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 ALCOHOL PHENOL ETHER
 Alcohols are derivatives of water molecule replacing one hydrogen atom by an alkyl group
O –H O
+R
H H R H
Water Alcohol

An alcohol is a compound containing one or more hydroxyl group (OH) directly attached to aliphatic carbon
atoms.
The simplest alcohol is methyl alcohol, (CH3OH) also called carbinol.

 GENERAL METHODS OF PREPARATION OF ALCOHOLS

(A) From alkanes by hydration (addition of water)

H2SO4
C = C + H2O dilute C—C
(i)
H OH
Acid catalyzed hydration follows Markonikov’s rule but rearrangement may also take place. e.g.,


H
CH3  CH  CH  CH 2 
 CH3 CH  C H  CH3
| |  2 
CH 3 CH3


rearrangement 2  CH H O
  3  2 C  OH  CH 2CH3


 CH3 C  CH 2CH3 
H transfer | H
CH 3

(ii) Hydration using mercuric acetate/NaBH4 (oxymercuration-demercuration) follows

Markovnikov’s rule but no rearrangement.

Hg(OOCCH3)2 NaBH 4
C=C H2O
—C—C— —C—C—
OH Hg(OOCCH3) OH H
From From
water NaBH4

i  Hg  OOCCH3 
2  CH  CH  CH  CH
CH 3  CH 2  CH  CH 2  3 2 3
H 2O |
(ii) NaBH 4 OH
Bu tan  2  ol
(iii) Hydroboration oxidation using B2H6/H2O2 & OH–, addition of water takes place according to anti
Markonikov’s rule
 BH3 
2  CH  CH  CH 2 2  CH CH CH OH H O
CH3  CH  CH 2   3 2 2 3  B  3 2 2
Propene OH Propan 1 ol
Trialkyl borane

(B) Reduction method

[1]
 R  CHO  All on reduction with
R  COCl   LiAlH 4 / H 2O or H 2 / Pd gives primary
(i)
R  COOH  alcohols

While ketone RCOR' yields secondary alcohols.

NaBH4, reduces only aldehyde, ketones and acid halide.
2 5 Na / C H OH
R  CO2 R    RCH 2OH  R OH
Ester
(C) From Grignard reagent (RMgX)
R—MgX is an organometallic compound. As carbon is more electronegative than metal, R group is present as
negative group or Nu– and attack at the e** deficient carbon.
The reaction is an example of nucleophilic addition reaction.

+
ether H 3O
C = O + R — MgX H3O+ R — C — OMgX R— C — OH
carbonyl group X
(aldehyde or ketone)
+Mg
OH
 i  ether
HCHO  R  MgX 

 R  CH 2OH
Methanol ii  H3O 1 alcohol
 i  ether
R   CHO  R  MgX 

 R   CH  R
Aldehyde  ii  H3O |
OH
2 alcohol
R
|
i  ether
R   COR  R   MgX 

 R  C  R 
ketone  ii  H3O |
OH
3 alcohol
O OH
|| |
2 R MgX
H / R  C OR  
 H / R C  R 
Ester |
R 
 Either 2 or 3 alcohol 
(D) Methanol is commercially prepared from CO + H2 in the presence of Cu — ZnO — Cr2O3 as a catalyst at high
temperature and pressure.
CO  2H 2  CH3OH CH3OH is called wood alcohol.
Ethanol is commercially manufactured by using fermentation process. Fermentation of sucrose gives ethanol.
Inverse
C12H 22O11  H 2O 
 C6 H12O 6  C6 H12O6
glu cos e fructose

zymase
 2C2 H5OH  2CO 2
C6H12O6 
glu cos e ethanol
(i) Boiling point : Alcohols have a higher boiling point than haloalkanes of same number of C-atom. This is
due to the fact that alcohols are associated via intermolecular hydrogen bonding. B.P. of alcohols increases
 down the homologous series. For the same alcohol, as the branching increases, b.p. decreases due to
decrease in surface area. Vander waal forces holding the molecules together decreases, b.p. decreases.
(ii) Solubility : Lower alcohols are completely miscible in water due to their ability to form hydrogen bonds
with water.
The solubility of alcohols decreases down the homologous series, for the same alcohol, as the branching
increases, solubility increases, t-butanol is more soluble in water than n-butanol.
(iii) Alcohols are weaker acids than water : O—H bond in alcohol is less polar as compared to O—H bond
in water. The acidic strength of alcohols decreases as the number of e– donating R groups increases at -
carbon.
R CH2OH > R CH — O H>
(1°)
most acidic
R (2°)

R CH — O H
R
(3°)
least acidic
The increasing O—H bond strength order is 1°RO—H < 2°RO—H < 3°RO—H and increasing C—O bond
strength order is 3°R—OH < 2°R—OH < 1°R—OH
 Reactions of alcohols involving cleavage of O—H bond

Na 1
(i) RO  H   RO Na   H 2
2

(ii) RO  H  R  MgBr  R   H  RO  MgBr

only 1alcohol alkane

 Reaction involving cleavage of C—O bond toward these type of reactions, the reactivity order is
1°R—OH < 2°R—OH < 3°R—OH
All these reactions require the presence of Lewis’s acid because OH is not a good leaving group as it is a very
strong base. Before removing OH, we have to decrease its basicity by developing a positive charge on oxygen
and decreasing C—O bond strength.
PCl
5  R  Cl  POCl  HCl
(i) R  OH  3
white
fumes

3  PX
(ii) 3R  OH   3R  X  H 3PO3
X  Cl, Br
P  I2
(iii) R  OH   R  I  H3PO3
(iv) R  OH  SOCl2
 R  Cl  SO 2  HCl
 Reaction with Lucas reagent
Lucas reagent is conc. HCl/anhyd. ZnCl2. The reagent is used to distinguish 1°, 2° and 3° alcohol.
 3° ROH gives cloudiness or turbidity with Lucas reagent immediately.
 2° R—OH gives cloudiness or turbidity after 5-10 minute.
 1° R—OH does not give cloudiness or turbidity at room temperature.

 Dehydration of alcohol (loss of H2O) gives different products at different temperatures with conc. H2SO4. For
example-
 25°C
CH3CH2OSO3H
ethyl hydrogen
sulphate

conc. 140°C
CH3 — CH2OH H2SO 4 CH3CH2OCH2CH3
diethyl ether

CH2 = CH2
170°C ethene
The ease of dehydration of three alcohols increases in the order
1° ROH < 2° ROH < 3° ROH
 Dehydration of alcohol to alkene proceeds via the formation of carbonium ion (which can undergo rearrangement)
e.g.

H
+ +
CH3 — CH — CH2OH protonation CH3 — CH — CH2OH2
CH3 CH3
Loss of
deproto water
nation + H ion
+ +
CH3 — C — CH3 shift CH3 — CH — CH2
(1°)
–H
+ CH3 CH3

CH3 — C = CH2
CH3

 Dehydrogenation (loss of H2) with copper at 573K is used to distinguish 1°, 2° and 3° alcohol.
1° alcohol gives an aldehyde with same number of C-atoms
Cu
R – CH2OH 573 K R – CHO + H2
an aldehyde
(1°)
2° alcohol gives ketones
Cu
R – CHOH 573 K R – CO + H2
R R
(Ketone)
3° alcohol undergo dehydration to form alkene (as there is no carbinol hydrogen)
CH3
|
Cu
CH3 C  OH 
 CH3 C  CH 2  H 2O
| 573 K |
CH3 CH3
2  methyl propene  2  ol 2  methyl propene
 Oxidation of alcohols involves the cleavage of O—H and C—H, final product of oxidation depends upon the
structure of the alcohol and the oxidizing agent used.
The ease of oxidation follows a order
3°R — OH < 2°R—OH < 1°R — OH
(3° alcohols do not have any -hydrogen)
  O  O
R  CH 2 OH 
 R  CHO 
 R  CHO
K 2 Cr2 O7 / H 2SO4 same no. of K 2 Cr2 O7 / H 2 SO4 acid with same
C  atoms no. of carbon

  O  
 R  CO  R  
R  CHOH   RCOOH  R COOH
O
| K2Cr2O7 / H2SO4 ketone with same K 2Cr2O7 / H 2SO4 each acid contains
R no. C atoms lesser no. of C atoms
 2 
R
|
R  C OH 
 No reaction
O 
|
R  3 
 Properties and uses of methanol
1. It is a colourless liquid and highly poisonous.
2. It is completely soluble in water.
3. It is used as solvent for paints, varnishes, and for making fomaldehyde.
 Ehtanol is a colourless liquid, higher b.p. than methanol. It is used as a solvent in paints industry. Denaturation of
ethanol (or alcohol) means making it unfit for drinking purposes by adding CuSO4 and pyridine.
 Ethylene glycol is an example of dihydric alcohol. Its IUPAC name is ehtane-1,2-diol. Its structureal formula is

CH2  CH2
| |
OH OH

 Preparation of ethylene glycol

Cl2 aq
CH2 — CH2 .K
O H
Cl Cl CH2 — CH2
H H2 O

1 O /Ag
51 4
/3 2 SO
K

CH2 = CH2 2 2 OH OH
400 K CH2 — CH2
ethene
O

KMnO4
CH2 — CH2
OH OH
 Properties of ethylene glycol
(i) It is colourless syrupy liquid
(ii) It has a high b.p. than ehtanol due to more network of intermolecular hydrogen
bonding.
Uses of ethylene glycol
(i) It is used as antifreeze in car radiator.
(ii) It is used in the preparation of polyester.
(iii) It is used as solvent.
 Reaction of Glycol
In glycol, both the OH groups are primary alcoholic groups.
 Cu/573K
CHO
Glyoxal
CHO

HNO3
CH2ONO2
Glycol dinitrate
CH2ONO2
CH2OH HI excess
CH2 — CH2I
CH2OH Iodoethane

HIO4
2HCHO
methanol

strong [O]
K2Cr2O7/H2SO4 COOH
COOH
Oxalic acid

 Glycerol or glycerine is an example of trihydric alcohol. Its IUPAC name is propane-1,2,3-triol. Its structural
formula is

CH 2  CH  CH 2
| | |
OH OH OH
 Glycerol is prepared commercially by the alkaline hydrolysis of fat or oil (which are called triglycerides).
O
||
C H2  O  C R
| O CH 2OH
| || |
C H  O  C  R  3NaOH  CHOH  3RCOONa
| O | Soap
| || CH 2OH
CH 2  O  C  R Glycerol
Triglyceride

The alkaline hydrolysis of an ester is called saponification.

 Properties of Glycerol
(i) It is highly viscous liquid with high b.p. This is due to extensive network of inter molecular hydrogen bonding.
(ii) It is colourless, hygroscopic liquid.
(iii) Glycerol is used in the preparation of polyesters, dyanamite and for medicines, cosmetics and the textile
processing.
 Reactions of glycerol
3HNO3
CH2 — CH — CH2
ONO2 ONO2 ONO2
Glyceryl trinitrate
or nitro glycerine

OH
conc. H2SO4
[CH2 = C = CH]
Tautomerism
CH2 = C — CHO
Acrolein or acraldelryde

1° 2° 1° CH2OH CHO
CH2 — CH — CH2 FeSO4/H2O2
Fenton's CO + CHOH
OH OH OH reagent
CH2OH CH2OH
Dihydroxy Glycer-
acetone aldehyde
Glycerose
excess HI
CH2 — CH — CH3
I

HIO4
2HCHO + HCOOH
PHENOL
 Phenols are compounds with an OH group attached directly to a carbon of an aromatic ring. The compound
phenol is C6H5OH.
OH

If OH group is present on the side chain, then it is called aliphatic alcohol. For example

CH2OH

 Phenols may be
OH
OH
OH
(i) monohydric, (ii) dihydric,
Catechol
OH

(iii) trihydric,
OH OH
Phloroglucinol
 Phenol name for OH is also accepted in IUPAC system. IUPAC and common names of some of the
phenolic compounds are given below :
CH3 OH OH
NO2

OH
OH o-nitrophenol
Resorcinol
p-cresol (2-nitrophenol)
(Benzene-1,3-diol)
(4-methylphenol)
 The structure of phenol is
136 pm

O
H
The C—O bond is slightly shorter than the C—O bond present in methanol. This is due to partial double bond
character as lone pair of electrons on oxygen participates into resonance with the benzene ring.
 Preparation of phenol
SO3H SO3Na ONa OH

H2SO4 NaOH NaOH H

+

SO3 fuse
(i)
sodium benzene
sulphonate
Cl ONa OH

NaOH, 623K dil.HCl

fuse (DOW's process)
(ii)
Chlorobenzene Sodium
phenoxide

+
NaN O2 + HCl + – H2O/H
NH2 0-4°C N2 Cl 160°C OH + N2 + HCl
(iii)
Aniline Aniline

 Phenol is prepared commercially by cumene-phenol process.

CH3
CH(CH3)2 CH3—C—O—O—H OH

CH 3CH = CH2 O2 H+
H2SO4 H2O + CH3COCH3
Cumene
 Phenols have a higher boiling point than the corresponding hydrocarbon or aryl halides. This is due to the presence
of intermolecular hydrogen bonding. Due to their ability to forms H-bonds with water, phenols are moderately
soluble in H2O.
 The phenols are acidic in nature and stronger acids than alcohols.
–
OH O

+
+ H2O + H3O
 The pair of oxygen in phenol is delocalized with the benzene ring. As a result, the strength of O—H bond
decreases and H as H+ ion can easily be removed.
 The presence of electrons withdrawing group (EWG) like NO2 group, increases the acidic strength and electron
donating groups (EDG) like R group decreases the acidic strength. Therefore, the acidic strength order is
OH OH OH

< <

CH3 NO2
The increasing acidic strength order of the three nitrophenols is
OH OH OH
NO2
< <
NO2
NO2
In m-nitro phenol, only –I effect no –R of NO2 present. In o-nitro phenol. –I, –R effect of NO2 both present but
weaker than para as there exists an intra molecular hydrogen bonding.
p-nitrophenol is the strongest acid due to –R, –I effect of NO2.
 Reaction of phenol involving the cleavage of O—H bond.
H2O
O– + H3O–

NaOH – +
O + Na + H2O
OH
RMgX
OMgX + RH

O
Acylation of phenol

CH2COCl
O — C — CH3 + HCl
Phenyl ethanoate
O
O — C — CH3 + CH3COOH
(CH3CO)2O Phenyl ethanoate

 Reactions of phenol involving cleavage of C—O bond

NH3
NH3/anhyd.
OH ZnCl2 + H2O
Aniline

Zn dust
+ ZnO
Benzene
 The presence of OH group on benzene increases the electron density on the benzene ring making it more
susceptible to attract by an electrophile. The reactions involving benzene ring are electrophilic substitution reactions.
The presence of OH group makes the ortho and para-carbon of benzene more electron rich than meta position.
The OH group is called o-, p-directing group.
+ + +
O—H O—H O—H O—H O—H

– –

–
 Electrophilic substitution reactions of phenol
OH OH
NO2
dil. HNO3
25°C +

(Major) NO2
OH
O2N NO2
2,4,6-trinitrophenol
(picric acid)
Conc. HNO3 yellow solid

NO2

OH OH
Br Br
Br2(aq.) 2,4,6-tribromophenol
(white ppt.)

Br
OH OH
Br
Br2 in CS2
+

Br
OH (Major)
COOH
2-hydroxybenzoic acid
NaOH/CO2 (Salicyclic acid)
400 K, (Kolbe reaction)
4-7 atm
dil. HCl
OH
KOH/CHCl3, CHO
2-hydroxybenzaldehyde
343 K (Salicyaldehyde)
dil. HCl (Reimer-Tiemann reaction)

 Esters of phenol gives phenolic ketones on rearrangement in the presence of anhydrous AlCl3. The reaction is
called Fires rearrangement.
Phenyl acetate yield phenolic ketones on treatment with anhydrous AlCl3.
 OCOCH3 OH OH

AlCl3 COCH3
+
O-hydroxy
acetophenole COCH3
P-hydroxy
aceto phenone

 Condensation reaction of phenol

With benzene diazonium chloride (Diazo coupling)

N2+Cl– + H OH N=N OH

p-hydroxyazobenzene
(azodye)

 Uses of Phenol
(i) It is used as an antiseptic, disinfectant.
(ii) It is used in the preparation of dyes, drugs.
(iii) It is used in the preparation of bakelite, Novalac.

ETHERS
 Ethers are derivatives of water, H2O, replacing both hydrogen by alkyl or aryl groups.
O
R R'
If R = R', then the ether is called simple ether. The common name is dialkyl ether. CH3CH2OCH2CH3 is diethyl
ether.
If R  R', then ether is called mixed ether. Then arrange the alkyl groups alphabetically and write a suffix ether..

CH3  O  CH  CH3 is isopropyl methyl ether. In IUPAC system, ethers are called alkoxy alkane.
|
CH3

CH3—OCH2CH3 is methoxy ethane and OCH3 is methoxy benzene. Its common name is methyl

phenyl ether (anisole).

Phenetole is a common name of ethoxy benzene.
 Preparation of ethers
(i) Dehydration of 1° alcohols
H SO
2 4  CH CH OCH CH
2CH3CH 2OH  3 2 2 3
413
2° and 3° alcohols on dehydration gives alkenes and not ethers.
(ii) From alkyl halides.

2 Ag O
2RX   R 2O  2AgX
dry
 (iii) From alkyl halides using Williamson’s synthesis (SN2 reaction).

RX  NaOR  
 R  O  R   NaX
(R = CH3,1°) sodium alkoxide
(R' = 1°, 2°, 3° or Ar)
The important method to prepare any type of ether. With 3° RX, alkenes are formed as alkoxide ion is also a
strong base, alkyl halide then undergoes elimination reaction.
CH3 CH3
| |
CH3Br  CH3 C  O Na   CH3  O C  CH3  NaBr
| |
CH3 CH3

CH 3
|
CH3 C  Br  Na  OCH3 
 CH3 C  CH 2  NaBr  CH3OH
| |
CH 3 CH 3
 Ethers and monohydric alcohols are functional isomers but ethers have a lower b.p. than alcohols due to their
inability to associate via intermolecular hydrogen bonding. Ethers are volatile.
 Ethers are polar in nature and have a net dipole moment even if the R groups are similar. This is due to their bent
O
structure.
R R
The oxygen atom is sp3 hybridized and C—O—C bond angle is more than 109° due to the repulsions between the
bulky large size R groups.
 Lower ethers (containing upto three carbon atoms) are completely miscible in water. The solubility of ethers
decreases as the number of carbon atoms increases.
 Due to the presence of electron donating R groups and lone pair on oxygen atoms, ethers are Bronsted bases as
well as Lewis bases.

R 2O  HX  R 2OH  X 
(X = Cl,Br) dialkyl oxonium halide

R 2O  BF3   R 2O  BF3 
Lewis Lewis
base acid

 Reactions of ethers involving C—O bond cleavage R—O—R + HI  ROH + RI simple ether
For a given ether, the reactivity of hydrogen halides follows a order:
HCl < HBr < HI (Strongest acid)
 In case of aromatic ether, reaction with HI results in the cleagvage of R—O bond because Ar—O bond has a
double bond character and is strong. Also breaking R—O bond results in the formation of phenoxide ion which is
resonance stabilized.
OR OH

+ HI + RI

 In case of mixed ether with the different R groups, the product depends on the nature of R groups.
When 1° or 2° R groups present, the lower R groups from alkyl iodide with HI (This is an S 2 reaction)
N
CH 3OCH 2CH3  HI  CH3I  CH3CH 2OH
 When one of the R group is 3° R group, then tertiary alkyl iodide is formed with HI.
CH 3 CH3
| |
CH 3  C  OCH3  HI 
 CH3 C  I  CH3OH
| |
CH 3 CH 3
Because 3° carbonium ion is more stable.
Some more examples :

HI
(i) O — C(CH3)3 OH + (CH3)3Cl

HI
(ii) CH2 — O — C(CH3)3 CH2I + (CH3)3COH

 The most important simple ether is ethoxy ethane. It is used as a solvent for oils, gums, resins, etc.
It is also used as an inhalation anaesthetic. Ethrane and isoflurane are also used as anaesthetic. Phenyl ether used
as a heat transfer medium because of its high boiling point.
 Some more reactions of ether
(i) R 2O  PCl5  2RCl  POCl3

(ii) H
 2ROH
R 2O  H 2O 

H
|
(iii) CH3OCH3  O2 
 CH3  C  O  O  H
|
H
dimethyl ether peroxide
 present as an impurity in ethers 

 RO-group on benzene ring is activating and o-, p-directing. Electrophilic substitution reactions of aromatic ether
are
OCH3 OCH3
Br
Br2 /CH3COOH
+

Br
OCH3 OCH3
NO2
HNO3 /H2 SO4
+
OCH3
o-nitroanisole
NO2
p-nitroanisole

OCH3 OCH3
Anisole CH3
CH3Cl/AlCl3
+
Friedel-Craft

CH3
OCH3 OCH3
OCCH3
+
CH3COCl/AlCl3

OCCH3
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