SRI CHAITANYA NARAYANA IIT ACADEMY

ORGANIC CHEMISTRY

IIT JEE 2019

HYDROCARBON

ALCOHOL,PHENOL

ETHER

T te

PREPARED BY: ASHISH SIR & NEHA MADAM

 SYNOPSIS

ALCOHOL PHENOL

EXERCISE-BASIC

1. Identify the product ?

O
OH

PCC

(A) (B) O
(i) LiAlH4
+
(ii) H3O

1. DIBAL-H, –78°C

3. H3O
+

O O
COOH CH2OH

(C)
O (i) LiAlH4
+
(ii) H3O
(D)
(i) LiAlH4
+
BH3
mate
(ii) H3O

OH OH

(E) Ac2O (F)

Ac2O

Me

OH

TsCl 1. SOCl2

(G) (H) OH 2. Mg, ether

Me 3. CO2

4. H3O
+

OH 1. PBr3 1. NaBH4
(I) (J) 2. H3O
+

2. Mg, ether
O 3. SOCl2

3. CO2
+

4. H3O

COOH

1. LiAlH4
1. PBr3 2
SN + E2

(K) + (L) 2. CH3ONa

2. H3O

3. PBr3
OH

OH 1. H2SO4, Heat 1. H2SO4, Heat

(M) (N) OH
2. Hg(OAc)2, CH3OH 2. Hg(OAc)2, CH3OH

3. NaBH4 3. NaBH4

OH CrO3 1. PBr3, Py
(O) (P)

H2SO4, Heat
2. Mg, ether
OH

O O

3.

4. H3O
+

OH OH

OH

(Q) 1. TsCl, Py
(R) HCHO, H
+

2. CH3CH2ONa

CH2OH + OH +
HCHO, H HCHO, H

(S) (T) OH
CH2OH

OH


EXERCISE - A

One or More answer correct :

1. Give the major product of given reaction -

OH
H

SOCl2

Pyridine
[M]

Product [M] is :

H Cl

Cl H

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

2. Product
a ios the major product of given reaction -

OH PBr3
[N]

Product [N] is :

Br

Br
Br

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

Me

3.
1. BH3, THF
– [L]

2. H2O2, OH (major)

Product (L) is :

Me Me Me OH HO H

OH OH H OH

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

+ +
Enantiomer Enantiomer

OH

1. PBr3 , Et2O
[P]

4. 2. NaI , Me2CO
3. NaN 3 , HCONMe 2

Product [P] will be -

N3 N3
Me Me

(A) (B) H N3 (C) H (D)

Et
Et N3

OH
1. PBr3 , Et2O

5. [Q]
2. NaI , Me2CO

3. NaN3 , HCONMe2
CH3

Product [Q] will be -

N3 N3 H
N3

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

N3

CH3 CH3 CH3 CH3

HO
Ph
Ph

Me Ph [T]
Me OH

6. + H2SO4 [S]
OH Ph

Me O

(Given, migratory order Aryl > Alkyl > H)

Find, the correct statement(s) -

(A) [T] can be [Ag(NH3)2]OH (B) [T] can be Fehling solution

(C) [T] can be NaOBr (D) [T] can be I2, NaOH

Br
Ph
Me

Ph Ph OH
H [X]
7. + AgNO3 [U]

OH Ph

Me O

(Given, migratory order Aryl > Alkyl > H)

Find, the correct statement(s) -

(A) [X] can be [Ag(NH3)2]OH (B) [X] can be HCHO, NaOH

(C) [X] can be NaOBr (D) [X] can be I2, NaOH

OH
1. NaOH

8. Br
H3C 2.

What is the product of the reaction shown above for para-cresol ?

O Na

(A) (B)
H 3C H 3C

O O Br

(C) (D)

H 3C H3C

9. Which of the following is the major product of the following reaction ?

Br

NaOEt, EtSH
?

(A) I because EtO– is a strong nucleophile

(B) I because EtO– is a strong base

(C)aII because EtSH is a much stronger nucleophile than EtO–

(D)aII because EtS– forms and is the stronger nucleophile

O2 H2SO4

10. Cumene [K] Acetone + [L]

hv H2O O

O , H

[M] O

Identify the correct statement(s)

(A) [M] is phenolphthalein indicator

(B) [L] gives CO2 effervescence with NaOH

(C) [K] formation involve carbocation intermediate

(D) [L] gives Red colour with neutral FeCl3

11. Which of the following pathways is the “BEST” for the synthesis of 2-butanol from ethane ?

(CH 3CH2) 2CuLi Cl2 KOH

(A) Light Heat

Cl (CH 3CH 2)2CuLi Cl2 KOH

2
(B) Light Light Heat

Cl
(C) Light
2 Mg CH3COCH3 H 3O
ether ether

Cl2 Mg CH3CHO H 3O
+

(D) Light ether ether

12. The product obtained in the following transformation is :

OH OH

H2SO4

(A) (B)

O O

(C) (D)

13. The major product formed in the following reaction sequence is :

H 3C
OH

1. PBr3
?

2. CH3CO2Na

CH3CO2H

H 3C OCOCH3

H 3C

(A) O (B)

H 3C H3C Br
H 3C

(C) + (D)

1. BH3, THF
[M] PCC
– [O]

2. H2O2, OH

14. CH3–CH=CH2
1. Hg(OAc)2, H2O PCC

[N] [P]
2. NaBH4

Relationship between products (O) and (P) is :

(A) Position isomers (B) Chain isomers

(C) Stereoisomers (D) Functional isomers

15. An optically active alcohol [A] reacts with SOCl2 to form product [B] as shown -

OH

H C2H5
SOCl2
2-chlorobutane
Dioxane

CH3

[A]

In this regard, which one of the following statements is true ?

(A) A and B are both R-isomers (B) A and B are both S-isomers

(C) A is R-isomer and B is S-isomer (D) A is S-isomer and B is R-isomer

16. The major product formed in the following reaction is :

Br2

CH3OH
O

Br Br OMe OMe

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

O Br O O Br O
OMe Br

17. Identify the final product ?

Ph CH3

Ph CH3
H2SO4
[M]

OH OH

CH3 Ph CH3 Ph CH 3
CH3

(A) Ph (B) Ph (C) (D) Ph–CH=CH2

CH3 CH3
O
Ph CH 3

18. On reaction with NaNO2 and HCl, which of the following amino alcohol(s) will yield compound [P] ?

CHO

[P]

NH2

(A) (B) NH 2

OH OH

NH2

(C) NH2 (D)

OH OH

19. When 10 mL of each liquid of liquid pairs listed below are mixed and then allowed to stand, which pair is most

likely to separate into two layers -

(A) Carbon tetra chloride & hexane (B) Ethanol and methanol

(C) Carbon tetrachloride and methanol (D) Hexane and pentane

Me

NH2 HNO2

Ph [N]
OH
20. Me

Ph

Product [N] is :

O Me Ph

Me

(A) Ph (B) Ph

Me Ph Me

Ph

(C) (D)

Ph Me Me Ph

Me

OH AgNO3 (aq)
Ph Br [O]

21. Me

Ph

Product [O] will be :

O Me Ph

Me Me
(A) Ph (B) Ph

Me
Ph O

O O

Ph Me
(C) Ph (D) Me

Me Ph
Me Ph

Me H

Ph AgNO3
[P]
22. Ph

OH

Br

(given, migratory apptituder order is Aryl > Akyl > H)

Identify product [P]

Me Ph Ph
(A) O (B) Me

Ph

Ph

Ph Ph
O

Ph

(C) Ph (D) Me CHO

Me

NH2 Me Me

H HNO2 [R] OH
Me
[Q]
Me Ph

23. Ph O

OH

(given, migratory order is Aryl > Alkyl > H)

Find the correct statement(s)

(A) [R] can be [Ag(NH3)2]OH (B) [R] can be Fehling solution

(C) [R] can be HCHO, NaOH (D) [R] can be I2, NaOH

24. The reaction that produces (CH3)3C.O.CH3 in highest yield is -

H2SO4

(A) NaOCH3 + (CH3)3C.Cl  (B) (CH3)3C.OH + CH3I

H2SO4

(C) (CH3)3CH + CH3OH (D) (CH3)3COK + CH3I 

25. The product obtained in the following conversion is :

O ?

O OH

(A) (B)

(C) (D)

26. The appropriate reagents required for carrying out the following transformation are -

CO2H

OH ?

(A) (i) PCC, CH2Cl2 ; (ii) Ph3P=CHCO2Et ; (iii) aq. NaOH, Heat then acidity

(B) (i) CrO3, H2SO4, aq. acetone ; (ii) Ac2O, NaOAc

(C) (i) MnO2 ; (ii) Ac2O / AcONa

(D) (i) PCC, CH2Cl2 ; (ii) CH3CH=O, NaOH ; (iii) CrO3, H2SO4, aq. acetone

27. Reaction of 4-aminophenol with one equivalent of acetylchloride in prsence of pyridine yields -

OH

NH2
[X]

O Me OH OH O OH

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

Me

NH2 NH Me NH2 NH2 O

28. In the following reactions, the major products E and F, respectively are -

OH

(i) NaOH, CO2

[E]
(CH3CO)2O
[F]

125ºC, 4-7 atm

+

(ii) H3O

OH OCOCH3 OH OCOCH3

COOH CO2CH3

(A) (B) and

and

CO2H CO2H

OH OCOCH3 OH OCOCH3
COOH CO2H

(C) and (D) and

CO2H CO2CH3

29. Which of the following statement(s) is/are true about the reaction given below ?

O O

NaOMe, MeOH
MeO *

Br

(A) In involves carbocation intermediate

(B) Rearrangement is due to SN1 mechanism

(C) It proceed via a concerted SN2 mechanism

(D) It involves neighbouring group participation

30. Which one of the following statements regarding compounds K, L, M is true ?

OH OH CH3

[K] [L] [M]

(A) [L] has the highest boiling point and the highest water solubility

(B) [K] is highest boiling and has the highest water solubility

(C) [L] is highest boiling , [M] has the lowest water solubility

(D) [K] is highest boiling , [L] has the highest water solubility

EXERCISE-B

CH2OH

1. H2SO4 /
[K] (major)

Identify [K] :-

CH2 CH3 CH3 CH2

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

OH

2. How would you carry out the following synthesis?

OH OCH2CH3

(A) Add PCC then CH3CH2OH (B) Add CrO3/H2O then SOCl2 then CH3 CH2OH

(C) Add LiAlH4 then SOCl2 then CH3CH2OH (D) Add PCC then SOCl2 then CH3CH2OH

OH

(1) TsCl / Pyridine

3. [K]

(2) CH3CO2Na

(3) H3O

OH
(A) (B)

OH

HO H H OH

(C) (D)

(1) aq.NaOH O

4. [L]
(2) NaI/Acetone

(3) Na

Br OH
(A) (B)

Br

(C) Cl (D) Cl

Br

OH
[R] = ?

5. Br

(A) (i) Thionyl chloride / Et3N (ii) NaOEt / EtOH / Heat (iii) NBS, Heat

(B) (i) PBr3 ` (ii) KOH / EtOH / Heat (iii) HBr

(C) (i) Br2, UV light (ii) H2O, Heat (iii) PBr3

(D) (i) HBr (ii) KOBut / t-BuOH/ (iii) HBr

OH
?

6. CH2
Me

(A) KO/H / EtOH / Heat

i
(B) (i) SOCl2 / Et3N ; (ii) KOH / EtOH / Heat

(C) t-BuOK / t-BuOH / Heat

(D) (i) SOCl 2 / Et3N ; (ii) t- Buok / t-BuOH / 

 Which of the following statement is true regarding to the synthesis of diethylether ?

H
–

OH
1. Na
O ONa+
O
2. EtBr

(II) H
(I)

(A) Method II is preferred because H2O is a better leaving group than OH .

(B) Method II is preferred because ethoxide is a better nucleophile than ethanol.

(C) Method I is preferred because ethanol is a very good nucleophile.

(D) Method I is preferred because both and nucleophile and electrophile are primary.

8. Compound [P] on treatment with CH2N2 (diazomethane) produces compound [Q]. Compound [Q] on reaction

with HI produces two alkyl iodides [R] and [S] . Alkyl iodided [S] with Higher number of carbon atoms on

reaction with KCN followed by hydrolysis gives 3-methyl-butanoic acid. The compound [P] is :-

(A) 2-butanol (B) 1-butanol

(C) 2-methyl-2-propanol (D) 2-methyl-1- propanol.

9. Identify the product [X] and [Y] in the following sequence :-

H2 (i) O sO

Ph Ph [X] (ii) Pb(OAc)

4
[Y]
Pd-BaSO 4 4

Ph , PhCHO
(A) (B) Ph Ph , PhCHO

Ph

OH OH

Ph Ph

(C) Ph , PhCHO (D) Ph , PhCHO

OH OH

10. Identify the major product in the following reaction -

Ph
H

O
Me

Ph OH

(A) Me OH (B)

Me

Ph

OH
(C) Ph (D) Me OH

Me

Ph

1. KMnO4, KOH

11. O

Ph
2. OH , TSOH , Heat

3. PCC, CH2 Cl2

Ph Ph Ph Ph
Ph Ph Ph Ph

(A) O O (B) O O (C) O O (D) O OH

COOH CHO

O O

CH2
12. 1. HBr

2. KOH, EtOH, Heat

[M]

3. O3 then H2O2

4. NaBH4

Identify [M] –

OH
O OH

(A) (B)

OH

OH OH O OH

(C) (D)

13. Find the product -

Br

1. Mg / THF then CO2

2. H3O
+

3. EtOH, H2SO4, Heat

+

4. DIBAL-H, THF then H3O

EtO O O

OEt

OH H OEt
(A) (B) (C) (D)

1. FeCl3

O 2. LiAlH4
14. [N]

Cl
3. H2SO4

4. NBS, UV light
5. NaOCH3, Heat

OCH3 Br

Br

(A) (B)

OCH3

(C) (D)

EXERCISE-C

* Answer all 10 Question -

* The following reaction scheme shows a possible synthesis of structure [Z]. From the list of reagents provided

in the table below, select the “BEST REAGENT COMBINATION” (meaining in some steps, you might need

more than one reagent) to carry out each of the reactions required at each numbered step.

O O

CH3OH
1 2 3

H H OH OH

Cl

O O O
O

O O
8 7 6

NH2 NO2 NO2

m

O 10 HO

N
N
H

[Z]

TABLE

(A) NaNO2/H2SO4 (I) SOCl2

(B) PCC/CH2Cl2 (J) AlCl3 (anhyd.)

(C) NaBH4 (K) CH3CH2Li then H3O

(D) CH3MgBr, then HBr Heat (L) Sn/HCl then NaOH

(E) K2Cr2O7/aq. H2SO4 (M) NaOH/H2O/Heat then H3O

(F) (CH3CO)2O/pyridine (N) CH3CO3H

(G) HNO3/H2SO4 (P) CH3I

(H) aq. HCl (Q) CH3MgBr followed by H2O

2. A compound of molecular formula C7H6i O is insoluble in water and dilute sodium bi carbonate but dissolve

aqueous sodium hydroxide and gives a characteristic colior with aqueous FeCl3. On treatment with bromine

water it readily gives a precipitate of C7H5Br3O

. Find the structure of [A] -

OMe OH OH

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

Me

Me

EXERCISE - D

MATCHING LIST

1. Ether is highly stable except under acidic condition. Different possible mechanism for hydrolysis of Ether are

shown below. Match each mechanism from List - I with an apropriate ether from List - II.

H H2O
(P) R–O–R R R – OH

– ROH –H

H H2O
(Q) R–O–R R – OH2 R – OH

– ROH –H

R – OH
i
H

R-O-R

+ H2O
OH2 OH
H

(R) C OR C C C OH
OR OR – ROH

H C O

(S) H

R O R No Hydrolysis

List - I List - II

(P) Mechanism P (1) O CH3

(Q) Mechanism Q (2) O CH2

(R) Mechanism R (3) O OCH3

(S) Mechanism S (4) O

Codes :

(P) (Q) (R) (S)

(A) 3 4 2 1

(B) 4 3 1 2

(C) 1 2 3 4

(D) 2 3 4 1


(Pair of Compound ) (Test of Distinguishing)

2. (Pair of Compound) (Test of Distinguished)

groats EsorsooEETards

LIST - I LIST - II

OH
OH

(1) , (P) NaOI

OH OCH3

(2) , (Q) Na - Metal

OH

(3) OH, (R) Conc. HCl + anhyd. ZnCl2

(4) OH (S) KMnO4/OH–

OH,

Codes :

(P) (Q) (R) (S)

(A) 1 2 3i 4 4s 3

(B) 4 2 3 1

(C) 4 2 1 3

(D) 3 1 2 4

3. List - I List - II

O O

(1) Me Me Me O + CHBr3 (P) NaOH + Br2

O OH

(2) Me Me Me Me (Q) KOBr

(3) R NH2 R – NH2 (R) LiAlH4 then H3O

(4) R NH2 R – CH2NH2 (S) DIBAL – H3 – 78°C

g

Codes :

(1) (2) (3) (4)

(A) P R Q R

(B) Q P S R

(C) P Q R R

(D) Q R S A

EXERCISE-E

INTEGER

1. If glycerol is allowed to react with acetaldehyde in presence of conc. H2SO4. What are the number of final

products (i.e. Acetal)

2. If glycerol is allowed to react with formaldehyde in presence of conc. H2SO4. What are the number of final

products (i.e., Acetal)

3. Among the following, total number of compounds soluble in aq. NaOH is -

OCH2CH3 OH OH CH2 OH

NO2
CH2OH

, , ,

NO2 NO2

OH COOH

COOH

, ,

Me Me

4. How many cyclic ester will give chiral dihydroxy compounds on reaction with LiAlH4 followed by H3O?

O
OH O O O O

O O O O O

,
e s
, , ,
o

O O O O

O O O O O

,
a ,
n
, ,
ro b

O O O

O O O

b , ,
r

5. How many out of the given structure(s) will give neutral FeCl3 test ?

OH OH OH

OCH3 CHO

O O ,
, ,

OCH3 OH
OH

OH
, , , ,

O O
O

CH3 OH

6. How many compound (of moleucular formula C8H10O) upon treatment with alkaline solution of iodine gives a

yellow precipitate. The filtrate on acidification gives a white solid (C7H6O2).

OH OH O O
G
O
Beg

OH
CH3 CH3 CH3

, ,

OH

O OCH3 OCH CHO

Be 3

, , ,
H3C

CH3 CH3

1. LiAlH4 . Et2O

7. [M]

Cyclic 2. H3O

(ester) 3. Red P/HI

i

(Lactone)
C6H10O2

Find the value of [M], (Including stereoisomerism)

Pyridine

8. [M] + (CH3CO)2O [N]

Molecular formula of [M] increases by C8H8O4. Find the number of Hydroxyl group (– OH) present in (M) is

(are) -

Pyridine
9. [K] + Ac2O [L]

Molecular Molecular mass = (m × 210)

mass (m)

Find the number of (OH) group in [K].

10. How many ether(s) (given below) on acidic hydrolysis give two alcohols, both of them give yellow pppt. with

alkaline solution of Iodine?

Me Me Me

O O

Me O Me
Me Me Me Me

Me H2C

Me
O O O

Me Me

CH3 Me Me

Me

OMe Me

Me

OMe

EXERCISE - F

Paragraph : (Q. 1 - Q.5)

PTHALEIN DYE TEST

Phenol condense with pthallic anhydride in presence of conc. H2SO4, phenol condense to give phenophthalein

which give pink color with NaOH, this is called Pthalein dye test.

1. Observe the given reaction -

OH
O

O + 2
Conc. H2SO4
Phenophthalein

Identify the phenophthalein -

go

(A) O (B)
HO

OH OH

OH

OH OH

OH
O

(C) O (D)

O O
OH

2. Find the correct statement(s) regarding phenophthalein -

(A) In aqueous solution, where the pH value is below 8.3, it colorless.

(B) At pH = 10, its color is purple

(C) In a very strongly basic medium (pH  14), it is again colorless.

(D) Coloured form is one of the resonating structure of anion

3. Which of the following resonating structure of anion gives color -

O
–
O
–
O O

(A) C (B) C

OH

COO
–
COO

O O
O O

onC C

(C) (D)

COO
COO

4. In a very strongly basic medium pH  14, the indicator is again colorless, it is due to -

O O O O

(A) C (B) C

OH

COO COO

O O O O

C
(C) C (D)

COO

COO

5. Which of the following will not give pthalein dye test -

OH OH

CH3

(A) (B)

CH3

(O - Cresol) (m - cresol)

OH OH

(C) (D)

CH3

(P - cresol)

EXERCISE-G [PHENOL OR CARBOLIC ACID]

NOTE : Phenol is converted by conc. HNO3 into picric acide but nitration is accompanied by considerable oxidation.

bacith
Picric acid prepared by treatment of 2,4-phenoldisulphonic d with O3. HN03

OH OH OH

NO2

1. Conc. HNO3 2. Dilute HNO3

[L] 20°C

(ortho major)

OH OH

NaNO2 HNO3

3. [M]
+

H2SO4

7° – 8°C

NO2

Para
(Major)

OH OH

Conc. H2SO4 Zn

4. 15° – 20°C
[N] (Ortho) 5. [P]

Conc. H2SO4
[O] (Para)

100°C

OH

NaOH , CO2

+ [Q] + [R]
6.

Can be Separate by
steam distillation

OH

(1) CHCl3, (aq. NaOH) HCl

7. , [R] [S] + [T]

70°C Steam

Volatile

(Major)

OH OH

CH3 aq. NaOH CH3

aq. NaHCO3

8. [U] 9. [V]

OH

O
aq. NaOH

10. + MeO S OMe [W]

(Methyl Sulphate)

OH OH Br

CH3 CH3

aq. NaOH aq. NaOH

11. + PhCH2Br [X] 12. + [Y]

(Benzyl bromide)

OH Cl OH

NO2

aq. NaOH H2SO4

13. + [Z] 14. + CH3COOH [D]

NO2 CH3

OH OH C Cl

Pyridine
15. + (CH3CO)2O [E] 16. + [F]

NO2

CH3
p - nitro

benzoyl

chloride

OH

aq. NaOH

17. + Ph S Cl [G]

CH3 (Benzen

Sulphonyl

Chloride)

(Hint : Similar to TsCl)

OH

18. + Ferric Chloride Solution [Observation]

CH3

OH OH

Ni
+ Bromine Water [I]
19. + H2 [H] 20.

200°C, 20 atm

OH OH

CS2 mild

21. + Br2 [J] 22. + p - nitro benzene [K]

diazonium Basic

chloride

OH OH

CH3

23. + 2Br2 (aq.) [L] 24. + 3Br2 (aq.) [M]

SO3H

OH RCOCl

[N]
NaOH

25. 26. OH + C Cl [P]

RSO2Cl

[O] O

CH3COONa

27. O2N OH + (CH3CO)2O [Q]

Br

OH
Pyridine

28. + CH3 SO2Cl [R]

– 

OH aq. NaOH OH anhyd. C2H5ONa

29. + C2H5I [S] 30. + C2H5I [T]

Heat

aq. NaOH
31. CH3 OH + Br.CH2 NO2 [U]

OH

(1) aq. NaOH

32. + CH2 – COOH [V]

(2) HCl

Cl

Me Me

O2 / hv
[W]
H3O
[X] + [Y]

33.
I2,

NaOH
PhN2.Cl

pH = 8

Orange Yellow
dye ppt.

OH
O CH3 25°C

Para

(1) (CH3CO)2O
AlCl3 Para (at Low Temp)

34. 35.
(2) AlCl3, 25°C

160°
Ortho

EXERCISE-H

OH

Conc. HBr HCl, ZnCl2

1. CH3 CH CH3 [A] 2. CH3CH2CH2CH2.OH [B]

(OR) Heat

NaBr, H2SO4

CH3
Conc. HBr [C] PBr3

3. CH3 C CH3 4. CH3 – CH2 CH – CH2OH [D]

Room temp.

OH CH3

PBr3 P + I2

5. CH – CH3 (E) 6. CH3CH2OH (F)

OH

OH
H2SO4 Al2O3

7. [G] + [H] 8. [I]

OH  200°C

CH3

H2SO4 Na
9. C CH3 [J] 10. CH3CH2OH [K] + H2

Heat Metal

OH

CH3

CH3
K
Al [M] + H2

11. CH3 C OH 12. CH3 C OH

Metal Metal

CH3

13. CH3CH2OH + CH3 S Cl [N]

O
K2Cr2O7 K2Cr2O7

[R – CH]
or

KMnO4
14. R – CH2OH R – COOH

KMnO4

K2Cr2O7

15. R – CH – OH [O]
(or)

CrO3

K2Cr2O7

CH3CH2OH CH3CH2 – CHO + H2

16. K2Cr2O7
KMnO4 CH3CH2COOH

CH3CH2OH CH3CH2 – COOH

CH3 CH3

HCl HCl

17. CH3 C OH [P] 18. CH3 C CH2OH [Q]

CH3 CH3


19. ROH + CH CNa [R]

20. RCH2OH + KMnO4 R – COO– K+ + MnO2 + KOH

(1°) (Brown)

RCH2OH + Cr2O7 n
R – CHO + Cr +++–

(Green)

K2Cr2O7

R – COOH

Mg

CH3 [Q] [P]

21. CH2 CH CH CH3

Cl 2/

CH3
OH

CH3

(R)
[S] HO.CH2 – CH – CH3

22. (a) R CH CH R' + HIO4 RCHO + R'CHO (+ HIO3)

OH OH

(b) R C C R' + HIO4 RCOOH + R'COOH

O O

(c) R CH C R' + HIO4 RCHO + R'COOH

OH O

(d) R CH CH CH R' + 2HIO4 RCHO + HCOOH + R'CHO

OH OH OH

(e) R C CH R' + HIO4 R2CO + R'CHO

OH OH

(f) R CH CH2 CH R' + HIO4 no reaction

OH OH

23. A + one mole HIO4  CH3COCH3 + HCHO

B + one mole HIO4  OHC (– CH2)4 – CHO

C + one mole HIO4  HOOC (CH2)4 CHO

D + 3HIO4  2HCOOH + 2HCHO

E + 3HIO4  2HCOOH + HCHO + CO2

F + 5HIO4  5HCOOH + HCHO

OH Conc. H SO OH Conc.
2 4 howdil.

25.
[U] 26.
[V]
Heat KMnO4

OH CrO3 OH conc.

27.
[W] 28.
[X]
H2SO4 aq. HBr

OH P + I2 OH Na

29.
[Y] 30.
[Z]

OH OH
CH3COOH CH3MgBr

31.
[A] 32.
[B]
H

OH
OH 1. Conc.H2SO4/

1. Conc. HBr
[C] [D]

33. 34.
2. Mg 2. C6H6, HF

OH 3. Conc. HNO3/H2SO4

3.

1. MeLi/then H3O
[E]

35. O 2. PDC/CH2Cl2

Me 3. m – CPBA

EXERCISE-I (ETHER)

 

H2O + CH2 – CH2 H [A] C2H5OH + CH2 – CH2 H [B]

1. 2.

O O

 
OH + CH2 CH2 H [C] 4. HBr + CH2 H

3. CH2 [D]

O O


–+ H –+

C2H5ONa + CH2 CH2 [E]

5. 6. ONa + CH2 CH2 [F]

NH3 + CH2 CH2 [G] [H]

7. 8. CH3MgBr + CH2 CH2

O O

CH3 CH3


18 H CH3ONa

9. CH3 C CH2 + H2O [I] 10. CH3 C CH2 + CH3OH [J]

O O

11. Write a balanced equation for each of the following. (If no reaction occurs, indicate “no reaction”.)

(a) Potassium tert - butoxide + ethyl iodide  [K]

(b) tert - butyl iodide + potassium ethoxide  [L]

(c) ethyl alcohol + H2SO4 (140°)  [M]

(d) n - butyl ether + boiling aqueous NaOH  [M]

(e) methyl ethyl ether + excess HI (hot)  [O]

(f) methyl ether + Na  [P]

(g) ethyl ether + cold conc. H2SO4  [Q]

(h) ethyl ether + hot conc. H2SO4  [R]

(i) C6H5OC2H5 + hot conc. HBr  [S]

(j) C6H5OC2H5 + HNO3, H2SO4  [T]

(k) p – CH3C6H4OCH3 + KMnO4 + KOH + heat  [U]

(l) C6H5OCH2C6H5 + Br2, Fe  [W]

EXERCISE - J (DIAZO COUPLING REACTION)

Hint :

OH OH

 pH = 8 – 10
(A) + PhN2.Cl

(mild basic

medium)

N = N – Ph
(Orange Colored)

N = N – Ph

OH OH
 pH = 8 – 10

(B) + PhN2.Cl
(mild basic)

(Dark Red Coloured)

1. Which statement(s) is (are) correct -

(A ) A niline on reaction with NaNO 2/HCl at 0°C followed by coupling with  - naphthol gives a dark blue

coloured dye)

(B) The color of the compound formed in the reaction of aniline with NaNO2/HCl at 0°C followed by coupling

with  - naphthol is due to extended conjugation

(C) It is an electrophillic substitution reaction

(D) All are correct

2. Among the compounds given, the one that would form a brilliant colored dye on treatment with NaNO2 in

dilute HCl followed by addition to an alkaline solution of  - naphthol is -

N(CH3)2 NHCH3 NH2 CH2NH2

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

CH3

3. For the identification of  - napthol using dye test, it is necessary to use -

(A) dichloromethane of  - naphthol (B) Acidic solution of  - naphthol

(C) Neutral solution of  - naphthol (D) alkaline solution of  - naphthol

4. The major product of the following reaction is -

OH

(i) NaNO2, HCl, 0°C

(ii) aq. NaOH

NH2

OH O Na+

(A) (B)

Cl N2Cl

fifty

(C) (D)

IN


5. The major product formed in the reaction given below is

O2N OMe

OH

Conc. H2SO4

HO

Me

O2N OMe MeO NO2

O O

(A) (B)

Me Me

NO2

Me NO2 O
O

(C) (D)

OMe
Me

MeO

6. The reagents and reaction conditions to carry out the transformations below are :

CH3O OCH3 (i) O (ii) OH (iii) O Na

(A) (i) dilute acid (ii) NaBH 4 followed by dilute acid (iii) dilute NaOH

(B) (i) dilute acid (ii) NaBH4 followed by dilute acid (iii) Na

(C) (i) dilute acid (ii) K2Cr2O7/H+ (iii) dilute NaOH

(D) (i) dilute base (ii) NaBH4 followed by dilute acid (iii) Na

OH

O O

7.
H3O+

Product

OH

Product can give positive test with

(A) 2, 4 DNP, FeCl3, Cerric ammonium nitrate and NaHCO3

(B) 2, 4 DNP, FeCl3, NaOH and NaHCO3

(C) FeCl3, Cerric ammonium nitrate and NaHCO3

(D) FeCl3, Cerric ammonium nitrate, NaOH and NaHCO3

Me 1. PBr3/Et3N

2. KOH, EtOH, Heat

8. ?

3. CH3CO3H

OH 4. aq. KOH

Me Me

OH OH
(A) (B)

OH OH

Me Me

OH

(C) (D) OH
OH

? OH

9. HO

(A) i. KMnO4, KOH, 0°C ii. HIO4 iii. excess MCPBA iv. aq. HCl, heat

(B) i. O3 ii. dimethyl sulfide iii. NaBH4

(C) i. O3 ii. dimethyl sulfide iii. LiAlH4 then H+ workup, iv. H2SO4 , heat

(D) O3 ii. H2O2 iii. LiAlH4 then H+ workup

OH
?

10. Ph

Ph
Ph

(A) (i) NBS, CH2Cl2 (ii) Mg (iii) excess benzyl bromide (iv) H3O+ workup

(B) (i) NBS, CH2Cl2 (ii) Mg ; (iii) methyl benzoate ; (iv) H3O workup

(C) (i) KMnO4/H+ / heat (ii) MeOH / H, heat (iii) excess PhMgBr, H3O+ workup

(D) (i) PDC, CH2Cl2 (ii) excess PhMgBr (iii) H3O+ workup

11. Which of the following reaction (s) will yield phenol?

Cl NH2

(i) Fusion with NaOH at 300 atm (i) NaNO2/HCl

(A) (B)

(ii) H2O/H (ii) H2O (warming)

Cl

(C)
(i) Oleum
(D)
(i) NaOH (aq.) 298K/1atm

(ii) NaOH (Heating) (ii) HCl

(iii) H

OH OH

pH = 10 – 11

12. + Ph – N2.Cl

N=N

Characteristics of above reaction is -

(A) C – N coupling reactions; carbanion is intermediate

(B) Product is red color dye

(C) It is an electrophillic substitution reaction

(D) C – N coupling reaction, carbocation is intermediate

13. Major product of the given reaction is -

OH

(i) Conc. H2SO4, 60°C

C6H5NO4
(ii) Conc. HNO3, Conc. H2SO4

OH

(ii) dilute H2SO4, Heat

OH

OH
NO2

O2N

(A) (B)

OH

OH

OH
OH

(C) (D)

OH

O2N OH

NO2

NH2

K2Cr2O7

14. ?
H2SO4

NH2

NO O OH O

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

NO O OH NH

15. Final product of the reaction sequence is -

NO2

(i) NH4HS

[R]
(ii) NaNO2 + H2SO4

NO2 (iii) H2O . boil

OH OH OH OH

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

OH NH2 NO2 NO2

OH

16. Phenol, when it first reacts with concentrated sulphuric acid and then with concentrated nitric acid, gives -

(A) 2, 4, 6 – trinitrophenol
Earnestine (B) O - nitrophenol

(C) p - nitrophenol (D) nitrobenzene

17. The major product(s) of given reaction -

OH

(aq. Br2)

(3 eq.)

SO3H

OH OH OH OH

Br Br Br
Br Br

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

Br Br Br Br Br

SO3H Br Br SO3H

18. In the reaction -

OH

NaOH(aq.) the intermediate(s) is (are) -

Br2

O O O O

Br

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

Br

Br
Br Br Br

19. Observe the given reaction and -

OMe O

+ O
(i) AlCl3
[P]
Zn(Hg)
[Q]
(ii) H3O HCl

MeO

H3PO4
[Q]

[S]

Find the correct statement (s) -

OMe O

(A) [P] is COOH

(B) Intermediate during (Q  S) formation is acylium ion

(C) Attack of acylium ion on benzen ring govern by + M effect

(D) [S] will give racemic mixture on reaction with Br2(1 eq) in NaOH

ANSWER KEY

EXERCISE-A

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

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

An I

11. (D) 12. (C) 13. (B) 14. (D)

X B
15. (D)

16. (B) 17. (B) I 18. (B) (C) 19. (C) 20. (B)

21. (A,C) 22. (A) (D) 23. (A,B,C) 24. (D) 25. (C)

26. (A,C) B) 27. (B) 28. (D) 29. (C,D) 30. (C)

i X
EXERCISE-B

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

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

X3
10. (A)

11. (D) 12. (A) 13. (C) 14. (C)

EXERCISE-C

1. 1-B ; 2-O ; 3-E ; 4- I ; 5-J ; 6-N ; 7-G ; 8-L ; 9-F ; 10-M 2. (D)

EXERCISE-D

1. (D) 2. (D) (A) 3. (A)

op

EXERCISE-E

1. (6) 2. (3) 3. (5) 4.

Has
(8) 5. (7)

6. (1) 7. (10) 8. (4) 9. (5) 10. (7)

EXERCISE-F

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

EXERCISE-J (DIAZO COUPLING REACTION)

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

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

11. (A,B,C) 12. (A,C) 13. (B,D) 14. (B) 15. (C)

16. (B) 17. (B) 18. (A,C) 19. (A,B,D)