ABC 2 (Theory Exercise)

ABC-1, 2, 3 & 4
(A) PHENOL
Preparation of phenol (5-Methods)
1. Cumene hydroperoxide method CH3 CH3 CH3
CH CH3–C–O–O–H OH
This is an industrial process to convert cumene O
O2/h H3O+
into phenol and acetone in the presence of + CH3–C–CH3
acetone
oxygen from air followed by hydrolysis. Cumene
hydroperoxide
2. Dow's process.
Cl (1) NaOH OH
350ºC
In this process chlorobenzene is heated at 350°C High pressure
+NaCl+ H2O
(2) HCl
(under high pressure) with sodium hydroxide
Chlorobenzene Phenol
which yields phenol.
3. Fusion of benzene sulphonic acid with
concentrated NaOH SO3H OH
(1) NaOH/high temp.
high pressure


This is commercial process for synthesizing (2) H
phenol. Benzene sulphonic acid is melted (fused) Benzene Phenol

Sulphonic acid
with sodium hydroxide at (300°C–320°C) followed
by hydrolysis which yields phenol.
4. Decarboxylation of salicylic acid OH OH OH
COONa COOH
or   
Soda lime
Distillation of salicyclic acid with soda-lime 
(NaOH + CaO) produces phenol.

5. Hydrolysis of benzene diazonium salt + –
NH2 NN Cl
Benzene diazonium salt is prepared by reacting  

NaNO2 , HCl
H2O, 5ºC
aromatic primary amine with NaNO2, HCl at low Aromatic Aryl diazonium salt
Primary amine
temperature.Then this aqueous solution is heated
+ –
to get phenol. NN Cl OH
Boiling H2O

Phenol
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ABC1TO4 - 18
ABC-1, 2, 3 & 4
Chemical reactions of phenol [5-Reactions]

1 (a) Reaction with Br2/H2O
OH OH
When bromine is added to Br Br
Br
solution of phenol in presence of 
2

 + HBr
EtOH/ H2O
ethanol or H2O, it forms white
precipitate of 2,4,6-tribromo- Br
White ppt.
phenol.
(b) Reaction with Br2/CS2 OH OH
OH
In presence of non-polar solvent Br
Br2, CS2
(like CS2) or acids like CH3COOH or CH3COOH
+
at low temperature, only < 5ºC
monobromo product is obtained. Br
2. Reimer Tiemann formylation OH OH OH
Phenol when heated with (1) CHCl , NaOH,  CHO
chloroform and NaOH followed by 
3
+
(2) H2O
H2O forms salicyladehyde.
Major CHO
3. Reimer Tiemann carboxylation OH OH OH
Phenol when heated with CCl4 and CCl4 , NaOH,  COOH


 +
sodium hydroxide followed by H
hydrolysis forms salicylic acid. COOH Major
Note: Salicyclic acid can be used O
in formation of aspirin. OH O–C–CH3
(Aspirin is used as painkiller) COOH COOH
AcCl or Ac O,

2

pyridine
Aspirin
4. Kolbe's Schmidt reaction OH O– OH OH
Phenol when reacted with  COO– COOH
( i) OH (iii) HCl
hydroxide ion in presence of CO2   +
( ii) CO2
forms a complex which on
acidification forms salicyclic acid. COOH Major
5. Bakelite formation OH OH OH
Bakelite is made by condensation CH2O CH2OH


reaction between phenol and NaOH
formaldehyde.
CH2OH
Polymerises
OH OH
OH OH
Bakelite
ABC1TO4 - 19
ABC-1, 2, 3 & 4
Lab test for phenol
1. Litmus test : Phenol turns blue litmus red. Phenols behave as weak acid because of presence of
polar O–H group, they ionise in aqueous solution to give H+ ions.
OH O
+ H2O  H3O+
Phenol Phenoxide
ion
2. Neutral FeCl3 : Phenols give a violet-coloured water soluble complex with neutral ferric chloride.
6Ph–OH + FeCl3  Fe(OPh)3– +
6 + 3H + 3HCl
Violet complex
NH2
(B) ANILINE
Preparation of aniline [3-Methods]
3. Hofmann bromamide
1. Reduction by Metals 2. Reduction by H2
degradation reaction
NH2 In this reaction an unsubstituted
amides (only 1°) treated with
Metal / Acid
NaOH/KOH and bromine to give a
primary amine that has one carbon
lesser than starting amide.
NO2 NH2 NO2 NH2
O
Sn / HCl Ni / H2 or Pd / H2 R–C–NH2 + Br2 + 4NaOH

+ 6H
NH2 R–NH2 + Na2CO3 + 2NaBr + 2H2O

R can be : Alkyl or phenyl
Fe/ HCl This method is used to prepar 1°
+ 6H aliphatic or aromatic amines.
Special :
NO2 NH2
 
(NH ) S
4 2
(various other sulphides can be used.)
Selective reduction
NO2 NO2
Chemical reactions of aniline :

1. Preparation of diazonium salt:
Aniline reacts with NaNO2/H+ to form diazonium salt.
+ –
NH2 N2 Cl
NaNO2/HCl
(0-5ºC)
Benzene
diazonium chloride
ABC1TO4 - 20
ABC-1, 2, 3 & 4
Note :
1. Primary aliphatic amines react with nitrous acid to form aliphatic diazonium salt which being unstable,
liberate nitrogen gas.
2. Primary aromatic amines form arene diazonium salts which are stable for a short time in solution at low
temperatures (273-278 K).Due to its instability, the diazonium salt is not generally stored and is used
immediately after its preparation.
2. Chemical reactions of diazonium salt

Diazonium salt opens the way to prepare many other compounds, see following chart.
ABC1TO4 - 21
ABC-1, 2, 3 & 4
OH
Boiling H2O
+
NN HSO4– Ph-OH
N=N OH
Orange-dye
dil. NaOH
Benzene diazonium salt

N=N NH2
Ph-NH2
Yellow-dye
dil. HCl
1. Complete the following reactions.

 
NNCl NNCl
CuCl/HCl CuBr/HBr
i. or ii.
Cu2Cl2/HCl
CH3 CH3
 
NNCl NNCl
Cu/HCl Cu/HBr
iii. iv.
CH3 CH3
 
NNCl NNCl
H3PO2 C2H5OH
v. vi.
CH3 CH3
 
NNCl NNCl
HBF4 H2O, 
vii. –HCl viii.
CH3 CH3
2. Conversion.
Ph–NO2 Ph–Cl
H2/Pd Sandmayer reaction
NaNO2/HCl
Ph–NH2
ABC1TO4 - 22
ABC-1, 2, 3 & 4
Lab test of aniline :
1. Carbylamine reaction
Primary amines (aliphatic as well as aromatic) react with chloroform (CHCl 3) on heating in the presence
of ethanolic solution of KOH to form isocyanides (also called carbylamines) which are foul smelling
substances. Secondary and tertiary amines do not undergo this reaction, therefore this reaction is used
as a test for primary amines (aliphatic as well as aromatic).
R–NH2 + CHCl3 + 3KOH Heat R–NC + 3KCl + 3H2O
Heat
Ex. CH3–NH2 + CHCl3 + 3KOH CH3–NC + 3KCl + 3H2O
NH2 NC
Ex. + CHCl3 + 3KOH

Heat
+ 3KCl + 3H2O
2. Azo dye test

Azo compounds are usually intensely colored because of the azo linkage (–N=N–). Azo compounds,
because of their intense color’s and because they can be synthesized from relatively inexpensive
compounds, are used extensively as dyes.
Synthesis of orange-red dye from 2-naphthol [-naphthol] and aniline.
OH N=N
NaNO2/H2SO4 OH
+
NH2 N2
(0–5°C) NaOH pH = 8-10
Orange-red Dye
3. Bromine water test (Br2 + H2O):

Aniline reacts with bromine water at room temperature to give a white precipitate of
2,4,6-tribromoaniline. Aniline also gives test with Br2 + CS2
NH2 NH2
Br Br
Br2 / H2O
+ 3Br2 + 3HBr
Aniline Br
2,4,6- Tribromoaniline
ABC1TO4 - 23
ABC-1, 2, 3 & 4
ONLY ONE OPTION CORRECT TYPE

1. The process of conversion of cumene in the presence of oxygen and light followed by hydrolysis lead to
the formation of _______ .
(A) Phenol (B) Aniline (C) Anisole (D) Benzene
2. Identify the product of following reaction.
CH3–CH–CH3
(i) O / h

2

(ii) H3O
CH3
OH
(A) (B) (C) (D) None of these
CH3 CH3
3. Identify the product of the following reaction.
Cl
(i ) NaOH
  
(ii) HCl
350 º C NaCl
High pressure H2O
Cl OH OH OH
Cl
(A) (B) (C) (D)
Cl Cl Cl
SO3H
(i) NaOH/ 
4.   
 ?
(ii) H
CH3
SO3H SO3H OH CH3
OH
(A) (B) (C) (D)
OH OH
CH3 CH3 CH3
5. Give the product for following reaction.
OH
COONa
  
Soda lime
C2H5
OH OH
COOH
C2H5 C2H5 C2H5
ABC1TO4 - 24
ABC-1, 2, 3 & 4
6. Identify the X and Y in the following reaction.
NH2

  X 
NaNO2 , HCl
Y
H2O, 5ºC H2O
+ –
OH N2Cl OH
(A) X = Y= (B) X = Y=
+ –
N2Cl OH N2Cl
(C) X = Y= (D) X = Y=
7. What will be the product of following reaction?

OH
Cl
2

EtOH / H2O
OH OH OH OH
Cl Cl Cl
(A) (B) (C) (D)
Cl
Cl Cl Cl
8. Find the product for the following reaction.

OH
Br

2

Cs2 , 5ºC
CH3
OH OH Br
Br
Br CH3
9. Give the major product for the following reaction.

OH
  
CHCl3 / NaOH

Me
OH OH OH OH
CHO Me COOH
(A) (B) (C) (D)
CHO Me Me Me
10. The reagent used for Reimer Tiemann carboxylation in order to form salicylic acid is _______ .
(A) CHCl3 / NaOH / H+ (B) CCl4 / NaOH / H+ (C) OH– / CO2 / HCl (D) None of these
ABC1TO4 - 25
ABC-1, 2, 3 & 4
11. Aspirin can be formed from following reaction using which reagent?
O
OH O–C–CH3
COOH COOH

O O
+
(A) (CH3–C–)2O / H (B) (C2H5–C–)2O / H+ (C) CHCl3 / NaOH (D) None of these
12. Give product for following reaction.

OH
 

CHCl3
KOH
CHO COOH
CHO OH OH
13. The reactant used in the reaction is :

OH
COOH
–
Reactant   
OH / CO2
HCl
OH
OH OH
COOH
(A) (B) (C) (D)
NO2
14. Sn/HCl R is :
+ 6H
R,
CH3
NO2 NH2 NH2 NH2
(A) (B) (C) (D)

CH3 CH3
Cl
NH2
Fe/HCl
15. R + 6H , R is :
NO2 NO2 NO2

NO2
(A) (B) (C) (D)
ABC1TO4 - 26
ABC-1, 2, 3 & 4
NH2
Ni/H2
16. R , R is :
CH3
NO2 NO2 NO2 NO2
(A) (B) (C) (D)
CH3
Br2/NaOH
17. R C2H5–NH2, R is :
CH3
(A) C2H5–CH2–C–NH2 (B) C2H5–CH–C–NH2
O O
CH3
(C) C2H5–C–NH2 (D) C2H5–CC–NH2
O CH3 O
+ –
N2Cl
H3C CH3
NaNO2/HCl R, is-
18. R (0–5°C)
CH3
NO2 NH2
H3 C CH3 H3 C CH3
(A) (B)
CH3 CH3
CH3 H3C CH3
(C) (D)
CH3 CH3
19. Which of them produces diazonium cation at 0°C ?
NH2 NH–CH3
CH3
(A) (B) (C) CH3–CH2–NH2 (D) CH3–C–NH2
CH3
+
–
N2Cl
P
20. , P is :
C2H5 C2H5
(A) Cu2Cl2/HCl (B) Cu/HCl (C) C2H5OH (D) HBF4
ABC1TO4 - 27
ABC-1, 2, 3 & 4
NC
CHCl3 + 3KOH/
21. R R is -
C2H5

–
N2Cl NO2
(A) (B)
C2H5 C2H5
NH2 CN
(C) (D)
C2H5 C2H5
NH2 OH
22. NaNO2/HCl
(X) NaOH (pH=8-10) (Y)
(0-5°C)
SO3H
Y is :
+ –
(A) HO3S O N2Cl (B) HO N=N SO3Na
+ – + –
(C) HO N2Cl (D) HO SO2 N2Cl
1. (A) 2. (A) 3. (C) 4. (C) 5. (B)
6. (C) 7. (D) 8. (B) 9. (B) 10. (B)
11. (A) 12. (B) 13. (C) 14. (C) 15. (C)
16. (B) 17. (C) 18. (B) 19. (A) 20. (C)
21. (C) 22. (B)
ABC1TO4 - 28

ABC 2 (Theory Exercise)

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ABC 2 (Theory Exercise)

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ABC-1, 2, 3 & 4

phenol. Benzene sulphonic acid is melted (fused) Benzene Phenol

(NaOH + CaO) produces phenol.

Benzene diazonium salt is prepared by reacting  

Chemical reactions of phenol [5-Reactions]

+ H2O  H3O+

Sn / HCl Ni / H2 or Pd / H2 R–C–NH2 + Br2 + 4NaOH

NH2 R–NH2 + Na2CO3 + 2NaBr + 2H2O

Chemical reactions of aniline :

2. Chemical reactions of diazonium salt

Benzene diazonium salt

1. Complete the following reactions.

H2/Pd Sandmayer reaction

Ex. + CHCl3 + 3KOH

2. Azo dye test

3. Bromine water test (Br2 + H2O):

ONLY ONE OPTION CORRECT TYPE

(A) (B) (C) (D) None of these

C2H5 C2H5 C2H5

7. What will be the product of following reaction?

8. Find the product for the following reaction.

9. Give the major product for the following reaction.

12. Give product for following reaction.

13. The reactant used in the reaction is :

(A) (B) (C) (D)

NO2 NO2 NO2

(A) (B) (C) (D)

(A) (B) (C) (D)

1. (A) 2. (A) 3. (C) 4. (C) 5. (B)

6. (C) 7. (D) 8. (B) 9. (B) 10. (B)

21. (C) 22. (B)

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