcohols in water is 1 > 2 > 3.
2. Boiling points of alcohols are much higher than those of the corresponding alkanes and ethers. It is due to
the formation of hydrogen bonding between the hydroxyl groups of the two molecules of an alcohol with
the result several molecules are associated to form a large molecules.
     
H  O ............ H  O ............ H  O
| | |
 
H H H 
Among the isomeric alcohols, b.p. show the following trend.

Primary > Secondary > Tertiary (e.g. visualise of C4 H9OH.)
3. Lower alcohols form solid addition compounds with anhydrous metallic salts like CaCl2 and MgCl2, viz.,
CaCl2.4C2H5OH and MgCl2.6C2H5OH.
By analogy to water of crystallisation, these alcohol molecules are referred to as alcohol of crystallisation.
For this reason, alcohols cannot be dried over anhydrous calcium chloride.
4. Methanol is highly toxic. Ingestion of even small quantities of methanol can cause blindness ; large quantities
can cause death. Methanol poisoning can also occur by inhalation of the vapours or by prolonged exposure
to the skin. Ethanol is a hypnotic (sleep producer). Ethanol is much less toxic than methanol.
Reactions of Alcohols
Let us examine the electron distribution in the alcoholic functional group,
and its impact on the reactivity :
(i) Oxygen atom of an alcohol polarizes both CO bonds and the OH bond of an alcohol. Polarization
of the OH bond makes the hydrogen partially positive and explains why alcohols are weak acids.
In such reactions alcohols act as acids and cleavage of the OH bond takes place. The order of
reactivity of different alcohols for such reactions is :
CH3OH > 1 > 2 > 3 alcohols.

(ii) Polarisation of the CO bond makes the carbon atom partially positive, and hence it would have
been susceptible to nucleophilic attack if OH– were not a strong base, i.e., if OH– were not a poor
leaving group.
Protonated alcohols easily undergo nucleophilic substitution which may be SN2 or SN1 depending
upon the class of alcohol.
Mechanism of Nucleophilic substitution reactions of Alcohols (SN 1 and SN 2 paths) :
Note that alcohols do not give typical nueleophilic substitution reaction since OH  ion being a strong base
is a poor leaving group.
But alcohols do give nucleophilic substitution in presence of halogen acids. In presence of acids, leaving
group is H 2O instead of  OH group. Primary alcohols having   carbon as 1 or 2 always give
S N 2 reaction. Secondary alcohols having   carbon as 1 also give S N 2 reaction. All tertiary alcohols
give S N 1 reaction.
S N 1 path :
+
1st step : HX
(CH3 )3 C OH 
(CH3 )3 C OH 2
fast
2nd step :
3rd step : (CH3 )3  C+ + X  

(CH3 )3  C X
Note that it is almost similar to S N 1 in alkyl halides. Allyl and benzyl alcohols also follow the same path
(S N 1).

HX +
S N 2 path : RCH 2OH 
 RCH 2 O H 2
Note : (i) In SN 2 reactions, X  being weak base do not bring elimination by removing   hydrogen. How
ever in SN 1 reaction, carbocations formed may lose proton to give alkenes (EI).
(ii) Another method to bring out substitution in alcohols especially by SN 2 path is to convert them into
halides with PX3 or into sulphonates with TsCl.
(iii) At a high temperature, and in the absence of a good nucleophile, protonated alcohols are capable of undergo-
ing elimination reactions.
1. With active metals:

Alcohols are acidic in nature and hence react with alkali metals to form metal alkoxides with the evolution of
hydrogen gas.
 2 R  O  M   H2
2 ROH  2 M  (where M  Na, K, Mg, Al, etc.)
2CH 3OH  2Na 

 2CH 3  O  Na  H 2
Note : (i) Alcohols behave like acids when O – H bond cleaves.

(ii) Reactivity of alcohols with metals is in order : CH3OH > 1 > 2 > 3
(iii) R – O Na+ can be decomposed by H2O to give back alcohol. However alcohols do not react with
NaOH.
RO Na   H 2O 
 ROH  NaOH
(iv) Since most alcohols are weaker acids than water, most alkoxide ions are stronger bases than the
hydroxide ions. (CH3)3 CO > C2H5O > OH > CH3O (Relative basic character).

Alcohols as acids
Alcohols have acidities similar to that of water. Methanol is a slightly stronger acid than water but most
alcohols are somewhat weaker acids. In general, the order of acidity of alcohols is as follows :
H 2O > CH3CH 2OH > (CH3 )2  CH  OH > (CH3 )3  C  OH.
The reason sterically hindered alcohols such as tert-butyl alcohol are less acidic arises from solvation effects.
With unhindered alcohols, water molecules are able to surround and solvate the negative oxygen of the alkoxide
ion formed when an alcohol loses a proton. Solvation stabilizes the alkoxide ion and increases the acidity of
the alcohol. Any factor that stabilizes the conjugate base of an acid increases its acidity.
If the R– group of the alcohol is bulky, solvation of the alkoxie ion is hindered, and the alkoxide ion is not as
effectively stabilized. The alcohol, consequently, is a weaker acid.
All alcohols, however, are much stronger acids than terminal alkynes, and are very much stronger acids than
hydrogen, ammonia, and alkanes.
Relative Acidity H2O > ROH > RC  CH > NH3 > RH > H2
The conjugate base of an alcohol is an alkoxide ion. Sodium and potassium alkoxide can be prepared by
treating alcohols with sodium or potassium metal or with the metal hydride. Because most alcohols are weaker
acids than water, most alkoxide ions are stronger bases than the hydroxide ion.
Relative basicity H– > R– > NH2– > RC  C– > RO– > OH–
Alcohols reacts with diazomethylene in presence of BF3 , Grignard reagent due to acidic nature.
+ BF
3  ROCH + N
ROH+ C H 2  N  N  3 2
Ether
ROH + CH3  MgBr  CH 4 + ROMgBr
2. Action of acids (Esterification):

* H * 


(a) Ester of Carboxylic acids : RCOOH  H  O R  
 RCO O R   H 2O [*  O18 ]
Reactivity in esterification :
 For alcohols : CH3OH > 1 > 2 > 3
 For acids : HCOOH > CH3COOH > RCH2COOH > R2CHCOOH > R3CCOOH.
Note : (i) Esterification reaction proceed by acylo-o-cleavage reaction mechanism.

(ii) Tert. alcohols react so slowly in acid-catalysed esterification that they usually undergo elimination to
form alkenes.
(iii) Esters are also formed by the reaction of alcohols with acyl chlorides or acid anhydrides.
CH 3  CO O  CO CH3 + H  OR 

 CH 3  CO OR + CH3  COOH

Unlike the reaction with carboxylic acids, these reactions are irreversible, hence yields of esters via
this route are always high.
(iv) Reaction with acyl chlorides or acid anhydrides is used to determine number of hydroxyl groups in
polyhydric alcohols.
Molar mass of product  Molar mass of polyhydric alcohol
Number of OH groups =
42
(v) Suitable hydroxycarboxylic acid undergoes intramolecular esterification to form cyclic ester. (Called
as Lactone)
The mechanism of the reaction will be discussed in Carboxylc Acids.
(b) Esters of Sulphonic acids :

base
CH3  SO 2  Cl + H  OC2 H5 
 CH3  SO2  OC2 H5 + HCl
Methyl Sulphonyl chloride Ethyl methyl sulphonate
(c) Esters of Inorganic acids : Alcohols react with inorganic acids, viz. HNO3, H2SO4, H3PO3
and H3PO 4 to form esters of inorganic acids.
H

ROH  HONO 2   RONO 2  H 2O
2CH3OH + H 2CO3 (CH3 )2 CO3 Dimethyl carbonate
 H 2O
CH OH
3  CH OSO OCH
CH 3OH  HO  SO 3H 
 CH 3OSO3H  3 2 3
Methyl hydrogen sulphate Dimethyl sulphate

3. Conversion of alcohols into alkyl halides :

2 ZnCl
(a) Reaction with halogen acids : R  OH  HX   R  X  H 2O
anhyd.
The order of reactivity of the hydrogen halides is HI > HBr > HCl (HF is generally unreac
tive), and the order of reactivity of alcohols is 3° > benzyl  allyl > 2° > 1° > CH 3 . This
reaction follows nucleophillic substitution mechanism.
Note : The mixture of HCl and anhydrous ZnCl2 at room temperature is called Lucas reagent and the reaction is
referred to as LUCAS TEST. (appearance of a white turbid solution). 3 alcohols give Lucas Test instantly
; 2 alcohols give it after sometime and 1 alcohols do not give this test.
Note : Mechanism : Secondary, tertiary, allylic, and benzylic alcohols appear to react by SN1 mechanism.
Step 1 :
Step 2 :
Step 3 :
Most of the primary alcohols and methyl alcohol react by SN2 mechanism.
Why CH3OH reacts faster than other primary alcohols ?

Actually, methyl substrate is least capable of heterolysis and thus reacts only by SN2 reaction. Although
most of the primary substrates also react by SN2 mechanism, but because of increased steric hinderance
they react less rapidly than the methyl.
(b) Reaction with Phosphorus halides :
 
3ROH  PCl3   3RCl  H 3PO 3 ; ROH  PCl5   RCl  POCl3  HCl
Generally, in place of PBr3, red P and Br2 can be used. Similarly for PI3, red P and I2 is used.
(c) Reaction with Thionyl chloride :
Pyridine
ROH  SOCl 2 
 R  Cl  SO 2   HCl 
SN 2
R  OH  SOCl 2 
 R  Cl  SO 2   HCl 
SNi

If reaction takes place on chiral carbon atom then product is formed with retention in configuration because
reaction proceed by intramolecular nucleophilic substitution (SN i) reaction mechanism.
Note : The reaction of alcohols with phosphorus and Sulphur halides involves no rearrangement unlike with HX.
4. Dehydration to Alkenes : Alcohols on reaction with conc. H2SO4/, H3PO4 or catalysts such as anhy-
drous zinc chloride or alumina, loose the water molecule and form alkenes.
conc. H SO  excess 
2 4
C 2 H 5OH 

 CH 2  CH 2
170 C
2 4 conc. H SO  excess 
CH 3CH 2 C H  CH 3  CH 3CH  CHCH 3  CH 3CH 2CH  CH 2
|  Major Minor
OH
 The ease of dehydration is 3 > 2 > 1 alcohols.
 The Dehydration always follow Saytzeff rule.
Al O
2 3  CH  CH
 In gas phase, alcohols are heated with alumina to give alkene. C 2 H 5OH 
 2 2
350 C
Note : (i) If alcohols are in excess, then ethers are formed.


140 C
C2 H 5OH  H 2SO 4  C 2 H 5  O  C 2 H 5  H 2O
(Excess) (conc.) Diethyl ether
200 C
C2 H5OH  Al 2O3  C 2H5  O  C2 H5
(Excess)
(ii) Note that , at 170C or above dehydration occurs and at around 140C, ethers are formed when
conc. H2SO4 is used.
(iii) When conc. H2SO4 is in excess, alkenes are formed and when alcohols are in excess, then ethers are
formed.
5. Reaction with Ammonia : When a mixture of the vapours of an alcohol and ammonia are passed over
heated alumina or thoria catalyst at 360C, a mixture of primary, secondary and tertiary amines is pro-
duced.
Al O
2 3  RNH  ROH ROH
ROH  NH 3  2  R 2 NH   R 3N
360 C Al 2 O3 Al 2 O3
1amine 2°amine 3°amine
6. Reaction with Grignard Reagent :

Re d P
7. Reduction : ROH  2HI  RH  I 2  H 2O

8. Oxidation : The oxidation of alcohols is used to distinguish between 1, 2, 3 alcohols.
O
1 alcohols : RCH 2OH 
 O  
 RCHO  RCOOH
25C
aldehyde acids
2 alcohols :
Secondary alcohols are oxidised to ketones by chromic anhydride (CrO3).

CrO
3  R  C R'
R  CH  R' 
| ||
OH O
O
3 alcohols : R 3C  OH   do not oxidise
Tertiary alcohols do not undergo oxidation reaction. Under strong reaction conditions such as strong oxidising
agents (KMnO4) and elevated temperatures, cleavage of various C–C bonds takes place and a mixture of
carboxylic acids containing lesser number of carbon atoms is formed.
The important oxidising agents are : KMnO4/H+, Na2Cr2O7/H+, Chromic acid (H2CrO4). Some examples
are :
2 H CrO
4  CH CHO 
2 4  CH COOH H CrO
CH 3CH 2OH  3 3 ;
Note : (i) H2CrO4 does not oxidises double or triple bond in alcohols unlike KMnO4 and K2Cr2O7.
OH O
| H 2 CrO 4
||
H 2C  CH  C H  CH 3   H 2C  CH  C  CH 3
(ii) Cycloalkanols in presence of 50% HNO3 at 55C undergo cleavage forming dioic acids.

(iii) It is difficult to stop oxidation at aldehydic stage in aqueous solution. Hence a special oxidising agent,
Pyridinium chlorochromate (PCC) in CH2Cl2, is used to convert alcohols to aldehydes.
PCC
CH 2  CH  CH 2CH 2OH 
 CH 2  CH  CH 2CHO
CH 2Cl 2
PCC only oxidises 1 and 2 alcohols, not unsaturated bonds. PCC does not oxidise 3 alcohols. It
is however mainly used for 1 alcohoos.
(iv) Manganese dioxide selectively oxidises the alcoholic group of allylic and benzylic 1 and 2 alcohols
to give aldehydes and ketones respectively.
MnO
2  CH  CH  CH  CHO
CH 3  CH  CH  CH 2  OH  3
MnO
2  C H  CHO
C 6H 5  CH 2  OH  6 5
(v) Jones Reagent : H2CrO4 in acetone at 35C oxidises 1 and 2 alcohols to aldehydes and ketones
respectively. It, however does not oxidise double bond. It is mainly used for 2 alcohols.
9. Dehydrogenation : (With hot Copper)

This reaction also serves as a test for 1, 2, 3 alcohols.
Cu
1 alcohols : CH 3CH 2OH  CH 3CHO  H 2
300C
Aldehyde
Cu
2 alcohols : CH 3  C H  OH   CH 3  C  O  H 2
573 K 2
|
CH 3
Cu
3 alcohols :  CH3 3 C  OH   CH3  2  C  CH 2  H 2O (Alkenes are formed)
573 K
10.Lucas Test : Lucas reagent (a mixture of conc. HCl and ZnCl2) reacts with alcohols to form correspond-
ing alkyl chlorides which are soluble.
2 ZnCl
1 alcohols : RCH 2OH  No reaction at room temperature.
HCl
ZnCl
2  R C  Cl
2 alcohols : R 2CH  OH  3 White turbidity after 5 – 10 minutes.
HCl
ZnCl
2  R C  Cl
3 alcohols : R 3C  OH  3 White turbidity instantaneously.
HCl
Note : Allyl and Benzyl alcohol reacts as rapidly as 3alcohol to form soluble chloride with Lucas reagent.

Function of ZnCl2 in Lucas reagent : Since chloride ion is a weaker nucleophilie than bromide or iodide
ions, HCl does not react with less reactive 1 and 2 alcohols unless some good Lewis acid like ZnCl2 is
added to the reaction mixture. Zinc chloride, a good Lewis acid, forms a complex withthe alcohol. The
complex provides a better leaving group for the reaction than H2O.
(i) In case of 2 and 3 alcohols, the function of acid is to help in the formation of carbocations.
(ii) In case of methyl and 1 alcohols, the function of acid is to produce a substrate in which the leaving
group is a weakly basic species ; H2O or [Zn(OH)Cl2]– rather than a strongly basic hydroxide ion.
(ii) 3and Benzyl alcohols are more reactive due to formation of more stable corresponding carbocations.
11. Victor Meyer Test : This test is based upon the fact that three types (1, 2 and 3) of nitroalkanes
(formed by alcohols) react differently with nitrous acids followed by the action of Sodium hydroxide(alkali).
P/I
2  RCH I  AgNO
2  RCH NO 
2  R – C – NO HNO
1° Alcohol : RCH 2OH  2 2 2 2
or HI ||
NOH
Nitrolic acid
 Nitrolic acid on treatment with alkali dissolve in it to give a red colouration.

 Pseudonitrol on treatment with alkali does not dissolve but gives blue colour.
P /I 2
2  R C  I  AgNO 2  No reaction. HNO
3° Alcohol : R 3C  OH  3  R 3C  NO 2 
NOW ATTEMPT IN-CHAPTER EXERCISE-A BEFORE PROCEEDING AHEAD IN THIS EBOOK
PHENOLS Section - 2
Phenols are compounds containing an hydroxyl group : OH group, attached directly to an aromatic ring.
These generally are derivative of main member phenol, C6H5OH (ph – OH). The compounds in which OH
group is not attached directly to the ring such as benzyl alcohol, C6H5CH2OH are not phenols. These are
called as side chain aromatic alcohols having properties similar to aliphatic alcohols.
Some important phenols are :
Preparation of Phenols
1. From Chlorobenzene :
2. From Benzene sulphonic acid :

3. From Cumene :
Reactions involved in above synthesis are as follows :
I. SE reaction II. Free radical III. Acid catalysed hydrolytic rearrangement
II.
III.
4. From Benzene Diazonium chloride :
5. From Benzene :

6. From Grignard Reagent :
Reactions of Phenol
(A) Reactions of –OH group :
1. Salt Formation : Phenol is a weak acid and turns FeCl3 solution violet, but fails to give litmus
test. It reacts with sodium and NaOH to give phenoxides. Phenol however does not react with
Na2CO3 and NaHCO3.
The reaction of phenol with aqueous sodium hydroxide indicates that phenols are stronger acids
than alcohols and water.
Due to the higher electronegativity of sp 2 hybridised carbon to which  OH is attached, electron

density decreases on oxygen. This increases the polarity of O – H bond and results in an increase
in ionisation of phenols than that of alcohols. Also phenoxide, the conjugate base of phenol is
more stabilised than alkoxide, the conjugate base of alcohols. The delocalization of negative
charge (structures I-V) makes phenoxide ion more stable and favours ionisation of phenol.

2. Formation of Ester : The acetylation and benzoylation of phenols are called as Shautan-Bauman
reactions.
3. Formation of Ethers :
4. With PCl5 : (Formation of Aryl halides)
5. With Zn-dust : (Reduction)
6. Oxidation :

7. Condensation with Pthalic anhydride : Phenol undergoes a special Friedal Craft acylation with
pthalicanhydride in presence of H2SO4 to form phenolphthalein (an acid-base neutralisation indica-
tor).
8. With NH3 :
(B) Reactions of Benzene group :

Phenol undergoes electrophillic substitution reactions much more readily as compared to benzene due to
electron releasing ability of OH group (activating agent). Also OH group over benzene is strongly ‘o’ and
‘p’ directing due to +M effect of OH group.
1. Halogenation :

Note : Halogenation of phenol takes place even in absence of Lewis acid (AlBr3 , FeBr3 ) due to the highly activat
-ing effect of  OH group.
Note : OH group is strongly activating, hence a tri-substituted product is formed. However, in CS2 at 0C, only
Ortho (o) and Para (p) derivatives are formed.
2. Nitration :
(Poor yield, because NO2 group is deactivating)
Note : With concentrated nitric acid, phenol forms 2, 4, 6 - Trinitrophenol, commonly known as Picric acid.With
dilute acid, however, a mixture of o- and p- nitrophenol is formed. This mixture can be separated by
steam distillation.

3. Sulphonation :
At 25C, phenol gives only o-hydroxy benzene sulphonic acid, whereas at 100C, it gives p-hydroxy
benzene sulphonic acid.
Picric acid is prepared in good yield by treating phenol first with concentrated H 2SO 4 which con-
verts it to phenol-2, 4-disulphonic acid, then with concentrated HNO3 to get 2, 4, 6-trinitrophenol.
4. Nitrosation :
5. Alkylation :
Phenols undergo Friedal Craft alkylation to give the product according to the most stable intermedi-
ate carbonium ion.
6. Reimer - Tiemann Reaction :

Ortho product is formed as major because :

(i) Ortho position is more activated
(ii) Stabilization by chelation
Mechanism of Reimer – Tiemann Reaction: The reaction involves electrophillic substitution on the
highlyreactive phenoxide ring. Here the electrophile is dichlorocarbene : CCl2 , generated from CHCl3 by
the action of a base.
7. Kolbe’s Reaction :
Mechanism of Kolbe’s Reaction : CO2 acts as an electrophile in this reaction.

Note : (i) Transition state is stabilized by small size of (ii) If the reaction is carried out on potassium phenox-
Na + ion. ide the salt of the p-acid becomes the major prod
uct.
Because transition state formed by attack at ortho

positions is not stabilize due to bigger size of K +
The salicyclic acid formed above in Kolbe’s reaction is used to produce a number of important derivatives
used as medicines.
NOW ATTEMPT IN-CHAPTER EXERCISE-B BEFORE PROCEEDING AHEAD IN THIS EBOOK

ETHERS Section - 3
In ethers, the oxygen atom is bonded to two carbon atoms. The hydrocarbon group may be alkyl (1, 2
and 3), allylic, vinyl, alkynyl or aryl. Consider some examples :
CH3 – O – CH3 C2H5 – O – CH3 CH2 = CH – O – CH3
Dimethyl ether Ethyl methyl ether (Phenetole) Methyl vinyl ether
CH2 = CH – O – CH = CH2 CH2 = CHCH2 – O – CH3 CH3 – O – C6H5

Divinyl ether Allyl methyl ether Methyl phenyl ether (Anisole)
There are various types of cyclic ethers. Cyclic ethers consisting of two carbons in a three member ether are
called oxirane or epoxides. Cyclic ethers consisting of three carbons in a four member ether are called
oxetanes. Cyclic ethers consisting of four carbons in a five member ether are called tetrahydrofurans.
Preparations of Ethers
1. From alcohols : Dehydration of alcohols by H2SO4 at 170C gives alkenes, whereas at 140C
gives ethers. The dehydration of alcohols to ether is helped by distilling the ether as it is formed.
H SO
2 4  CH  CH
CH 3CH 2OH  2 2 (Alkene)
170 C
H SO
2 4  CH CH  O  CH CH
CH 3CH 2OH  3 2 2 3 (Ether)
140C
The formation of ethers occurs by SN2 mechanism with one molecule of alcohols acting as the nucleo
phile and another protonated molecules of the alcohols acting as the substrate. The mechanism of the
reaction is given below.
Step : 1 The alcohol accepts a proton from the acid to give a protonated alcohol.
Step : 2 The other molecule of alcohol acts a nucleophile and attacks the protonated alcohol in an
SN2 reaction to give a protonated ether.

Step : 3 The protonated ether transfers the proton to water molecule to give ether.
Note : (i) In case, when alkyl groups are 3, SN1 type path is followed. 3 alkyl alcohol forms a carbocation
(stable) and second alcohol acting as a nucleophile adds to it (solvolysis). An elimination product is
also formed as a minor product.
CH 3 CH 3 CH 3 CH 3
| | H 2SO 4
| |
CH 3  C  OH  CH 3  C OH 
140C
 CH 3  C O  C H  CH 3   CH 3 2 C  CH 2
| | | (Minor product)
CH 3 H CH 3
(ii) This method is generally limited to the preparation of symmetrical ethers, because a combination of
two alcohols usually yields a mixture of three ethers.
2. Williamson’s Synthesis : This is the most important method of formation of ethers (nucleophillic substitu
tion reaction), also known as Williamson’s synthesis. It consists of SN2 attack by alkoxide ion on an alkyl
halide, alkyl sulphate or alkyl sulphonate.
The alkoxide ion reacts with substrate in an SN2 reaction to give an ether. The substrate must have a good
leaving group. Important leaving groups are : halides (X), sulphates (OSO2OR) and sulphonates
(OSO2R). The substrate must have a primary alkyl group for good yield. In case of tertiary substrate,
elimination occurs. The other factor which contributes to substitution is low temperature.
Note : The aromatic ethers are formed when phenoxides reacts with alkyl sulphates in an SN2 reaction.
C 6 H 5 O Na  CH 3  OSO 2O  CH 3 
 C 6 H 5OCH 3  NaOSO 2OCH 3
Sodium phenoxide Dimethyl sulphate Methyl phenyl ether
3. Gas phase reaction :
2 3 Al O
2ROH  g  
 
R  O  R  H 2O
260  280 C
vapours

4. Oxymercuration - Demercuration :
Note : If water is used instead of alcohols and acid, an alkene is formed as per Markonikov’s addition.
5. By the action of Diazomethane : Methyl ethers can also be prepared by the action of diazomethane
(CH2N2) on alcohols in presence of HBF4 as catalyst.
4 HBF
CH 3CH 2OH  CH 2 N 2  CH 3CH 2  O  CH 3  N 2
6. From Grignard Reagents : Higher ethers can be prepared by treating -halo ethers with suitable Grignard
reagents. For example,
Dry
 CH 3  O  CH 2CH 3  Mg  I  Cl
CH 3  O  CH 2Cl  CH 3MgI 
ether
7. By treating Alkyl halide with dry Silver oxide :
2(CH 3 ) 2 CHCl  Ag 2O 
 (CH 3 ) 2 CH  O  CH(CH 3 ) 2  2 AgCl
Physical properties of Ethers :

(i) Dimethyl ether and ethyl methyl ether are gases. All others are colourless liquids with pleasant odours.
(ii) They are lighter than water. Lower ethers are highly volatile and very inflammable.
(iii) They are sparingly soluble in water but readily soluble in organic solvents. Solubility of ethers in water
in presence of small amount of alcohols perthaps due to hydrogen bonding between ether and water
 
molecules (R 2 O  H  OH). Ethers themselves are very good solvents.
(iv) Boiling points of ethers show a gradual increase with increase in molecular mass. Ethers have low
boiling points than isomeric alcohols as there is no association between the molecules as in alcohols
due to hydrogen bonding. The boiling points of ethers are close to the boiling points of alkanes.
(v) On account of R – O – Rbond angle being 100°, two dipoles do not cancel each other and mol-
ecules have small net dipole moment making the ethers somewhat polar.

Reactions of Ethers
Ethers are in general are less reactive and react only with acids. The reactive sites in ethers are : C – H
bonds (as in alkanes) and – O – group of ether bond. Ethers resist the attack of nucleophiles and bases.
However ethers are very good solvents in many organic reactions due to their ability to solvate cations by
donating the electron pair from oxygen atom.
1. Halogenation of ethers : Ethers like alkanes undergo halogenation in dark to give halogenated
ethers. The hydrogen atom attached to the carbon atom directly linked to oxygen atom is replaced
by halogens.
Cl
2  CH CH  O  C HCH 
2  CH C H  O  C HCH Cl
CH 3CH 2  O  CH 2CH 3  3 2 3 3 3
| | |
Cl Cl Cl
2. Ethers as Base : The oxygen atom of ethers makes them basic. They react with a proton donor to
give oxonium salts.
H
|
 CH 3CH 2  O  CH 2CH 3 Br 
CH 3CH 2  O  CH 2CH 3  H  Br 

3. Reaction with acids :
Ethers undergo cleavage under quite vigorous conditions, such as concentrated acids (usually HI and
HBr) and high temperatures.

R  O  R '  HX   RX  R 'OH
If the acid is present in excess, then the alcohol formed, further reacts with HX to give a halide
(Nucleophillic substitution).
 A di-alkyl ether (symmetric ether) yields two alkyl halide molecules, if HX is present is excess,
under hot conc. conditions.
R  O  R  HX 
 ROH  RX ; ROH  HX 
 RX  H 2O
HX
R  O  R 
 2 RX
excess
( hot conc.)
 For Mixed Ethers

(i) In case when both alkyl groups are 1 or 2 (i.e. R or R '  3 ), then SN2 path occurs.
I– as a nucleophile attacks the smaller of the two alkyl groups to give an alkyl iodide.
As I– makes an SN2 attack, consider steric factors. So, the smaller of the alkyl groups
goes with the iodide ion and the larger group forms alcohols.
(ii) If any one of R or R is 3, then we have different products via different mechanism. Here SN1
type of path is followed. Let R be 3.
 
H slow
R '  O  R 
 R '  O  R   R 'OH  R  (3 carbocation, highly stable)
step
|
H
R   I  
RI (Hence 3R forms iodide)
Note :  Excess of HX gives a mixture of alkyl halides.

 Reactivity of halogen acids : HI > HBr > HCl
 Alkyl aryl ethers are cleaved at the alkyl – oxygen bond due to the more stable aryl-oxygen bond. The
reaction yields phenol and alkyl halide.
Phenols do not react further to give halide (Nucleophillic substitution does not take place in aromatic
compounds).
Important :
Since it is SN2 path, X– should be a strong nucleophile. Hence in cleavage of aromatic ether, only HI (I
being strong nucleophile) can be used.
 With hot concentrated H2SO4 : Secondary and tertiary ethers react with hot conc. H2SO4 to give
a mixture of alcohols and alkenes.
H SO
2 4  CH
 CH3 3  C  O  CH 3 
hot conc.
 3 2  C  CH 2  CH 3OH
Note : Ease of formation of alkene follows : 3 > 2 > 1 (with respect to alkyl group).

4. With Phosphorus pentachloride : Phosphorus pentachloride also brings about the cleavage of C – O
bond of ethers leading to the formation of alkyl halides.
CH3CH 2  O  CH 2CH 3  PCl5 

 2 CH 3CH 2  Cl  POCl3
5. Reaction with Acid chloride and Anhydrides : Acid chlorides and anhydrides react with ethers when
heated in the presence of anhydrous. ZnCl2 or AlCl3 to form alkyl halides and esters.
2  C H Clanhyd. ZnCl
Et  O  Et  CH 3COCl  2 5  CH 3COOEt

Diethyl ether Acetyl chloride Ethyl chloride Ethyl acetate
However with anhydrides only esters are formed.

3 anhyd. AlCl
 C2 H 5 2 O   CH 3CO  2 O 

2 CH 3COOC 2H 5
Diethyl ether Acetic anhydride Ethyl acetate
6. Action of Air and Light : (Formation of Peroxides) : When exposed to air and light for a long time,
ethers are oxidised to form hydro-peroxides or simply peroxides.
light
Et  O  Et  O 2 
 CH 3  C H  O  Et
Diethyl ether |
O O  H
1 - Ethoxyethyl hydroperoxide
Therefore, serious explosions may occur during distillation of old samples of ethers if peroxides are not
removed. Presence of peroxides in old samples of ethers may be detected by shaking them with a freshly
prepared solution of FeSO4 followed by addition of KCNS. Appearance of a red colour indicates the
presence of peroxides. A simple method to remove peroxides is to shake an old sample of ether with
aqueous solution of KI or ferrous salt.
7. Hydrolysis of Ethers : Ethers when treated with dilute aqueous acids give alcohols.
3 H O
2  2 ROH H O
R  O  R 
Oxirane (Epoxide)
Epoxides are cyclic ethers with three membered rings. In IUPAC system, epoxides are called as Oxiranes.
The most common epoxide is ethylene oxide.

Preparation of Oxiranes
1. Oxidation of Ethylene : Epoxide or ethylene oxide is prepared by partial oxidation of ethylene in
presence of Ag2O.
2. Epoxidation : The most important method of formation of epoxides is the reaction of an alkene with
an organic peroxy acid or peracid, such as perbenzoic acid (C6H5COOOH) or peracetic acid
(CH3COOOH) or mCPBA (m-chloroperoxobenzoic acid). This process is known as epoxidation.
Note : The above reaction is a stereo specific reaction i.e., it involves cis-addition of an electrophillic oxygen atom.
It means cis-alkene will give only cis-epoxide and a trans-alkene will give only trans-epoxide.
Reactions of Oxiranes
Due to the strain in the ring, epoxides are highly reactive towards nucleophillic substitution reaction
(unlike ethers). They undergo ring opening reactions so as to release the strain. Epoxides undergo acid
catalysed and base catalysed opening of the ring.
1. Acid Catalysed Opening : The acid reacts with epoxides to produce a protonated epoxide. The
protonated epoxide undergoes ring opening by attack of nucleophile (A–) on sterically hindered car-
bon atom, because acid catalysed ring opening is SN 1type reaction
2. Base Catalysed Opening : Epoxides can also undergo base-catalysed ring opening provided the
attacking nucleophile is also a strong base such as an alkoxide or hydroxide ion. A strong nucleophile
(alkoxide, RO) is able to open the ring by a backside attack (as observed in a SN2 reaction)

Note :  Under acidic conditions, ring opening in protonated epoxide occurs to give a more stable (3)
carbonium ion.
 Under basic conditions, the alkoxide simply attacks the less hindered carbon atom in an SN2 type
displacement.
 Symmetrically substituted epoxides give the same product in both the acid-catalysed and base-catalysed
ring openings. An unsymmetrical epoxide gives different products under acid-catalysed and base-
catalysed conditions,
3. Cleavage of Oxiranes by Grignard Reagent and LiAlH4: In case of Grignard reagent, the Nu end, i.e.,
R attacks on the carbon atom of the epoxide. Here nucleophile attacks at less substituted ring carbon in the
base catalysed ring opening (As explained above).
Epoxides are reduced to alcohols an treatment with LiAlH4 ; hydride ion (as Nu–) is transferred to the less
crowded carbon.
Electrophillic substitution reaction in Aromatic Ethers

The alkoxy group is an Activating and ortho and para directing, just like – OH group in phenol. The following
SE reactions are observed.
(i)
Anisol undergoes bromination with Br2 in ethanoic acid, even in the absence of Iron (III) bromide
catalyst.

(ii) Friedel - Crafts Reactions :
(iii) Nitration :
Claisen Rearrangement of Allyl phenyl ether :

Allyl phenyl ether can be prepared by following reaction.

NOW ATTEMPT IN-CHAPTER EXERCISE-C BEFORE PROCEEDING AHEAD IN THIS EBOOK
DIHYDRIC ALCOHOLS Section - 4
Dihydric alcohols are called as diols. There are two types of diols :
(i) Geminal diol (ii) Vicinal diol
Geminal diols are unstable because of steric reason. There are hydrates of carbonyl compounds.
Some geminal diols are stable due to intramolecular H-bonding.
The viccinal type of dihydric alcohols are called as Glycols (Di-ols). Some Important Glycols are given
below :
Pinnacol(s) : Completely substituted vicinal diol is called as pinacol.

Preparations of Glycols
1. Hydroxylation of Alkenes
Note :  The reaction involves ‘syn’ addition.
2. Hydrolysis of Halohydrins
HOCl aq
CH 3CH  CH 2  CH 3  C H – C H 2  CH 3 – C H – C H 2
KOH
| | | |
OH Cl OH OH
(Halohydrins)
3. Acidic Hydrolysis of Oxiranes
aq
4. Hydrolysis of Viccinal Dihalides C H 2 – C H 2  C H 2 – C H 2
KOH
| | | |
Br Br OH OH
Viccinal dihalides
5. Reductive hydrolysis of carbonyl compounds (An important method for Pinncols)

 CH 3 – CO 
 1. Mg
 
|   CH 3  2  C  C   CH 3 2 (Pinnacol)
 CH 3  2. H 2O
| |
 
OH OH
H H
| |
1.Mg
2 CH 3CHO   CH 3 – C – C – CH 3
2.H 2 O
| |
OH OH
6. Reduction of Glyoxal(s)
Reactions of Glycol
1.
2. Reactions with Organic and Inorganic Acids

3. Polymerisation
4. Acetal (ketal) formation (cyclic acetals : dioxolan)
Note : (i) Acetals are stable in alkaline medium and are not reduced. Hence keto groups are protected in acetal
forms. Acetals are very easily hydrolysed in acidic medium to give back aldehyde and ketones.
(ii) Aldehydes are more reactive than ketones in this reaction.
5. (a) Oxidation

(b) Oxidative Cleavage

By using HIO4 : per iodic acid or Pb(OAc) 4
Lead tetra acetate
4 HIO
CH 3 – C H – C H 2  CH 3 – CHO  HCHO
| |
OH OH
Note : (i) ‘trans’ shows cleavage with resistance, whereas ‘cis’ shows cleavage instantly.
O
||
(ii) Special Case : In case when –CHOH and  C  groups are adjacent to each other, HIO4 also
breaks them as follows :
6. Intramolecular Condensation

7. Acid Catalysed “Pinnacol-Pinnacolone” Rearrangement
CH 3 CH 3 CH 3
| | H 2SO 4
|
CH 3 – C – C – CH 3   CH 3 – C – C – CH 3
| | || |
OH OH O CH 3
(Pinnacol) (Pinnacolone)
Methyltert.butylAcetone
Mechanism :
Note : The mechanism follows :

 Protonation of one hydroxyl group.
 Loss of proton.
 Migration of H– /ph– /Me–
 Loss of proton to give ketone.
Important :
1. Watch for the stability of carbocation in case of other diols.
2. Follow the order of migration as : ‘H’ followed by ‘phenyl’, followed by Ethyl followed by Methyl

 Ring expansion or ring contraction may also takes place if possible.
Tri-hydric Alcohol (Glycerol)
Preparations of Glycerol
1. Saponification of oils/fats (glycerides)
2. Synthetic glycerol
CH 2 CH 2Cl CH 2OH CH 2OH CH 2OH

|| Cl 2
| | | |
aq HOCl aq
C H   C H   C H   C HOH   C HOH
500C KOH KOH
| || || | |
CH 3 CH 2 CH 2 CH 2Cl CH 2OH
(propene) allylchloride allylalcohol
Reactions of Glycerol
1. With conc. HNO3

2. Reaction with Oxalic acid
Note : If T = 260°C , allyl alcohol is formed.
3. Action of HI
 If excess of glycerol of used.
 If excess of HI is used.
CH 2 CH 3 CH 3 CH 3
|| | –I 2
| |
HI HI
C H   C HI   C H   CH – I
| | || |
CH 2 I CH 2 I CH 2 CH 3
(Isopropy iodide)
4. Dehydration
CH 2OH CH 2
| KHSO
||
C HOH 4  C H (acrolein)

| |
CH 2OH CHO

Note :  A mixture of glyceryl trinitrate and glycernyl dinitrate absorbed on kieselguhr (Porous earth) is dyna-
mite, an explosive.
 Glycerol is used in the manufacture of polyster called glyptal, in medicines, cosmetics and in textile
processing.
 Glycerol is miscible in water and is sweet in taste.
NOW ATTEMPT IN-CHAPTER EXERCISE-D BEFORE PROCEEDING AHEAD IN THIS EBOOK
ILLUSTRATIONS Section - 5
Illustration - 1 An optically active alcohol A(C6H10O) absorbs two moles of hydrogen per mole of A upon
catalytic hydrogenation and gives a product B. The compound B is resistant to oxidation by CrO3 and does
not show any optical activity. Deduce the structures of A and B.
SOLUTION :
2 2H (O)
C6H10O (A)   B  resists oxidation
CrO3
(Optically active)
Clearly, A has a – C  C – bond and B should be a 3° alcohol as they resist oxidation.

Now visualise the structure of A keeping in mind a chiral centre (optically active).
Illustration - 2 3, 3-Dimethylbutan-2-ol loses a molecule of water in the presence of hot conc. H2SO4 to
give tetramethyl ethylene as the major product. Suggest a proper mechanism. Also identify the minor product.
SOLUTION :

Illustration - 3 A compound of molecular formula C7H8O is insoluble in water and dil. Na2CO3 but dissolves
in dil. NaOH solution. On treatment with Br2 / H 2O, it readily gives a precipitate of C7H5OBr3. What is the
structure of compound ?
SOLUTION :
The possible structures of compounds having molecular formula as C7H8O are :
It can not be benzyl alcohol or anisole as alcohols and ether (o, p, m) are insoluble in NaOH. It can be only
be cresol. Note that phenols are soluble in dil. NaOH forming phenoxides.
Now cresol can be o, p or m. How to identify it ?
Observe that it is SE (electrophilic substitution) giving a tri-substituted product as  OH is a strongly activating

group (+M effect). The only possible isomer giving a trisubtituted derivative can be m-cresol.
Note that both – OH and – CH3 activate same positions (i.e. o and p). Though, due to sterie factor,
bromination at the position between  OH and  Me group is quite difficult.

Illustration - 4 A compound X(C5H8O) does not react appreciably with Lucas reagent at room temperature
but gives a precipitate with ammonical AgNO3. With excess of MeMgBr, 0.42 gm of X gives 224 mL of CH4
at STP. Treatment of X with H2 in presence of Pt catalyst followed by boiling with excess HI gives n-pentane.
Suggest the structure of X and give all reactions involved.
SOLUTION :
3 AgNO
X   precipitate
 X contains – C  C – H group, which is confirmed by action of MeMgBr to give CH4.
0.42
mol of X  0.005 mol.
84
224
224 mL CH4 (STP)  mol  0.01 mol of X
22400
 1 mol X  2 mol CH4
Hence X contains two acidic H-atoms.
 
The structure of X should be : HC  CH 2CH 2CH 2 OH
Note that ‘X’ has to be 1° alcohol as it does not give Lucas test. Also note that 2 alcohol react with Grignard
Reapent to give alkanes, hence Lucas test is very important here.
2 H HI
Finally checking : HC  C  CH 2CH 2CH 2OH    H3C  CH 2  CH 2CH 2CH3
Pt
(n  Pentane)
Illustration - 5

SOLUTION :
Illustration - 6 Identify the products in the following reactions and comment on the stereochemistry of the
products.
(i) (ii)
SOLUTION :
(i) Observe that alcohol has a chiral centre.
Et Et Et
| Na
| _ CH3CH 2 Br
|
 (A)
H  C  OH   H  C  O Na   H  C O  CH 2CH3
SN 2
| | |
Me Me Me
Note that here O – H bond breaks to give alkoxide and in SN2 reaction ether is formed retaining the
configuration of alcohol.
Et Et
| TsCl
|
H  C  OH  H  C  OTs ;
| |
Me Me

HS will make an SN 2 attack from the back at   carbon (chiral) to give an inverted configuration.
Note that TsO is a very good leaving group assisting SN 2 reaction.
(ii) Reaction of alcohol with SOCl2 proceed by intramolecular nucleophilie substitution reaction (SN i)
mechanism, hence there is retention in configuration.
In second reaction product B is formed by SN 2 reaction mechanism of necleophilic substitution reaction

hence there is inversion in configuration of chiral carbon atom.
Illustration - 7 Give the possible products in the following reactions. Also comment upon the type of
pathways.
2 4  ? ?? H SO
(a) CH 3CH 2OH  CH 3CH 2CH 2OH 
T ~ 140C
H SO
2 4  ? ??
(b) CH 3CH 2OH   CH 3 3  C  OH 
T ~ 140C
SOLUTION :
2 4 H SO
(a) CH 3CH 2OH  CH3CH 2CH 2OH 
T ~140C
Note that both alcohols are 1 alcohols, so none of these is capable of carbocation formation (1 carbocations
being poorly stable). So here, ethers will be formed via SN2 pathway as temperature is around 140C.

In the first step, either or both of two alcohols can form oxonium ion (R O H 2 ) and then the second step, the
other one will make an SN2 attack on -carbon to give a protonated ether which eventually will give ether as
final product.

Due to absence of steric factors in two alcohols, possible products are :

H 
CH 3CH 2OH 
 CH3CH 2 O H 2
Hence the products (I, II, III) are formed via SN2 path.
H SO
2 4 ?
(b) CH3CH2OH   CH3   C  OH 
3
Note that one of these is tertiary butyl alcohol (3), so it will form stable carbocation which will finally give
ether as the main product via SN1 path.
Note :  A stable carbocation also give alkenes as minor product via E1 path.
H 
 CH3 3  C  CH3  C  CH 2
|
CH3 (E1)
 If T ~ 160 – 170C, E1 will be the major product.

Illustration - 8 Identify the products in the following :
(a) (b)
SOLUTION :
(a)
Note that if reagent is OH–, then visualise its action as a base.

(usually alcoholic KOH is visualised as : OH– as a base)
(b)

Illustration - 9 Identify compounds A, B, C . . . . in the following reaction setup.

CH CO H
3 3  A
CH 3  C  CH 2 
|
CH 3
SOLUTION :
Note :  Observe that Nu– (i.e., H2O18) attaches to more alkylated carbon in an acid catalysed ring opening.
It is SN 1type ring opening
[ CH3O  will attack at least steric hindered carbon atom in an

SN2 attack].
O 
O
| CH3 O H
|
CH3  C  CH 2OCH3   CH 3  C  CH 2OCH3 (C)
| |
CH3 CH3
 Observe that Nu– (CH3O–) attaches to less alkylated carbon in a base catalysed ring opening.
CH3
| conc.
B: CH 3  C  C H 2 
| | H 2 SO4
18OH OH

Visualise Pinnacol - Pinnacolone Rearrangement in glycols.
Note that the wrong answer is : CH 3  C  CH 2CH3

||
18O
Illustration - 10 Identify the products A, B, C and D and describe the pathways.
SOLUTION :
conc. HI solvent in H2O
CH 3 CH3
|  |   _ 
H SN 1 I (Nu )
CH 3  C  O  CH3  CH3  C  O CH3    CH3   C  CH3OH   CH 3  C  I 
3
| | | + (B) (A)
3°C ; stable
CH 3 CH 3 H
When solvent is ether, it being less polar favours SN2 path with I– as a strong nucleophile will make an SN2
attack at –CH3 group (no steric hindrance).

Illustration - 11 Identify A, B, C, . . . . in the following reactions :
ph ph
| | H 2 SO4 conc. LiAlH 4 H 2 SO4  conc.
(a) ph  C  C  Me   A   B  C
170C
| |
OH OH
(b)
NBS KOH  aq. 1. Na HI  conc.

(c) CH 3CH  CH 2 
 A 
 B  C 
DE
CCl4 2. MeBr 
SOLUTION :
C6H5 CH3
| | conc.
(a) C6H 5  C  C  CH3  ? It is a case of Pinnacol-Pinnacolone type of rearrangement.
| | H 2SO 4
OH OH
Observe that first visualise the most stable carbocation and then follow migration in order : H ph  R.
Rewriting (A) as :

(b)
+
Note : In general, R C O does not undergo rearrangement but if R is 3 then it breaks as mentioned below
:
For Example :
Note : If R is 1° or 2° (RCOCl) ; it will be simply Friedal craft acylation.
(c)

Illustration - 12 (a) How will you convert cyclohexanol to 1, 4-Dibromo-2-cyclohexene in not more than
4-steps ?
(b) How will you prepare 2, 3-Dimethyl-2-butanol from 2-Propanol as the only starting organic material ?
SOLUTION :
(a)
CH3 CH3
| |
(b) CH 3 C H  CH3 
 CH3  C  C H  CH3
| |
OH OH
2, 3-Dimethyl-2-butanol
2 alcohol 
 3 alcohol
(Think of Grignard reagent)
CH3 CH3
PCl5 Mg / Et 2 O (CH3 ) 2 CO
| |
CH 3 C H  CH 3   CH3  C H  CH 3   CH3  C H  CH 3   CH3  C  C H  CH3
| | | H 2O |
OH Cl MgCl OH
Illustration - 13 Propose mechanism for the following reactions.
(a)
(b)

SOLUTION :
(a)
Looking at the product . . . . . . Pick the structure II.
(b)

Observe carefully that this step will lead to nowhere as O H 2 is attached to phenyl ring. So think of alternative
path.

Illustration - 14
1. Br / H O
2 2  A 
3 CH C  CH .
3  C  CH I HI ( conc.)
CH3CH  CH 2 

 B   DE
2. OH Na 0C
SOLUTION :
Visualise base catalysed (SN2) ring opening (consider steric factors).
Note : I– as strong Nu– will atack at the least hindered CH3 group.
NOW ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK

Vidyamandir Classes
My Chapter Notes
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Vidyamandir Classes Oxygen Containing Organic Compounds - I

Oxygen Containing Organic Compounds - I

Some important Monohydric alcohols are :

 CH3 3 C  Br  NaOH  conc. 

Self Study Course for IITJEE with Online Support Section 1 1

(c) Oxymercuration and demercuration : Mercuric acetate (Hg(OAc)2 ) in presence of water -

2 Section 1 Self Study Course for IITJEE with Online Support

Self Study Course for IITJEE with Online Support Section 1 3

4. Hydrolysis of Ester : (Base or Acid catalysed)

(b) With concentrated HI :

4 Section 1 Self Study Course for IITJEE with Online Support

7. Reduction of Carboxylic acid and its derivatives :

Self Study Course for IITJEE with Online Support Section 1 5

(c) Tertiary alcohols :

(ii) From Water gas (Synthetic method) :

A mixture of CuO, ZnO, Cr2O3 is used as catalyst for this reaction.

6 Section 1 Self Study Course for IITJEE with Online Support

(iii) Oxidation of Methane :

(b) Ethanol : [C2H5OH]

(ii) From Starch (C6H10O5)n :

(c) For 1° alcohols (OXO - Process) :

high temp. pressure

Self Study Course for IITJEE with Online Support Section 1 7

Among the isomeric alcohols, b.p. show the following trend.

8 Section 1 Self Study Course for IITJEE with Online Support

Mechanism of Nucleophilic substitution reactions of Alcohols (SN 1 and SN 2 paths) :

3rd step : (CH3 )3  C+ + X  

Self Study Course for IITJEE with Online Support Section 1 9

1. With active metals:

2CH 3OH  2Na 

Note : (i) Alcohols behave like acids when O – H bond cleaves.

10 Section 1 Self Study Course for IITJEE with Online Support

2. Action of acids (Esterification):

Note : (i) Esterification reaction proceed by acylo-o-cleavage reaction mechanism.

CH 3  CO O  CO CH3 + H  OR 

Self Study Course for IITJEE with Online Support Section 1 11

(b) Esters of Sulphonic acids :

12 Section 1 Self Study Course for IITJEE with Online Support

3. Conversion of alcohols into alkyl halides :

Why CH3OH reacts faster than other primary alcohols ?

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Note : (i) If alcohols are in excess, then ethers are formed.

6. Reaction with Grignard Reagent :

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Secondary alcohols are oxidised to ketones by chromic anhydride (CrO3).

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9. Dehydrogenation : (With hot Copper)

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 Nitrolic acid on treatment with alkali dissolve in it to give a red colouration.

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NOW ATTEMPT IN-CHAPTER EXERCISE-A BEFORE PROCEEDING AHEAD IN THIS EBOOK

2. From Benzene sulphonic acid :

18 Section 2 Self Study Course for IITJEE with Online Support

Reactions involved in above synthesis are as follows :

I. SE reaction II. Free radical III. Acid catalysed hydrolytic rearrangement

4. From Benzene Diazonium chloride :

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6. From Grignard Reagent :

Due to the higher electronegativity of sp 2 hybridised carbon to which  OH is attached, electron

20 Section 2 Self Study Course for IITJEE with Online Support

4. With PCl5 : (Formation of Aryl halides)

5. With Zn-dust : (Reduction)

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