PHENOL

Total No.of questions in Phenol are -

In chapter Examples .................................................................. 07

Solved Examples ........................................ ............................ 21

Total No. of questions .............................................................. 28

 2.3 From Salicylic acid -
1. INTRODUCTION
Salicylic acid, on heating with sodalime, initially
(a) It is also called as carbolic acid. forms sodium phenoxide which gives phenol on
(b) The compounds in which —OH group is di- acidic hydrolysis.
rectly attached with benzene ring are called
as 'Phenol'
(c) It is discovered by the scientist 'Runge' 2NaOHCaO
  
(d) The scientist 'Hofmann', prepared it first from
'coaltar'.
(e) Aromatic hydroxy compounds in which a (salicylic acid)
single —OH group is attached with benzene
OH
ring are called phenols. HCl
eg.    
NaCl
OH
2.4 From Grignard reagent -
2 Al O
3
C6H5 - Mg - Br + O2  
 C6H5 - O -O - MgBr
C H5MgBr hydrolysis
phenol (monohydroxy) 6   C6H5OMgBr    2C6H5OH
(f) If two or three OH groups are attached at
2.5 Industrial Methods -
benzene ring then they are called dihydroxy
or trihydroxy phenols respectively. 2.5.1 From middle oil fraction of coaltar -
eg. Phenol is obtained from the middle oil fraction of
coaltar after removing other homologous of
OH
phenol, Cresol and naphthalene.
OH
Middle oil
o, m - or - p - dihydroxy benzene On cooling
(dihydroxy)
Solid naphthalene Mother liquor
OH
OH (i) Dil. NaOH
(ii) Passing CO2
(iii) Washing with water
OH and fractional distillation
pyrogallol
(trihydroxy) 183ºC 191-218ºC Xylenol mixture
Phenol Mixture of
OH OH
cresols
2.5.2 From Cumene -
OH
anhy. AlCl3
C6H6 + CH3 - CH = CH2   
OH
fluoroglucinol
(Obtained from petroleum)
(trihydroxy)
C6H5 - CH - (CH3)2
1. METHODS OF PREPARATION cumene
metal catalyst
2.1 From Benzene sulphonic acid -
  
O 2 / 130 º
300º C
C6H5 - SO3H + NaOH   C6H5-ONa
C6H5C(CH3)2 - O - OH
sodium phenoxide
cumene hydroperoxide
HCl

 C6H5OH
dil. H2SO 4
2.2 From Benzene diazonium chloride - C6H5C(CH3)2 - O - OH   
On heating with water, it gives phenol. Cumene hydroperoxide
 C6H5OH + CH3COCH3
C6H5N2Cl + HOH  C6H5OH + N2 + HCl
Phenol Acetone
2.5.3 From Rasching process - Ex.2 Identify 'Z' in the reaction given below -

1 CuFe
C6H6 + HCl + O2   C6H5Cl + H2O
2 200 C
1. HNO2 ( 280K ) NaOH
   X 

SiO 2 2. H2O ;Boil
C6H5Cl + H2O  C6H5OH + HCl
450º
CH I
2.5.4 From Dow's process - Y 
3
 Z -

Cu Fe,300 º NH2
C6H5Cl + NaOH   
 C6H5OH + NaCl H3C CH3
200 atm.

C6H5Cl + Na2CO3 + H2O C6H5OH + NaHCO3

(A) (B)
+ NaCl
CH3
Examples
based on methods of preparation
Ex.1 In chlorobenzene, the — Cl group -
(A) Activates the benzene ring more, via
resonance effect than deactivating it via (C) (D)
inductive effect.
(B) Deactivates the benzene ring more, via
(Ans. C)
inductive effect than activating it via reso-
HNO
nance effect. Sol. C 6H 5 NH 2 
2
 C 6 H 5OH NaOH

H 2O , 
(C) Activates the benzene ring via resonance
C6H5ONa CH3I
effect and deactivates it via inductive ef-  C6H5OCH3
fect. Both these effect are evenly
matched.
Ex.3 forms
(D) It is a net deactivating group with director
characteristics. on reaction with -
(Ans. B) (A) CH3 – CHO (B)

(C) CH3 – CH2 – CHO (D)

Sol. (Ans. B)

Sol. +

+ H2O

(Resonance activating o-and p-position)

Also electron withdrawing nature or + H2O
— I.E. decreases this activation.
+
3. PHYSICAL PROPERTIES 5. CHEMICAL PROPERTIES

(i) It is colourless crystalline solid with specific Chemical properties of phenol are classifi ed in
smell. the following four categories.
(ii) It is partially soluble in water. 5.1 Reactions of —H atom of —OH group.
5.2 Reactions of —OH group of phenol.
(iii) Due to oxidation, it becomes pink in open air.
5.3 Reactions of Benzene ring.
(iv) It is poisonous.
5.4 Other Reactions.
(v) It is soluble in organic solvents.
5.1 Reactions of —H atom of —OH group
(vi) Melting. point is 40ºC & boiling point is 182ºC
5.1.1Reaction with Na Metal -
4. RESONATING STRUCTURES OF PHENOL 2C6H5 – OH + 2Na  2C6H5ONa + H2 
(a) Resonance in phenol molecule - NOTE :
Phenol reacts with strong bases like NaOH but
does not reacts with weak bases like Na2CO 3.
The reaction is used for difference between
carboxylic acid and phenol.
5.1.2 Reaction with Alkyl halide -
 

C6H5 — O– H + HO —Na  C6H5 —O Na
H2O

       
RX
C6H5 — O Na  C6H5 — O — R
 
(I) (II) (III)  
C6H5 — O Na+Cl—CH3
NaCl C6H5 — O — CH3

anisole
(methyl phenyl ether)
 C6H5—O—Na+Cl—C2H5 
 C6H5—O— C2H5
phenetole
(ethyl phenyl ether)
5.1.3 Esterification -
(IV) (V)
CH COCl or
It is evident from the above structures that (i) C6H5OH    C6H5OCOCH3
3

( CH CO ) O
– OH group of phenol is o & p-directing as 3 2

there are electron richer places so (phenyl acetate)

electrophile attack at these places. C6H5COCl
   C6H5OCOC6H5 + HCl
(ii) C6H5OH
(b) Resonance in phenate ion -
(phenyl benzoate)
NOTE : The above reaction is called ' Schotten -
Baumann' reaction.
5.1.4 Etherification -
(i) C6H5OH + CH2N2  C6H5OCH3 + N2
(anisole)
etc. NaOH
(ii) C6H5OH + 

[equivalent configurations more stable] Acetone or Dimethyl sulphoxide
RX
C6H5ONa  C6H5 OR + NaX.
Phenate ion is resonance stabilised that is
NaOH
why phenol shows acidic character. The next (iii) C6H5 — OH   C6H5ONa
point to remember is —OH group in phenol ( CH ) SO
3 2 4
    C6H5OCH3 + Na (CH3) SO 4
is attached with enolic carbon. This is also
a reason for showing its acidic character.
5.1.5 Reaction with Benzene sulphonyl chloride- 5.3.2 Nitration -
C H SO Cl
C6H5OH 6 5 2
 C6H5SO2OC6H5
(phenyl benzene sulphonate)
(i) dil. HNO 3 +
5.1.6 Reaction with Benzoic acid or benzoyl  
chloride -

C H COOH
C6H5OH 6 
5

 C6H5COOC6H5
or C6H5 COCl

(phenyl benzoate) conc . HNO

3
(ii)    
 
conc . H2SO 4
5.2 Reactions — OH group of phenol
5.2.1 Reaction with Zn dust (Deoxygenation)-

(picric acid)
C6H5 — O + Zn   C6H6
|
300 º C NOTE : Picric acid is yellowish crystalline solid. It is
H used in dynamite.
5.2.2 Reaction with Ammonia- 5.3.3 Sulphonation -
anhy . ZnCl
C6H5OH + NH3   
2
 C6H5NH2 + H2O
300 º C

5.2.3 Reaction with PCl5 -

conc.H2SO4
C6H5OH + PCl5  C6H5Cl + POCl3 + HCl C6H5OH   +

5.2.4 Reaction with POCl 3 -

(p-phenol sulphonic acid) (o-bromo phenol)
3C6H5OH + POCl3  (C6H5 )3PO 4 + 3HCl
(triphenyl phosphate)
5.3.4 Friedel-Craft's reaction –
5.2.5 Oxidation -

2 2CrO Cl
OH  
 O= =O 3 AlCl
(i) Alkylation – C6H5OH + CH3 - Cl 
 
(p-benzoquinone)
5.3 Reactions of benzene ring -
5.3.1 Bromination
+

(i) C6H5OH + 3Br2  (o-cresol) (p-cresol)

(ii) Acetylation –
3AlCl
C6H5OH + CH3COCl 
 
2,4,6, - tribromophenol (white precipitate)
CS2 or CCl4
(ii) C6H5OH + Br2   
0

(o - hydroxy acetopenone) (p-hydroxy acetophenone)

(o-bromo phenol) (p-bromo phenol)
5.3.5 Fries rearrangement reaction –
When phenyl ester is heated in nitrobenzene
solution, in the presence of anhy. AlCl3 then
rearrangement takes place in which acyl group H O
3 
 + NH4Cl
is transferred at o - & p-positions of phenolic
group. Up to 60ºC, para product is obtained
mainly and above 160ºC ortho products are
obtained as major product.
(p-hydroxy benzaldehyde )
NOTE : The reacting species in the above reaction is
aldimine.

+ CH3COCl  
 HCl
5.3.7 Carboxylation -
(i) Kolbe or Kolbe Schmidt reaction -

nitrobenze ne CO 2 / 125 º
    +
   
anhy .AlCl3 /  High pressure

(p-acetyl (o-acetyl phenol)

phenol)
5.3.6 Formylation - H2O

 NaOH
(i) Reimer - Tiemann reaction -
The basic solution of phenol, on reaction with
chloroform forms salicylaldehyde as major IMPORTANT NOTE :
product. (i) If it reacts with CO 2 at 25ºC, unstable
C6H5OCOONa is formed.
(ii) If C6H5ONa reacts with CO2 at 250 - 300ºC

+ CHCl 3 + 3KOH  the product is HO COOH

(ii) Reimer - Tiemann reaction -
(salicylaldehyde)
C 6 H 5 OH + CCl 4 + 4KOH 
+ 3KCl + 3H2O
(ii) Gattermann reaction -
W hen phenol reacts with (HCl + HCN) + 4KCl + 3H2O
mixture in the presence of ZnCl2 catalyst and
the obtained intermediate aldimine is (salicylic acid)
hydrolysed then p-hydroxy benzaldehyde is
formed as major product. 5.3.8 Mercuration -
2 ZnCl
HCl + HCN 
  Cl — CH = NH

+ (CH3COO)2Hg 

OH
+Cl—CH= NH 
Hg – O – C – CH3
|| + CH3COOH
O
5.3.9 Hydrogenation - 5.4.3 Reaction with Benzene diazonium chloride-
Pd or Ni
C6H5OH + 3H2 
 C6H111 — OH
(cyclohexanol) –
5.3.10 Nitrosoation -
+ HCl
2NaNO
C6H5OH   + (p-hydroxy azo benzene)
H2SO 4
5.4.4 Lederer - Manasse reaction -
(o – product) (p – product)
Phenol gives condensation reactions with aliphatic
(main product)
and aromatic aldehydes at o – & p –positions. At
5.4 Other Reactions - low temperature, formaldehyde condenses with
5.4.1 Reaction with Acetone -
phenol in the presence of dil. acid or base and
p-hydroxy benzyl alcohol is formed as major
product.

dil. acid
 
or dil. alkali

HO CH2OH +

conc .HCl
 
H2 O

Examples
based on chemical reaction
(bis-phenol A)
5.4.2 Reaction with Phthalic anhydride - Ex. 4 The correct order of reactivity towards
electrophilic substitution is -
(A) Phenol > Benzene > Chlorobenzene >
OH OH
Benzoic acid
(B) Benzoic acid > Chlorobenzene > Benzene
> Phenol
(C) Phenol > Chlorobenzene > Benzene >
H O H Benzoic acid
C conc .H SO
2 4 (D) Benzoic acid > Phenol > Benzene >
    
Chlorobenzene (Ans.A)
O
C Sol. Presence of o-, p- directing groups in
benzene nucleus activates ring for SE
O reaction. Presence of m-directing group
deactivates ring for SE reactions. Also
(pthalic anhydride) halogens are deactivating gp. due to — IE.
HO inspite of o-and p-directing nature.
OH
Ex.5 Which among the following is the strongest
o-, p-directing group in benzene is -
C (A) –OH (B) –Cl (C) –OCH3 (D) –CH3
O (Ans.A)
C Sol. –OH gp. posses the maximum tendency to
throw electron pair towards benzene nucleus.
O
(phenolphthalein)
Ex.6 Identify 'Z' in the reaction - Ex.7 Phenol on oxidation gives chloranil. The
oxidant used is -
(A) K2S2O 8 (B) KMnO 4
CHCl NaOH NaOH (C) KClO3 + HCl (D) None (Ans.C)
3
 X   Z
conc . Sol. K 2 S 2 O 8 gives quinol ; KMnO 4 giv es
mesotartaric acid

(A)

KClO
3
  
HCl
(B) +

(chloranil)

(C)

(D)

(Ans.B)

Sol. X is which undergoes

Cannizzaro's reaction to give Z.

 SOLVED EXAMPLE
Ex.1 The compound represented by the molecular Sol. They exhibit intramolecular H-Bonding.
formula C7H8O are - Therefore, they are unable to form H-bonding
(A) Only alcohol with water.
(B) Only ether
(C) Only phenolic compound Ex.5 Rate of substitution reaction in phenol is -
(D) All the three types of compounds (A) Slower than the rate of benzene
(Ans.D) (B) Faster than the rate of benzene
Sol. Benzyl alcohol, anisole and o —, m—, p— (C) Equal to the rate of benzene
cresols can be written by the molecular (D) None (Ans.B)
formula C7H8O.
Sol. – OH group is activating group towards
Ex.2 Indenif y A, B, and C in the following electrophilic substitution reactions.
reactions–
Ex.6 Which is least soluble in water -
(A) Phenol (B) Ethanol
(C) Benzoic acid (D) Benzene
A
(a)   (Ans.D)

Sol. Benzene can not form H-bonding thus, it is
least soluble.

(b)
Zn
 B Ex..7 Anisole is obtained by the reaction of phenol
 with -
(A) NaOH + CHCl3 (B) NaOH + CH3l
C 2H5l (C) NaOH + C2H5l (D) NaOH + CO2
(c) C   
(Ans.B)
(A) Sodalime, benzene, potassium phenoxide Sol. Anisole is obtained by the reaction of phenol
(B) Zn, benzene, sodium ethoxide with NaOH and CH3I. It is phenyl methyl ether
(C) Zn, cyclohexanone, sodium ethoxide
(D) None of the above (Ans.A)
Sol. Sodalime, benzene, potassium phenoxide are
the A, B and C compounds respectively. + NaOH ——   + H2 O

Ex.3 Water insoluble aromatic compound dissolves

in sodium hydroxide but remain insoluble in sodium phenate
sodium bicarbonate. Hence the expected
compound should be - [where  = C6H5]
(A) —COOH (B) OH + I-CH3
(C) CO—CH3 (D) NH2
(Ans.B)
sodium phenate methyliodide
Sol. Phenol is a weak acid. It does not
decompose sodium bicarbonate.
Ex.4 Salicylaldehyde and o-nitrophenol are less —— + NaI
soluble in water because -
(A) Their molecular weights are high anisole (methyl phenyl ether
(B) They exhibit intra molecular H-bonding or methoxy benzene)
(C) They are aromatic compounds
(D) –CHO and – NO2 groups are not polar
(Ans.B)
Ex.8 The reaction of phenol with benzoyl chloride
in the presence of alkali gives - Zn
Ex.11 

ZnO
(A) Benzyl phenate
(B) Benzyl benzoate The above process is not a....... .
(C) Phenyl benzoate (A) Deoxygenation
(D) Benzoyl phenate (Ans.C) (B) Reduction
(C) O.N. of carbon attached to —OH group
Sol. The reaction of phenol with benzoyl chloride changes from + 1 to – 1.
in the presence of alkali gives phenyl (D) Dehydroxylation
benzoate, an ester. (Ans.D)
C6H5 COCl + HOC6H5 — C6H5COOC6H5 Sol. Here —OH is replaced by —H. Therefore, it
benzoyl chloride phenol phenyl benzoate is not a dehydroxylation process.

(A)
Ex.12 Excess of phenol on reaction with PCl5 yields
CO  HCl
Ex.9 C6H5OH  C6H6    (B) finally -
anhy . AlCl3
In the above reaction sequence A and B are- (A) C6H5Cl
(A) Red P + HI and benzoic acid (B) Triphenyl phosphate
(B) Red P + HI and benzaldehyde (C) C6H6
(C) Zn powder and benzaldehyde (D) Triphenyl phosphene (Ans.B)
(D) Zn powder and benzoic acid Sol. Excess of phenol on reaction with PCl5 yields
(Ans.C) finally triphenyl phosphate. The reaction takes
Sol. (Gattermann Kosch reaction). place as follows
C6H5OH on reacting with Zn gives benzene.
Benzene reacts with CO + HCl in the
presence of anhy. AlCl 3 to f orm + PCl5 — + POCl3 + HCl
benzaldehyde.
phenol chlorobenzene
Ex.10 Identify (A), (B) and (C) in the following
reaction sequence - 3C6H5OH + POCl3 —(C6H5)3 PO4 + 3HCl
phenol triphenyl phosphate
(A)
 C6H6 (B)
C6H5OH   C6H5NO 2

(C) Ex.13 What amount of bromine will be required to
 Azoxybenzene
 conv ert 2 gm of phenol into 2,4,6-
(A) (A) = NaOH + CaO, (B) = conc, H2SO 4 tribromophenol -
+ conc. HNO3, 60 - 70ºC, (C) = glucose (A) 4.00 (B) 6.00
+ NaOH (C) 10.22 (D) 20.44
(B) (A) = Zn powder, (B) = conc. H2SO 4 + (Ans.C)
conc. HNO3, 100ºC, (C) = NH4Cl + Zn
(C) (A) = Zn, (B) = conc. H2SO 4 + conc.
HNO3, 60 - 70ºC, (C) = glucose + NaOH
(D) (A) = NaOH + CaO, (B) = conc, HNO3 + Sol. + 3Br2 
conc. H2SO4, Reflux 24 hrs. (C) = CH3OH
+ Na
(Ans.C) phenol 480 g 2,4,6 tribromophenol
Zn powder 94 g
Sol. C6H5OH    C6H6
94 g of phenol requires 480 g Br2
conc . HNO 3 ,60 70 º
     
 C6H5NO 2 2g of phenol requires
conc .H2SO 4

glu cos e  NaOH

480
    Azoxybenzene = x 2 = 10.22 g bromine
94
Ex.14 Which of the following reagen (s) cannot be Sol. C6H5OH + 3H2  C6H11OH
used to distinguish between phenol and cylohexanol
benzyl alcohol -
(A) NaOH (B) NaHCO3 Ex.19 The compound which gives violet colouration
(C) Br2/CCl 4 (D) FeCl3 with FeCl3 soln. is :
(Ans.C)
Sol. Only phenol reacts with NaOH, NaHCO3 and
FeCl3 none of the two compounds react with (A) (B)
Br2/CCl4.

Ex.15 Phenol condenses with formaldehyde to form-

(A) Bakelite (B) Asbestos
(C) Polyacrylaldehyde (D) Polyester (C) (D)
(Ans.A)
Sol. When phenol and formaldehyde react in (Ans.D)
presence of dilute alkali, p-hydroxybenzyl Phenol gives violet colouration with FeCl3
alcohol is obtained as a major product on solution. It is due to the complex formation
further heating for some time, a cross-linked of [Fe(OC6H5)3]–3, as follows:
polymer, called phenol- formaldehyde resin
or bakelite is formed.
6 + FeCl3 —— [Fe(OC6H5)6] –3

Ex.16 + CHCl3 + NaOH complex

phenol + 3H+ +3 HCl

 
Ex.20 Which of the following tests is not given by
carbolic acid -
The above reaction is called -
(A) It turns blue litmus red
(A) Gattermann Kosch aldehyde synthesis
(B) Gattermann aldehyde synthesis (B) It liberates H2 on reaction with Na
(C) Reimer Tiemann reaction (C) It forms ester with other acids
(D) Ledrer Mannase reaction (D) It liberates CO2 from NaHCO3 soln.
(Ans.C) (Ans.D)
Sol. The above reaction is Reimer Tiemann
reaction. Sol Carbolic acid is also known as phenol. It is
acidic in nature but does not contain a carboxyl
group, hence it does not exhibit the test of
carboxylic acid to liberate CO2 form NaHCO3
Chloroform
Ex.17 
 solution.However phenol turns blue litmus red.
Caustic soda

The above reaction is -

(A) Electrophilic substitution
(B) Nucleophilic substitution
(C) Free radical addition phenol (carbolic acid)
(D) Electrophilic addition (Ans.A)
Ex.21 A characteristic group-test for phenolic –OH -
Sol. Attacking species in the above reaction is (A) Libermann's nitroso reaction
dichlorocarbene which is an electrophile. (B) Coupling reaction with diazonium salt
Ex.18 Hydrogenation of phenol gives – (C) Aq. FeCl3 solution
(A) p-Benzoquinone (B) Cyclohexanol (D) All (Ans.D)
(C) Salicylic acid (D) None of these
Sol. All tests are characteristic of phenol.
(Ans.B)