ALCOHOL, PHENOL AND

CHAPTER
11
ETHER
Organic compounds exist in which a hydrogen atom, joined to the
carbon, acquires acid properties as a result of the proximity of certain
functional groupings.

''VICTOR GRIGNARD''

INTRODUCTION

A
lcohols and phenols are formed when a hydrogen atom in a hydrocarbon, aliphatic
and aromatic respectively, is replaced by –OH group. These classes of compounds
find wide applications in industry as well as in day-to-day life. For instance, ordinary
spirit used for polishing wooden furniture is chiefly a compound containing hydroxyl
group, ethanol. The sugar we eat, the cotton used for fabrics, the paper we use for
writing, are all made up of compounds containing –OH groups.
The substitution of a hydrogen atom in a hydrocarbon by an alkoxy or aryloxy
group (R–O/Ar–O) yields another class of compounds known as ‘ethers’, for
example, CH3OCH3 (dimethyl ether). Ethers as compounds formed by substituting
the hydrogen atom of hydroxyl group of an alcohol or phenol by an alkyl or aryl
group.
 Hydroxy derivatives

Aliphatic hydroxy derivatives Aromatic hydroxy derivatives

Alcohols have sp3 hybridized oxygen atoms, but the C – O – H bond angle in methanol (108.9°) is considerably
larger than the H – O – H bond angle in water (104.5°) because the methyl group is much larger than a hydrogen
atom. The bulky methyl group counteracts the bond angle compression caused by oxygen’s nonbonding pairs of
electrons. The O – H bond lengths are about the same in water and methanol (0.96 Å), but the C – O bond is
considerably longer (1.4 Å), reflecting the larger covalent radius of carbon compared to hydrogen.

•• •• •• ••

O O
H
H 104.5° H C 108.9° H
H
water H
methyl alcohol

(I) Aliphatic hydroxy derivatives :

Hydroxy derivatives in which —OH is directly attached to sp3 C (Alcoholic compounds).
(II) Aromatic hydroxy derivatives :
Hydroxy derivatives in which —OH is directly attached to sp2 C or benzene ring (Phenolic compounds).

(I) Aliphatic hydroxy derivatives

(a) Classification according to number of —OH groups :
(i) Monohydric [one –OH]  CH3CH2—OH

(ii) Dihydric [two –OH]  CH2 CH2

OH OH

(iii) Trihydric [three –OH]  CH 2 CH CH 2

OH OH OH

(iv) Polyhydric [n –OH]  CH 2 CH -------------CH 2

OH OH OH

(b) Classification according to nature of carbon :

(i) p or 1° – alcohol  CH3CH2 – OH
(ii) s or 2° – alcohol  (CH3)2CH – OH
(i) t or 3° – alcohol  (CH3)3C – OH

2
 ALCOHOLS
Structure of alcohol : 3 :O: sp
sp

3
3
Alcohols are bent molecules. The carbon atom (linked with sp 108.5° 1s
'O' atom of –OH group) is sp3
hybridised. The central 'O'
atom is also in sp3 state of hybridisation. The bond angle is H3C 3 H
sp 1s
108.50 . In sp3 hybridisation of O - 2s2,2px2 2py1 2pz1 orbitals Structure of CH3OH
hybridised to form sp3 orbitals

In these four orbitals two containing one electron

each and two containing two electrons each. Orbitals
containing two electrons do not take part in bonding. Other
two half filled orbitals form  bond with s-orbitals of H -atom
and hybridised orbital of C-atom (O—C).

Due to lone pair effect the bond angle of tetrahedral oxygen

atom is lesser than normal tetrahedral structure (109028').

(I) Monohydric alcohol

General methods of preparation :
(a) From alkanes (By oxidation) :

H / KMnO4
(CH3)3 C—H (CH3)3 C — OH
Δ

(b) From alkenes :

(i) By hydration :

H
CH3 — CH = CH2 H2O

(ii) By hydroboration oxidation :

BH3
CH3— CH = CH2 H2O2/HO CH 3 CH 2 CH2 (1° alcohol)

OH
(iii) By oxymercuration demercuration :
(i) Hg(OAc)2,H2O
CH3—CH CH2 CH3 CH CH 3
(ii) NaBH4,HO

OH

(c) From alkyl halides (By hydrolysis) :

Aq. KOH
CH3—CH2—Cl or Moist Ag2O
CH3CH2 — OH

3
 (d) From carbonyl compounds (By reduction) :
>C O Reducing agent > CH—OH

 Reducing agents may be,

LiAlH4/H NaBH4/H
Na + EtOH [Bouveault-blanc Reduction]
NaH [Darzen reduction]
Ni / H2
LiAlH4
R— CHO  R—CH2—OH
H
NaBH4
R C R R CH R
H
O OH

CH3 C CH3 LiAlH4

 ?
H
O
Mechanism :

LiAlH4
CH3—CH CH—CHO  CH3—CH CH—CH2—OH
H
Crotonaldehyde
LiAlH4
Ph—CH = CH—CHO   Ph—CH2—CH2—CH2—OH
H /OH
Cinnamaldehyde

(e) From ethers :

dil. H2SO4
R—O—R R—OH + R—OH
dil. H2SO4
CH3—O—CH2CH3 CH3—OH + CH3CH2—OH

4
(f) From acid and derivatives (By reduction) :
LiAlH4
R— COOH  R— CH2— OH + H2O
H
LiAlH4
R C Cl  R— CH2— OH + HCl
H
O
LiAlH4
R C OR  R — CH2— OH + R— OH
H
O
LiAlH4
R C O C OR  R— CH2— OH + R — CH2— OH
H
O O
LiAlH4
R C NH2  R — CH2— NH2 + H2O
H
O

(g) From esters (By hydrolysis) :

(i) By alkaline hydrolysis :
NaOH
R C OR R C ONa + R OH
O O
(ii) By acidic hydrolysis :

R C OR R C OH + R OH

O O

H3O
CH 3 C OC 2H5 CH 3 C OH + C2H5OH

O O
This reaction is reversible reaction and it's order is 1 and it is also called Pseudo-Unimolecular reaction.
(h) From p-amines :
NaNO2+HCl
R—NH2 or HNO2
R—OH + N2 + H2O

CH3CH2—NH2 HNO2 CH3CH2—OH + N2 + H2O

Mechanism :
NaNO2+HCl
CH3CH2 –NH2 CH3CH2– N2 Cl CH 3CH2+ N2 + Cl

Unstable

OH [Major]

Inter mediate is carbocation so rearrangement may be possible.

5
Ex. CH3CH2CH2—NH2 NaNO2+HCl ?
Sol. Mechanism :

 1 
NaNO2+HCl
CH3CH2CH2—NH2 CH3CH2CH2— N2 Cl  CH 3CH 2 CH 2

Exception : CH 3 – NH 2 HNO2 CH 3 – O – CH 3

(i) From Grignard reagent :

(i) p-alcohol :
H2O
R—Mg—X + [O]  R — O — MgX R—OH
[Same C-p-alcohol]

OH [one C more p-alcohol]

(ii) s-alcohol :

(iii) t-alcohol :

6
(j) Industrial method :
Azeotropic distillation are used.j

Rectified spirit 65°C

ethanol + benzene + H2O
+ (18.5%) (74.1%) (7.4%)
distillation
Benzene (excess) (ternary mixture

mixture with 68°C

Benzene + ethanol
(80%) (20%)
distillation
no water content (binary mixture)

mixture with 78.3%C

absolute alcohol
distillation
no water and benzene (100% alcohol)

Physical properties :
(i) C1 to C11 are colourless liquids and high alcohols are solids.
(ii) Density of monohydric alcohol is less than H2O.
(iii) Density  mol. wt. (for monohydric alcohol).
(iv) Solubility :
 The first three members are completely miscible with water. The higher members are almost insoluble in
water but are soluble in organic solvents like benzene, ether etc.
 The solubility of lower alcohols is due to the existence of hydrogen bonds between water and polar O–H
groups of alcohol molecules.
 The solubility of alcohols in water decreases with increase in molecular mass.
 Among the isomeric alcohols the solubility decrease with branching of chain increases.
C1 to C3 and t-butyl alcohol is completely soluble in H2O due to H–bonding.

1
solubility  No. of side chains  
molecular weight

Order of solubility :
C4H9OH > C5H11OH > C6H13OH

CH3

CH3CH2CH2CH2OH < CH 3CH 2CH OH < CH3 C OH

CH3 CH3

CH 3CH2CH 2 < CH 3 CH CH 2 < CH2 CH CH2

OH OH OH OH OH OH
[Number of —OH increases, H-bonding increases]

7
 (v) Boiling points : B.P.  molecular weight

1
If molecular wt. is same then B.P. 
branching

Order of BP : C4H9OH < C5H11OH < C6H13OH

CH3
CH3CH2CH2CH2OH > CH3CH2CH OH > CH3 C OH
CH3 CH3
CH 3CH2CH 2 < CH 3 CH CH 2 < CH2 CH CH2

OH OH OH OH OH OH
[Number of OH increases, H-bonding increases]

Ex. Boiling point of alcohol is more than corresponding ether. Why ?

Sol. Reason : H-bonding in alcohol.
O H ---------- O H ------------- O H ------------- O H ----------
R R R R

Ex. Boiling point of alcohol is less than corresponding carboxylic acid. Why ?
Sol. Reason : Dimer formation in carboxylic acid.
O H O
R C C R
OH O

Chemical properties :
Monohydric alcohol show following reactions

(A) Reaction involving cleavage of O H

(B) Reaction involving cleavage of C OH

(C) Reaction involving complete molecule of alcohol

(A) Reaction involving cleavage of O H : Reactivity order (Acidic nature) is

CH3—OH > CH3CH2—OH > (CH3)2CH—OH > (CH3)3C—OH
(i) Acidic nature :
H2O > R—OH > CH CH > NH3 (Acidic strength)
Alcohols are less acidic than H2O and neutral for litmus paper and gives H2 with active metals (Na, K)
1
R—OH + Na  R—ONa + H
2 2
1
R—OH + K  R—OK + H
2 2

8
(ii) Reaction with CS2 :
1
R— OH + Na  R— ONa + H
2 2
R— ONa + S C S  R O C S Na
S
Sodium alkyl xanthate (Used as floating agent)

(iii) Alkylation:
R— OH CH2N 2/ R—O—CH2—H
R— OH Na R— ONa RX R—O—R
(Williamson synthesis)

(iv) Acylation :
R OH + Cl C R  R O C R
O O
(Acylation)

R OH + Cl C CH3  R O C CH3

O O
(Acetylation)

OH O C R

CH3COCl O
COOH COOH

Salicylic acid Acetoxy benzoic acid

Acetyl salicylic acid
Aspirin [Used as analgesic]

(v) Benzoylation : (Schotten Baumann's Reaction) :

R OH + Cl C Ph  R O C Ph
O O
(Benzoylation)

(vi) Esterification : Conc. H2SO4 is used as catalyst and dehydrating agent.

R C OH + R OH  Conc. H2SO4  R C OR + H2O

O O

9
 Mechanism :

H2SO4 H+ + HSO4–

: :
+
R—C—O—H + H R—C—O—H
O OH

Note : This is a laboratory method to prepare ester.

Ex. CH3 C OH + H OC 2H5  conc. H2 SO4  CH3 C OC2 H5 + H2O

O O
18 18
Ex. Ph C OH + H OC2H5  conc. H2SO4  Ph C OC2H5 + H2O
O O
Dry HCl can be used as dehydrating agent.
Ex. CH3 C OH + H OC 2H5 Dry HCl CH3 C OC2 H5 + H2O
O
O

ETO
KOEY
S KPO
EYIN
PO
TSINTS
1
(a) Reactivity for esterification  .
Steric hinderence
(b) Reactivity of R – OH [If acid is same] : CH3 – OH > 1° > 2° > 3° alcohol
(c) Reactivity of RCOOH [If alcohol is same] :
CH3

H C OH > CH3 C OH > CH3 CH C OH > CH3 C C OH

O O CH3 O CH3 O

(vii) Reaction with CH  CH :

BF3/HgO CH CH OCH3
CH CH + 2CH3—OH   3
 OCH3
Methylal

BF3/HgO OC2H5
CH CH + 2CH3CH2— OH CH3CH
 OC2H5
Ethylal

10
 (viii) Reaction with carbonyl compounds :
OR
R—CHO + 2R—OH R CH
OR
Acetal

R OR
R C R + 2R OH  C
R OR
O Ketal

OCH3
CH3CHO + 2CH3—OH  CH3CH
OCH3
Methylal
(ix) Reaction with Grignard reagent :
X
R—Mg—X + H—OR R H + Mg
OR
(x) Reaction with Ketene : Ketene is used as acetylating agent.

OR OR

CH2 = C = O + R—OH  CH2 C OH    CH3 C O

OC 2H 5 OC 2H5

CH2 C O + C2H5—OH  CH2 C OH    CH3 C O

Ethyl acetate
(xi) Reaction with isocyanic acid : Ethyl urethane is used in preparation of urea

OC2H5 OC2H5
NH C O + H—OC2H5  NH C OH    NH2 C O
Ethyl urethane
(xii) Reaction with oxirane :
OR
+
H
R OH + CH2 CH2 CH2 CH2
O
OH

(B) Reaction involving cleavage of C OH : Reactivity order or basic nature is

CH3—OH < CH3CH2—OH< (CH3)2CH—OH < (CH3)3 C—OH
(i) Reaction with halogen acid :
ZnCl2
R—CH2—OH + HCl R—CH2—Cl + H 2O

ZnCl2
R2CH—OH + HCl R2CH—Cl + H2O

20 alcohol
Reactivity of the acids is HI > HBr > HCl > HF

11
 (ii) Reaction with inorganic acids :



Nitric acid Alkyl nitrate

R—OH + HHSO4  R—HSO4 + H2O

Alkyl hydrogen sulphate

(iii) Reaction with phosphorous halides :

3R—OH + PCl3  3RCl + H3PO3
R—OH + PCl5  R—Cl + POCl3 + HCl

(iv) Reaction with thionyl chloride (SOCl2) :

R—OH + SOCl2 Pyridine R—Cl + SO2  + HCl
(gas)

(v) Reaction with NH3 : Alumina (Al2O3) is used as dehydrating agent.

Al2O3
R OH + HNH2 R—NH2 + H2O
250°C

(vi) Reaction with halogens : Oxidation and chlorination takes place simultaneously.
CH3CH2OH + Cl2(dry)  CH3CHO + 2HCl (Oxidation)
CH3CHO + 3Cl2  CCl3CHO + 3HCl (chlorination)
chloral

(vii) E1 Reaction of Alcohols :

Dehydration requires an acidic catalyst to protonate the the hydroxyl group of the alcohol and convert it to a
good leaving group. Loss of water, followed by loss of proton, gives the alkene. An equilibrium is established
between reactants and products.
For E1 mechanism reagents are (i) H3 PO4/ (ii) H2SO4/160°

acid
C C C C + H2O (Rearrangement may occur)
H OH

Mechanism :

Step 1 :

Step 2 :

12
 Step 3 :

Remarks : In first step, an acid-base reaction a proton is rapidly transferred from the acid to one of the unshared
electron pairs of the alcohol.
In second step the carbon oxygen bond breaks. The leaving group is molecule of water :
Finally, in third step the carbocation transfers a proton to a molecule of water. The result is the formation of a
hydronium ion and an alkene.
Reactivity of ROH : 3° > 2° > 1°

Ex. (a)

(b)

(c)

(c) Reaction involving complete molecule of alcohol :

(i) Dehydration : Removal of H2O by two type
(a) Intermolecularly removal of H2O [form ether]
(b) Intramolecularly removal of H2O [form alkene]
0°C
(C2H5)2 SO4
100°C
C2 H5 OH + H2SO4 C2H5HSO4
(conc.) 140°C
C2H5 O C2H5 (Williomson's synthesis)
170°C
CH2 CH2 (Elimination)

250°C
C2H5 OH +Al2O3 C 2H 5 O C 2H 5
(Alumina) 350°C
CH2 CH 2
Ease of dehydration follow the order : 3° ROH > 2° ROH > 1° ROH > CH3OH

13
 (ii) Catalytic Dehydrogenation : This reaction is useful in distinction of 1°, 2° and 3° alcohols.
Cu
CH3CH2OH  CH3CHO + H2
300°C
(p- alcohol ) (Acetaldehyde)
Cu
CH3 CH CH3 CH3 C CH3 + H2
300°C

OH O
(s- alcohol) (acetone)

CH3 CH3
Cu CH3 C CH2 + H2O [dehydration]
CH3 C OH 300°C
(Iso - butylene)
CH3
(t. alcohol)

(iii) Oxidation : This reaction is useful in distinction of 1°, 2° and 3° alcohols.

H/KMnO4or [O]
R—CH2—OH  
H /K2Cr 2O7
RCHO Room temp. RCOOH

(p-alcohol) (same carbon acid)

Acids (less carbon)

R
[O]
R C R Room temp.
No reaction

OH
high temp.
(t-alcohol) Acids (less carbon)

[O]
CH3CH2 CH CH3 CH3CH2 C CH3 [O] CH3COOH + CH3COOH
high temp.
OH O
Carbonyl group goes with smaller alkyl group

(iv) Reaction with phosphorous pentasulphide :

R—OH + P2S5  R—SH + P2O5
Thio alcohol
(v) Reaction with salts :

CuSO4
CuSO4. 2CH3OH
CaCl2
CH3OH CaCl2. 4CH3OH
MgCl2
MgCl2 . 6CH3OH

14
(vi) Distinction between 1°, 2° and 3° alcohols :
(a) Lucas test : A mixture of HCl(conc.) and anhydrous ZnCl2 is called Lucas reagent.
ZnCl2 + HCl
p-alcohol No turbidity at room temp. [On heating within 30 minutes.]
ZnCl2 + HCl
s-alcohol Turbidity appears within 5 minutes.
ZnCl2 + HCl
t-alcohol Turbidity appears within 1 minute.

(b) Victor - Meyer test : This is colour test for alcohol (pri. sec. & tert.) .
p-alcohol  Red colour
s-alcohol  Blue colour
t-alcohol  No colour

R—CH2—OH [1°] R2CH—OH [2°] R3C—OH [3°]

R—CH2—I R2CH—I R3C—I

RCH2—NO2 R2CH—NO2 R3C—NO2

R—C—NO2 R2C—NO2 No reaction

N OH N

Soluble (Red) Insoluble (Blue) Colourless (White)

(vii) Dichromate test :

H/K2Cr2O7
1° Alcohol orange [Cr+6]
Acid + Cr+3
[green]

H/K2Cr2O7
2° Alcohol orange [Cr+6]
Ketone + Cr+3
[green]

H/K2Cr2O7
3° Alcohol orange [Cr+6]
No oxidation, No green

15
 (viii) Test of alcoholic group :

1
R—OH Na R—ONa + H
2 2
[effervescence of H2]
PCl5 NH3
R—OH R—Cl + POCl3 + HCl NH4Cl
[White fumes]
R—OH Cerric ammonium nitrate Red colour

(ix) Distinction between CH3 – OH and C2H5OH :

CH3 OH CH3 CH2 OH

B.P. 65°C 78°C
I2 + NaOH No ppt Yellow ppt of CHI3
Cu/300°C Smell of formalin [HCHO] No smell
Salicylic acid Smell of oil of wintergreen No smell

OH
CH3OH COOH3 Methyl salicylate
(Oil of wintergreen)

OH OH

COOH
Ph—OH COOPh Phenyl salicylate
Salol (Internal antiseptic)
O C CH3
Aspirin
CH3COCl O (Analgesic)
COOH

Additional reactions
(a) Oxidation by HIO4 [per iodic acid] :

CH2 CH 2 HIO4 CH2 OH + HO CH2  2H O

2 HCHO + HCHO
OH OH OH OH

CH2 CH CH2 HIO4 HO CH 2+HO CH OH + HO CH 2  3H O

2 HCHO+HCOOH+HCHO
OH OH OH OH OH OH
(Glycerol)

16
Condition for oxidation by HIO4 :
At least 2 —OH or 2 >C=O or 1 —OH and 1 >C=O should be at adjacent carbons.

(b) Pinacole - Pinacolone Rearrangement :

CH3 CH3 CH3

CH3 C C CH3 conc. H2SO4 CH3 C C CH3

OH OH O CH3

Pinacole Pinacolone

Mechanism :

17
Aromatic Hydroxy Derivatives
Phenolic compounds :
Compounds in which —OH group is directly attached to sp2 C [Benzene ring]

OH OH OH
CH3 COOH

Phenol o-cresol Salicylic acid

OH
OH OH
OH
OH OH

catechol resorcinol quinol

All phenolic compounds give characteristic colour with neutral FeCl3.\

neutral FeCl3
Ph—OH Violet colour
neutral FeCl3
CH3CH2—OH No colour

PHENOL
Formula C6H5OH

OH

Structure

Phenol is also known as carbolic acid or Benzenol or hydroxy benzene.In phenol —OH group is attached with sp2
hybridised carbon.It was discovered by Runge in the middle oil fraction of coaltar distillation and named it carbolic
acid (carbo = coal; oleum = oil) .It is also present in traces in human urine.

General Methods of preparation :

(i) From benzene sulphonic acid :
When sodium salt of benzene sulphonic acid is fused with NaOH phenol is obtained.
C6H5SO3Na + NaOH  C6H5OH + Na2SO3

(ii) From benzene diazonium chloride :

When benzene diazonium chloride solution is warmed, phenol is obtained with evolution of nitrogen.

NCl
2 OH
(Steam distilled) H2O
 + N2 + HCl

18
(iii) By distilling a phenolic acid with sodalime (decarboxylation):
OH OH
COOH
NaOH + CaO + Na2CO3

Salicylic acid

(iv) From Grignard reagent : (The Grignard reagent on reaction with oxygen and subsequent hydrolysis by acid yields phenol)

Br
[O] H2O
C6H5MgBr C6H5OMgBr C6H5OH + Mg
OH
(v) From benzene :
OH
V2O5
+ [O]
300°C

(vi) From chloro benzene :

Ph — Cl Aq. NaOH No NSR at normal condition
Stable by resonance
R — Cl Aq. NaOH R — OH [NSR]
Ph—Cl Aq. NaOH Ph—ONa
300°C
Order of NSR :

Cl Cl Cl Cl
NO2 NO2 NO2 NO2
< < <

NO2 NO2
max. –I, –M
Aq. NaOH min. ed Aq. NaOH
min. ESR 25°C
300°C max. NSR
OH OH
NO2 NO2

NO2
2, 4, 6–Trinitrophenol (Picric acid)
(vii) Industrial preparation of phenol:
Phenol can be prepared commercially by :
(a) Middle oil fraction of coaltar distillation
(b) Cumene
(c) Raschig process
(d) Dow's process

19
 (a) Middle oil fraction of coaltar:

(b) From cumene (Isopropyl benzene) : Cumene is oxidised with oxygen into cumene hydroperoxide in presence
of a catalyst. This is decomposed by dil. H2SO4 into phenol and acetone.

O OH
CH3 CH3
CH C(CH3)2 OH
O2 H2SO4, H2O + CH3 C CH3
+
130°C H /100°C
O
Cumene Cumene hydroperoxide
o
(c) Raschig process : Chlorobenzene is formed by the interaction of benzene, HCl and air at 300 C in presence of
o
catalyst CuCl2 + FeCl3. It is hydrolysed by superheated steam at 425 C to form phenol and HCl.

1 CaCl2 / FeCl3
C6H6 + HCl + O C6H5Cl + H2O
2 2 300°C

C6H5Cl + H2O 425°C C6H5OH + HCl

(super heated steam)

(d) Dow process : This process involves alkaline hydrolysis of chloro benzene-(large quantities of phenol formed).

OH
Cu  Fe
C6H5Cl + NaOH + NaCl

Physical properties :
(i) Phenol is a colourless, hygroscopic crystalline solid.
(ii) It attains pink colour on exposure to air and light. (slow oxidation)

C6H5OH-------- O O ----------- HOC6H5

Phenoquinone(pink colour)
(iii) It is poisonous in nature but acts as antiseptic and disinfectant.
(iv) Phenol is slightly soluble in water, readily soluble in organic solvents.

20
 (v) Solublity of phenol in water is much lower than alcohols because of larger hydrocarbon part in the molecule.
(vi) Due to intermolecular H-Bonding, phenol has relatively high boiling point than the corresponding
hydrocarbons, aryl halides etc. but intermolecular H-bonding in o–derivatives is used in the preparation of
dyes, drugs, bakelite and it's melting point (MP) is 43° C and boiling point (BP) is 182° C .

Chemical Properties :
(A) Reactions due to –OH group :
Acidic Nature
Phenol is a weak acid. The acidic nature of phenol due to formation of stable phenoxide ion in solution. The
phenoxide ion is stable due to resonance. The negative charge is spread through out the benzene ring which is
stabilising factor in the phenoxide ion. Electron withdrawing groups (–NO2, –Cl) increase the acidity of phenol
while electron releasing groups (–CH3 etc.) decrease the acidity of phenol.
1 
C6 H 5OH    C 6 H 5 O + H 3O
Phenol is stronger acid than alcohols but weaker than the carboxylic acids and even carbonic acid.
The acidic nature of phenol is observed in the following:
(i) Phenol changes blue litmas to red.
(ii) Highly electro positive metals react with phenol.
2C6H5OH + 2Na  2C6H5ONa + H2
(iii) Phenol reacts with strong alkalies to form phenoxides.
1 
C 6 H 5 OH + NaOH  C 6 H 5 O N a +H 2O
(iv) However phenol does not decompose Na2CO3 or NaHCO3 because phenol is weaker than carbonic acid.
C6H5OH + Na2CO3 or NaHCO3  No reaction
Ph — OH + NaHCO3 Ph—ONa + H2CO3
Acid-I Base-I Base-II Acid-II

Acid-I < Acid-II

Reaction in reverse direction .
Base-I < Base-II
(v) Phenol does not react with NaHCO3.
CH3 C OH + NaHCO3 CH3 C ONa + H2CO3 [H2O + CO2]

O O
Acid-I Base-I Base-II Acid-II

Acid-I > Acid-II

Reaction in forward direction .
Base-I > Base-II
(vi) Acetic acid reacts with NaHCO3 and gives effervesence of CO2.

Reaction with PCl5 : Phenol reacts with PCl5 to form chloro benzene. The yield of chlorobenzene is poor and
mainly triphenyl phosphate is formed.
C6H5OH + PCl5  C6H5Cl + POCl3 + HCl
3C6H5OH + POCl3  (C6H5)3PO4 + 3HCl

Reaction with Zn dust: When phenol is distilled with zinc dust benzene is obtained.
C6H5OH + Zn  C6H6 + ZnO

21
 CH2 OH
Ex. Zn ?

Sol. No reaction

CH3
OH
Ex. Zn ?

CH3

Sol.

CH3
CH3
Ex. Zn ?

Sol. No reaction

COOH
OH
Ex. Zn ?

COOH

Sol.

Reaction with NH3( Bucherer reaction): Phenol reacts with NH3 in presence of anhydrous ZnCl2 to form aniline.
Anhydrous ZnCl 2 or (NH 4) 2 SO 3 / NH 3 150°C
C6H5OH + NH3 C6H5NH2 + H2O

Reaction with FeCl3: Phenol gives violet colouration with FeCl3 solution (neutral) due to formation of a complex.
C6H5OH + FeCl3  Voilet colour
This reaction is used to differentiate phenol from alcohols.

Acetylation (Schotten-Baumann reaction) : Phenol reacts with acid chlorides or acid anhydrides in alkali
solution to form phenyl esters.
NaOH C6H5 O— C — CH3
C6H5OH + ClCOCH3  HCl
O
C6H5OH + Cl C C6H5 NaOH C6H5O C — C6H5
 HCl
O O

22
 Ether formation (Alkylation) : Phenol reacts with alkyl halides in alkali solution to form phenyl ethers.
(Williamson's synthesis)
C6H5OH + NaOH  alkali solution
C6H5ONa RX
 C6H5OR
–NaX

Sodium phenoxide
C6H5OH + CH2N2  C6H5OCH3 + N2 
Reaction with P2S5 : 5C6H5OH + P2S5  5C6H5SH + P2O5

(B) Reaction of Benzene Ring : The —OH group is ortho and para directing. It activates the benzene nucleus.
(a) Halogenation : Phenol reacts with bromine in CCl4 to form mixture of o–and p–bromo phenol.

OH OH OH
CHCl 3 or CS2 or CHCl 4 Br
+ Br2 low temp.
+

Br
Phenol reacts with bromine water to form a white ppt. of 2,4,6 tribromo phenol.

OH
OH Br Br
+ 3Br2 H2O + 3HBr
Br
(b) Nitration : Phenol reacts with dil. HNO3 at 0°–10° C to form o- and p- nitro phenols.

OH OH OH
dil. HNO3 NO2
+
0 - 10°C

(40%)
NO2 (10%)
When phenol is treated with nitrating mixture to form 2,4,6- trinitro phenol (picric acid)
OH
OH NO2 NO2
conc. HNO3
conc. H2SO4
[2, 4, 6–Trinitrophenol (Picric acid)]
NO2
(c) Sulphonation: Phenol reacts with fuming H2SO4 to form o–and p–hydydroxy benzene sulphonic acid at
different temperatures.

OH
25°C
SO3H
OH

+ conc. H2SO4
OH
100°C

SO3H

23
 (d) Friedel-Craft's reaction : Phenol when treated with methyl chloride in presence of anhydrous AlCl3
p-cresol is main product.
OH
OH OH
Anhydrous AlCl3
CH3
+ CH3Cl +

CH3
o-cresol p-cresol

OH OH
OH
COCH3
+ CH3COCl
Anhydrous AlCl3 +

COCH3
o – and p – hydroxy acetophenone
(e) Gattermann aldehyde synthesis : When phenol is treated with liquid HCN and HCl gas in presence of anhydrous
AlCl3 yields mainly p- hydroxy benzaldehyde (formylation)
HCl + HCN AlCl3 HN CHCl

OH OH OH
AlCl3 H2O
+ HN CHCl NH3
HCl

CH NH CHO
(f) Riemer-Tiemann reaction : Phenol on refluxing with chloroform and NaOH (aqueous) followed by acid
hydrolysis yields o–hydroxy benzaldehyde. When CCl4 is used salicylic acid is formed.

Mechanism :
CCl2 is neutral attacking electrophile (formed by elimination reaction)
CHCl3 KOH : CCl2

24
 (g) Kolbe 's Schmidt reaction : This involves the reaction of C6H5ONa with CO2 at 1400 C followed by acid
hydrolysis salicylic acid is formed followed.

(h) Hydrogenation: Phenol when hydrogenated in presence of Ni at 150-2000C forms cyclohexanol.

(i) Fries rearrangement reaction :

Anhydrous AlCl3
C6H5OH + CH3COCl C6H5OCOCH3

(j) Duff 's reaction: This method gives only the o-compound which is hindered by the presence of a –I group in
the ring.

(k)Coupling reactions: Phenol couples with benzene diazonium chloride in presence of an alkaline solution to
form a dye (p- hydroxy azobenzene) red only.

25
 Phenol couples with phthalic anhydride in presence of conc. H2SO4 to form a dye (phenolphthalien) used as
an indicator.

(l) Lederer Manasse (Condensation with formaldehyde) : Phenol condenses with HCHO (excess) in presence of
NaOH or weak acid (H+) to form a polymer known as bakelite (aresin).

(m) Leibermann's nitroso reaction : When phenol is reacted with NaNO2 and conc. H2SO4 it gives a deep green
or blue colour which changes to red on dilution with water. When made alkaline with NaOH original green or
blue colour is restrored.
This reaction is used as a test of phenol.
2NaNO2 + H2SO4  2HNO2 + Na2SO4

(n) Reaction with acetone: (Condensation with acetone)

26
 (o) Oxidation:

Tests of Phenol :
(i) Phenol turns blue litmus to red.
(ii) Aqeous solution of phenol gives a violet colour with a drop of ferric chloride.
(iii) Phenol gives Lieber mann 's nitroso test.
NaNO2
Phenol in conc. H2SO4 excess of water
Red colour NaOH excess Blue colour
(iv) Aqeous solution of phenol gives a white ppt. of 2,4,6 tribromophenol with bromine water.
(v) Phenol combines with phthalic anhydride in presence of conc. H2SO4 to form phenolphthalein which gives
pink colour with alkali.
(vi) With ammonia and sodium hypochlorite , phenol gives blue colour.

Differences between phenol and alcohol (C2H5OH) :

(i) Phenol is more acidic than aliphatic alcohol due to resonance in phenoxide ion.
(ii) Phenol gives violet colour with FeCl3 while aliphatic alcohol does not give.
(iii) Phenol gives triphenyl phosphate with PCl5 while aliphatic alcohol gives alkyl chloride.
(iv) Phenol has phenolic odour whereas alcohol has pleasent odour.
(v) Phenol on oxidation gives quinone while alcohol gives aldehyde or ketone and acids.

Uses of Phenol : Phenol is used

(a) As an antiseptic in soaps and lotions. "Dettol" (2,4-Dichloro-3,5-dimethyl phenol)
(b) In manufacture of azodyes, phenolphthalein , picric acid (explosive), cyclohexanol (Solvent for rubber), plastics
(bakelite) etc.
(c) In manufacture of drugs like aspirin salol, phenacetin etc.
(d) As preservative for ink.

ETHER
Like water, ethers have a bent structure, with an sp3 hybrid oxygen atom giving a nearly tetrahedral bond angle.

•• •• •• •• •• ••
O O O
H H
C 110° C H 105°H (CH3)3C 132° C(CH3)3
H H
Water Di-ter.butyl ether
H H
dimethyl ether

27
 Bonding in ethers is readily understood by comparing ethers with water and alcohol. Van der Waals strain involving
alkyl groups causes the bond angle at oxygen to the larger in ethers than in alcohol, and larger in alcohols than in
water. An extreme example is di-tert-butyl ether, where steric hindrance between the tert-butyl groups is responsible
for a dramatic increase in the C – O – C bond angle.
R—O—R (Dialkyl ether), alkoxy alkane. It's General formula is CnH2n + 2O.
CH3—O—CH2CH3 (Methoxy ethane) or ethyl methyl ether or 2–oxa butane
Ether is monoalkyl derivative of R–OH and dialkyl derivative of H2O
R — OH H +R
R—O—R 2H H — O — H
+2R

Classification : They may be classified as :

(a) Simple or symmetrical ether. e.g. R–O–R
(b) Mixed or unsymmetrical ether e.g. R–O–R'
Structure :
The molecule of ether is bent due to lone pair of electron on oxygen
atom- bond electron repulsion. The bond angle is 1100. It is greater
than that of water 1050 due to the repulsion between bulky alkyl groups.
Due to bent structure, it posses dipole moment and hence are polar
molecules.

General Methods of Preparation :

(A) From alkyl halides :
(i) By Williamson's synthesis :
R — X + Na — O — R  R — O — R + NaX [ SN2 Reaction]
CH3 — I + C2H5 O– Na+  CH3 — CH2O — CH3 + NaI

Mechanism : [ SN2 Reaction]

H H H H
Slow Fast
C2H5O C— I C2H5O ------ C ----- I C2H5—O—CH3+ I
H H

3° RX fails to give ether

CH3 CH3

CH3 C ONa + CH3 CH2 Cl  CH3 C O CH2 CH3

CH3 CH3
CH2 CH—Cl + CH3CH2 — ONa  No reaction
[Stable by Resonance]

28
 (ii) Reaction with Dry Ag2O :

2RX + Ag2O  R—O—R + 2AgX

2CH3—CH2—Cl + Ag2O  CH3CH2OCH2CH3 + 2AgCl

(B) From R–OH:

conc. H2SO4
(i) By dehydration : R — OH ?


(ii) Reaction with CH2N2 (diazomethane) :


R — OH + CH2 — N2 
BF  R — O — CH2 — H + N2
3

Physical Properties :
(i) CH3OCH3 , CH3OCH2CH3 are gases and higher are volatile liquids.
(ii) Ether are less polar [=1.18D].
(iii) Ethers are less soluble in H2O.
(iv) Ethers have less BP then corresponding alcohol.

Ex. Ethers are less soluble in H2O . Why ?

Sol. Reason : Due to less polar, it forms weaker H–Bonding with H2O.

Ex. Ethers have less BP then corresponding alcohol. Why ?

Sol. Reason : No H–Bonding in ether molecules.

Chemical properties :
Ethers are less polar so less reactive and do not react with active metals [Na,K], cold dil. acid, oxidising and
reducing agent.
Reason : They do not have any active functional group.
1. Basic nature : Due to presence of .p on oxygen atom ether behave as lewis base
Ethers react with cold conc. acid and form oxonium ion

(diethyl oxonium chloride)

(diethyl oxonium hydrogen sulphate)

29
 Ether form dative bond with Lewis acids like BF3, AlCl3, RMgX etc.
R R
..
O
..
R .. F
O: B F R Mg X [Ether is used as solvent] for Grignard reagent.
R F ..
O
..
R R

2. Halogenation :

3. Formation of peroxides : Ether add up atmospheric oxygen or ozonised oxygen. It is explained by Free radical
mechanism as intermediates is free radical.
O2 (nonpolar)
C2H5—O—C2H5 Long contact CH3CH2 O CHCH3
O O H
(Non polar) sunlight or UV

O2 
CH3CH2 — O — CH2 — Ph Long contact CH3 — CH2 — O — CH — Ph O2 CH3 CH2 O CH Ph
O O H
stable by resonance
Peroxides are unstable and explosives.

Test for peroxides

FeSO4 /KCNS
ether (peroxide)  Red colour
ether (Peroxides) + Fe +2  Fe +3 
CNS
 Fe(CNS) 3
(Red)

hot dil.
4. Reaction with hot dil. H2SO4 : R—O—R H2SO4 2R—OH
hot conc. H2SO4
5. Reaction with hot conc. H2SO4 : R—O—R 2RHSO4
cold dil.
No Reaction

cold conc.
Oxonium salt
H2SO4
CH3 CH2 O CH2 CH3
hot dil.
Ethyl alcohol
hot conc.
Ethyl hydrogen sulphate

30
6. Reaction with PCl5 : ROR + PCl5  heat 2RCl + POCl3
7. Reaction with BCl3 : 3ROR + BCl3  3RCl + (RO)3B
AlCl3
8. Reaction with RCOCl : ROR + RCOCl ZnCl2 heat
RCOOR +RCl

BF3/HgO 500 atm

9. Reaction with CO : ROR + CO RCOOR
150° C

10. Reaction with C2H5Na :  CH3CH2OH + CH2 CH2+C2H6

11. Dehydration :

Red P + HI
12. Reduction : CH3CH2OCH2CH3 heat
2CH3CH3
13. Oxidation :
+
H /K2Cr 2O7 [O] [O]
CH3CH2 — O — CH2CH3 2CH3CH2OH 2CH3CHO 2CH3COOH

14. Combustion : C2H5OC2H5 + 6O2 4CO2 + 5H2O

(explosive mixture)

15. Reaction with HX : Reactivity of HX HI > HBr > HCl

Reaction with cold conc. HX :

Ethers forms oxonium salt with cold and conc. HCl (less reactive)
Cold conc. HI and HBr (more reactive) break C–O bond.

CH3
cold & conc.
Ex. CH3 C O CH2 CH3 ?
HI
CH3

Sol. Mechanism

  
If oxonium ion gives more stable carbocation [ Ph CH 2 , CH2 CH— C H2, (CH3)3 C ] then SN1 reaction occurs.

  
If oxonium ion gives less stable carbocation [P h , CH2 = C H, CH3 C H2] then SN2 reaction occurs, and X
attacks at less hindered carbon.

31
 Cold conc.
Ex. CH3CH2—O—CH2Ph CH3CH2—OH + PhCH2—I, write mechanism of given reaction.
HI
Sol. Mechanism :
I
CH3CH2OH + Ph CH2 PhCH2I + CH3CH2–OH

anhy. HI
Ex. CH3CH2 — O — CH3 ?

Sol.

Oxonium ion gives less stable carbocation

SN2 reaction I attacks at less hinderd carbon.

Ex. CH3 — CH2 — O — Ph aq. HBr ?

Sol. Mechanism :

If excess of HI is used then two moles of alkyl hallides are formed.

CH3CH2 — O — CH2Ph HI CH3CH2OH + PhCH2I HI CH 3CH 2 – I + PhCH 2 – I

Reaction with hot and conc. HX :

CH3CH2 — O — CH3 hot & conc. HI CH3CH2 — I + CH3 — I

hot & conc. HBr

Ex. C2H5 — O — C2H5 ?+?

Sol. C2H5 — Br + C2H5 — Br

Uses of ether :
(i) General anaesthetics agent.
(ii) Refrigerant a mixture of ether and dry ice gives temperature as low 110°C.
(iii) Solvent for oil, fats, resins, Grignard reagent.
(iv) For providing inert & moist free medium to organic reaction example : Wurtz reactions.
(v) In perfumery.
(vi) Di-isopropyl ether Petrol as an antiknock comp.
(vii) Mixture of alcohol and ether is used as a substitute of petrol. Trade name "Natalite"
(viii) Halothane (CF3CHClBr) used as an anaesthetic because it produces unconsciousness without affecting lung and heat.

32
SOME IMPORTANT REACTIONS OF EPOXIDES
O O
Ex. C=C + R–C–OOH C—C + R–C–OH

O
Peroxy acid Epoxide

Ex.

O O

Ex. + CH3–C–OOH O + CH3–C–OH

R2C = CR2 

x2
Ex. H 2o

H H
OH
NaOH
O
Ex.
OH
Br H
trans-2-bromocyclohexanol 1, 2-epoxycyclohexane
(i) diethylether
Ex. RMgX + H2C––CH2 +
RCH2CH2OH (primary alcohol)
(ii) H3O
O

(i) diethylether
Ex. CH2MgCl + H2C––CH2 + CH2CH2CH2OH
(ii) H3O
O
Benzyl magnesium Ethylene 3-phenyl-1-propanol
chloride oxide

H
H
OH
HBr
O
OH
Ex. H H
1,2-Epoxycyclohexane trans -2-bromo cyclohexanol

H3C CH3 OCH3

CH 3OH
Ex. C––– C H 2SO 4 CH3––CH––C––CH3
H O CH3 HO CH3
2,2,3-trimethyl oxirane 3-methoxy-3-methyl-2-butanol

33
1. Preparation and reactions of glycol :

(ii) aq. NaHCO3

CH2OCOCH3

HIO4

–CH2–OH

2. General Reactions of Glycerol :

34