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IIT-JEE ChEmistry by N.J.

sir

ORGANIC ChemIstRy

S
.
J
.

REACTION
MECHANISM

r
i

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IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO-01

Time: 15 minutes

Q.1

(b)

CH3

_____

CH3CH2CH2

(o)

_ _ _ _ _ _ _

(c)

CHOH
2

_____

CH3 C C = O: _ _ _ _ _ _ _ _ _
:

(a)

(p)

_______ _

CH3
(d)

CH3CH2CH2CCH2

_ _ _ _ _

CH2
(q)

_________

(r)

_________

(s)

CH3
(e)

(f)

CH2

________

_________

S
.
J
.
`

(g)

PhCH2CH2
CH3

_ _ _ _

(h)

CH3CHCH2CH2

Ph Me

(i)

Ph
CH3O

CCH2CH2CH2

(l)

OH

(m)

CH3 Me
(n)

_ __ _ _ _ _ _

CH3CHCH2OH

(t)

_________

(u)

_______ _

(v)

_________

___

_ _ _

Ph

(k)

________

____

PhC CHCH2CH2
D

(j)

r
i

OH

(w)

_ _ _ _ _ _

_________

_ _ _ _ _ _ _ _ _

OH
(x)

________

CH3C Cet _ _ _ _ _ _ _ _ _
OH

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IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO-02

Time: 15 minutes

Dehydration of Alcohol
Conc.H2SO4 CH3CH=CH2 Q.11
Q.1
CH3CH2CH2OH

H / _ _ _ _ _ _ _
OH

170C

Mechanism:
(1)

Q.8

CH3 CH2 CH2 O


H

+ H+

CH 3 CH2 CH2
rds

CHCHCH
3

(2)

3, 3Dimethylbutan2ol loses a molecule of


water in the presence of concentrated sulphuric
acid to give tetramethylethylene as a major product.
Suggest a suitable mechanism.

Electrophilic addition:
CH3 CH2 CH2 +

CH3 CH CH3 + :O:

C=C

ENu

CC
E

CH3CH=CH2+ H3O+
Mechanism:

H
Energy profile diagram:

C=C

r
i
Nu

+ E C C

Reaction

Q.2
OH

OH

/ _ _ _ _ _ _ _

H / _ _ _ _ _ _ _
OH

Q.4
Q.5

OH
OH

H _ _ _ _ _ _ _

OH

Q.8

OH

(b)

C C

CH = CH2

CH = CH2

(iv)
CH = CH2

CN

(ii)
CH = CH2

O Me

NH2
(v)

(iv)

(iii)

COOH

(c)
(i)
(d)

H / _ _ _ _ _ _ _

(iii)

(i)
CH = CH2

Conc.H2SO4

_ _ _ _ _ _ _

OH

(ii)

NO2

H / _ _ _ _ _ _ _

Q.9

Q.10

Nu

E
Compare rate of electrophilic addition on alkenes:
(i)

Conc.H2SO4

_ _ _ _ _ _ _

Conc.H2SO4

_ _ _ _ _ _ _

OH

Q.6

Q.1

Nu

(a)

Q.3

Q.7

S
.
J
.

H / _ _ _ _ _ _ _
OH
H / _ _ _ _ _ _ _

Q.1

(ii)

Ph CH = CH2
(i)

(iii)

(iv)

(v)

PH CH = CH Ph
(ii)

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HI

Q.1

CH2 = CH2 _ _ _ _ _ _ _ _ _ _

Q.2

KBr
CH2 = CH2

__________

HI
__________

KBr

Q.3

Q.15

HCl(2eq.)
CH3 C CH
__________

Q.16

HCl _ _ _ _ _ _ _ _ _ _

Q.17

dil.H2SO4

__________

H /H2O

__________

Q.18
Q.4

HI
__________
C = CH2
KBr

HI _ _ _ _ _ _ _ _ _ _

KF

Q.5

Q.19

H /ROH _ _ _ _ _ _ _ _ _ _

Q.20

H /H2O

__________

Me
HI _ _ _ _ _ _ _ _ _ _

Q.6

Q.21

S
.
J
.
CH = CH2

HCl

Q.7

__________

Q.8

HI _ _ _ _ _ _ _ _ _ _

D /D2O

__________

Q.22

H+

Q.23

HI _ _ _ _ _ _ _ _ _
(Ph)2 CHCHCH=CH2

Me
Q.10

Q.11

Q.12

HBr

C = CHPh

__________

Q.13

HCl _ _ _ _ _ _ _ _ _ _
CH2 = CH Cl

Q.14

HCl(2eq.)
CH CH
__________

H
__________

Q.25

HCl _ _ _ _ _ _ _
CH C CH2 CH = CH2

Q.26

CH C CH = CH2

Q.27

H
HOCH2CH2CH2CH = CH2
___
MeOH

HCl _ _ _ _ _ _ _ _ _ _

HBr
__________

HBr
__________

Q.24

Q.9

r
i

HCl _ _ _ _ _ _ _ _ _ _

HCl

__________

OH

Q.28

H /MeOH _ _ _ _ _ _
CH2= CHCHCH=CH2

H _ _ _ _ _ _ _ _ _ _

Q.29
O
H

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IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO-03

Time: 15 minutes

Q.1
O

CH3CHCHCH3

CH3CH2CCH3

Q.3

OH OH
H
H

OH OH

OH
Mechanism:
(1)
CH3 CHCHCH 3

+H

+
H2 O + CH 3CHCHCH 3

:
:OH OH

OH

:
OH
+

CHO
3

CH3 CH 3

S
.
J
.

NaNO2 + HCl HON=O + NaCl

(2)

H O N = O + H H2O +

(1)

N=O
+

N = O RN N = O RNN = OH

: :

RN= NOH

N2 R R N N : RN = N

+ O

NaNO2

R N N :
R N2
HCl

R NH2

Mechanism:

RN: +

Diazotization of primary amine:

H
Ph C CH 2

OH OH

(3)

Q.6

Q.7

Ph

OH

OH OH

H
Et C C Et

OH OH

Q.2

CC

OH

OH

r
i

OH OH

+
CH3 CH 2CCH 3 CH3 CH 2CCH 3

Q.1

CH 3

Q.4

Q.5
s

OH

CH3

RN = NO:

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Demjanov Reaction:
OH NH2

OH

NaNO2
CH3 CHCHCH3
CH 3 CCH 2CH3
HCl

SbCl5
__________

Cl OH

OH

NH2

NaNO2
CH3 CHCHCH3 + N2
CH3 CHCHCH3
HCl

OH

O
H

OH
Br
AlBr3

Q.6

OH

NH2

NaNO2

__
OCH3
HCl

CH CH
NH2

Q.2

OH

NH 2

NaNO2

HCl

__________
Q.8

NaNO2

__________
HCl

Q.3

DPP NO-04
Non Classical Carbocation:

Q.4

Nu

ENu

C C
E

Mechanism:
C C

C=C
E

+ Nu

Nu

N
Nu

C C

Q.2

Q.3

aq.AgNO3

__________

2
CH2 = CH2
_______
Br2 _ _ _ _ _ _ _
CH2 = CH2
O
H
H

ORGANIC chemistry
Time: 15 minutes

Br2

_ _ _ _ _ _ _
CCl4

Q.5

ICl _ _ _ _ _ _ _
CH3 CH = CH2

Q.6

HOCl _ _ _ _ _ _ _
CH3 CH = CH2

Q.7

Cl2

_ _ _ _ _ _ _
CCl4

Q.8

Br2

_ _ _ _ _ _ _ _ _
CCl4

Q.9

Br2 /H2O

_______

Q.10

Br2

_______
H2O

Br

OH

S
.
J
.

IIT-JEE ChEmistry by N.J. sir


C=C

OH

OH

r
i

AgI

__________

Q.7
I

Q.1

__________

+ CH3 CCH2CH3 CH3 CCH2CH3

Q.1

(1)

NaNO2

_______
HCl

CH3 CH CH

Q.5

Mechanism:
(1)
OH

Q.4

NH2

Q.11

Br2 /CCl4

_______
(1eq.)

Br2

_ _ _ _ _ _ _
CCl4

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H
N

Q.12
Q.13

Diels Alder Reaction:

Br2 (CCl4 )

_______
(1eq.)

+ ||

HCl _ _ _ _ _ _
CH3 CH = CH2

COOH

Q.1

CH3Cl / AlCl3

COOH

COOH

CH3Cl
Q.2
H

Q.14

HO

CH3

______

HCl _ _ _ _ _ _

CH3

Q.13

The reaction of propene with HOCl proceeds via


the addition of
[IIT '2001]
Q.5
(A) H+ in first step
+
(B) Cl in first step
(C) OH in first step
Q.6
(D) Cl+ and OH in single step
B
OH

Q.18

Ans.
Q.23

Q.4

H 2O

NO
NO

(C) CH3 CH2 CH


Cl

Q.26

The number of stereoisomers


bromination of trans-2-butene is
(A) 1
(B) 2
(C) 3
A

Write down the structures of the stereoismers


formed when cis-2-butene is reacted with bromine.
[IIT '1995]

Ans.

H
Br

Me

Me

H
Br

Q.10

obtained by
[IIT '2007]
(D) 4

Q.5

Br + Br
H
H

(D) CH2 CH2 CH2


Cl
NO

Q.9

r
i

S
.
J
.

NO Cl

Ans.

Me

Br2

5 compounds of
(mixture)
Q.7
molecular formula C4H8Br2
[IIT '2003]
Number of compounds in X will be :
(A) 2
(B) 3
(C) 4
(D) 5
B
Q.8
CH3 CH = CH2 + NOCl P
[IIT '2006]
Identify the adduct.
(A) CH3 CH CH2
(B) CH3 CH CH2
H

Cl

Ans.

+
NO2

Q.15

Ans.

HOOC
Q.3

Q.11

Q.12

Me

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IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO- 05

Time: 15 minutes

Fill in the blanks:


O

Q.1

CH3
OH
OH
H

CH3
OH
OH
H

+ H+ H

Mechanism :
(i)

(ii)

O
H

Intermediatecarbocation
Rearrargemet

Intermediatecarbocation

Re arrangedcarbocation
O

(iii)

H +

Re arrangedcarbocation
(iv)

[H ] = - - - - - - - - - - - - - - t

(v)

Name of Reaction is - - - - - - - - - - - - - - - -

Q.2

OH

OH

S
.
J
.

CH3 O

CH3

Mechanism :
CH3 O

OH

OH

Product

CH3 +

r
i

H Intermediate Carbocation

Intermediate Carbocation rearrangedCarbocation

Q.3

(i)

(ii)

RearrangedCarbocation H+
Pr oduct

PH

NH2

OH

NaNO2 |HCl.

Pr oduct

NH2
PH

CH3

Mechanism :
(i)

C
H

OH

CH3

NaNO2 |HCl.

---- ---------

Rearrangement

H+ + - - - - - - - - - - - - - - - - - - - - - - None of Reaction - - - - - - - - - - - - - -

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CH3

Q.4

CH3

CH3

C +

CH3

CH3

CH3

Q.6

Q.5 CH3 CH2 + CH3 CH2


(Major Pr oduct)
(Major Pr oduct)

Q.7
(explain)

Ph

CH 3

CH3

O
+

CH = CH 2 H / Ph

Mechanism :
(i)
Ph

CH 3

CH 3

+H
CH = CH2

(Intermediate1 )

(Rearrangement)
Nucleophile
Pr oduct
Intermediate3 (Intermediate2 )

HCl | CCl 4

Q.8

HBr
CCl4

PhCH= CH 2

HCl
ROOR/CCl 4

Ph

S
.
J
.

HBr
(ROOR)/CCl 4

CH3

Q.9

CH3

CH3

CH2

Br /h

aq.KOH

2
2
A

CH3

CH3

CH2

r
i
CH3

OH

Conc. H2SO4

HBr(ROOR)
C
B
CCl4

A & C are Idenitcal / Isomers / Positon Isomers.


Q.10

Ph

Ph

NaOH
OH
electrolysis

Ph

Anode
(I)

_ _ _ _ _ _ _ _ _ e +

Ph

Cathode

(i)

2H2O + 2e _ _ _ _ _ _

Ph

Ph

(ii)

Ph

(iii)

Intermediate - - - - - - - - - - -

Ph

CO2 +
Intermediate

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IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO- 06
1.

Time: 15 minutes

Which of following carbocation will undergo


rearrangement?
+
+
CH2
CH2
(a)

(b)

(c)

(f)

Ph C Ph
CH2 CH3

(g)

(A) , Major product (A) is


(major)

+
+

CH2 CH2 OH

3.

(d)
+
+

(e)

Ph CH Ph

(h)

(A)
O

r
i

Ph CH Ph

Ph
+

CH CH3

(i) CH2 O CH2 CH2 CH2


(B)

(j)

Ph CH Ph
+
CH2

(k)

(l)

S
.
J
.
(C)

CH3

(m)

Ph

Ph C OH

Ph

(n) CH2 CH2 CH2

(o)

+
CH

(q)

(r) CH3CH2CH2+

(t) (CH3)3 C CHCH3


CH2OH
2.

CH2 CH3

+
(p) CH2 C
=O

CH3 CH2 O

CH CH2

(D)

4.

OH

Reaction-1

(s) (CH3)2 CH CHCH3

(u) (CH3CH2)3CCH2+

H (A)

Reaction-2

OH

(A) an heating isomerizes to (B). What is the


structure of (B).
CH3
OH

Reaction-3

(A)

Sum of -hydrogen (A + B + C) is.

(B)

(C)

(D)

5.

OH

(A)

OH

(A)
(major)

(A)
(major)

(A)
(major)

H (x)

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10

(B)

OH

OH

H (y)

H (B)

Reaction-2

OH
H (z)

(C)

OH

H (p)

(D)

Reaction-3

H (C)

OH
Total number of products obtained in above
reactions including minor products is (include
stereoisomer)
x y z p

6.

In which of following reaction rearrangement take


place with change is carbon skeleton.
CH3
+
(A) CH C CH
(B) CH3 CH2 CH2
3
2

H (D)

Reaction-4

Sum of -hydrogen is
8.

+
CH3 CH CH2 CH2

CH2OH

S
.
J
.
OH

(B)

CH3

(D) CH3 CH CH3

r
i
A+B+C+D=

In which of following reaction resonance stabilized


product will form.
(A)

CH3

(C)

OH

CH3

7.

Sum of -hydrogen in major product of the


reaction.
OH

Reaction-1

(C)

OH

(D) All

H (A)

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11

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO- 07
Q.1

Time: 15 minutes
OH

Compare rate of dehydration (acid-catalyzed)

OH

OH

A+B

(h)

(i)

H
OH

H
CH3

(a)

A+B

CH3

OH

OH

A+B

(j)
OH

(b)

OH

OH

(c)

OH

(d)

OH

OH

H2 SO4

(m)

OH

CH3

(e)

S
.
J
.
OH

(n)

Q.2

Q.3

Predict the major product


dehydration of alcohols
(A) 2-pentanol
(B) 1-methyl cyclopentanol
(C) 2-methyl cyclohexanol
(D) 2, 2-dimethyl-1-propanol

of

(o)

(b)

H SO

CH2 OH

H PO

CH3

(f)

(r)

CH3

OH

(s)

Q.4

OH

H3PO4

Write Mechanism

(a)

OH

H2 SO4

(b)

CH3CH2CH C CH3

OH

(g)

Cl

H3PO4

3
4
CH CH2 CH3

OH

(e)

D
D

OH
CH3
D
H
D

2
4

CH3CH2C CHCH3

OH

(d)

(q)

CH3 CH3

OH

(p)

(c)

H2 SO4

CD3
OH

H2 SO4

OH

OH

acid-catalyzed

Identify-Product
(a)

KHSO4

170 C

H2 SO4

(l)
OH

OH

r
i

OH

(k)

OH

(c)
18
+ H2 O

H
OH

CH2 CH CH2 CH2 CH2


OH
18

OH

CH 3

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12

Q.5

HCl

(a)

CH2

Me

Me

Predict Major Product


(i)

HCl

(b)

(j)

HCl

(c)

HCl

(d)

2-methyl propene

(e)

Hl
1-methyl cyclohexene

(k)

OH

OH

(l)

OH

OH

(n)

(o)

CD3

(b)

D
(q) D

OH

OH

(p)

(c)

S
.
J
.
(r)

(d)

OH

OH
OH

OH

r
i
(m)

Ans.1 (a)

(s)

Cl

Cl

(e)

Ans.5 (a)

(b)

(c)

(d)

Ans.2 (A)

Ans.3 (a)

(B)

(C)

(b)

(D)

CC=CC

(c)

(e)

(f)

(h)

(d)

N
(g)

Cl

Cl
I

(e)

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13

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO- 08
Q.1

Time: 15 minutes

Identify major products:


CH3
HgSO4
(a)

CH3 C C CH H2 SO4

(d)

H
Ph

CH3
HgSO
2

(c)

CH3

(f)

Q.3

CH

(d)
C

HgSO4

H2 SO4

Ph

DCl (x)
D3O+
(y)

HgSO4

H2 SO4

CC

H3 O

HBr

CCl4

(e)

4
CH3 C CH

H SO

(b)

H
C=C

What will be major product obtained from


addition of HBr to each of the following
compounds.
(a)
CH3 CH2 CH = CH2

r
i

CH3

CH
H3 O

(e)

(f)

HgSO4
H2 SO4

(b)

CH2

(c)

CH3
CH3 C CH

CH
H3 O

(d)

(h)

H3 O
l-phenyl cyclohexene

(i)

H3 O
l-methyl cyclopetene

HBr

(j)

(e)

H2C = C

(f)

CH3 CH = CH CH3

(g)

HO

(h)

CH3 CH CH2 CH = CH2

Find total product in following reaction ? (including


stereoisomer)

(a)

OH

(x) products

N
Br2

HBr
CCl4

(y) (products) (Markonikoff products)

(i)

CCl4

OH
(c)

(j)

1.

(a)

(b)

H
HBr

(A)
(B)

CCl4

Br2

CH3

Ans.

OH
(b)

CH = CH2

(k)

(z) (products)

CCl4

CH2 CH3

CH3

HBr
Ph CH2 CH = CH2

CCl

(k)
Q.2

S
.
J
.
CH3

(g)

CH3 CH = C CH3

(c)

Me

(C)

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14

O
3.

(d)

(a)

Br

(c)

CHD2

(g)

(e)

OH

Ph

OH

2.

M. I.

(a) x 3 ; y 2 ; z 5
(b)
A 1 ; B 1 ; C 2
(c) 3
(d) 2
(e) 4
(f) x 4 ; y 4

HO

M. I.

*
Br

Br
(h)

(j)

HO
Br

r
i

M. I. (i)

S
.
J
.
(k)

Br

(g)

Br

(k)

(f)

Br

(i)

Br
(j)

(d)

Br

(f)

(h)

Br

Br

(e)

M. I. (b)

Br

Me

M. I.

Br

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15

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO- 09
Q.1

Time: 15 minutes

How will prepare following compound using alkene


as the starting material ?
OH

Ans.
1.

(a)

(b)

OH

Br
(c)

H3 O

(a)

(b)

H3 O

or

(d)

or
Br
CH3

(e)

Br

(f)
CH3 O C CH3
(c)

CH3

OCH3

Q.2

or

OH (i)

(g)

Identify reactant in following reaction


(a)
(b)

Br2
CCl4

Br

Br

2
(B)

CCl
4

Br

(d)

HBr
(C)

CCl
4

Br

HBr
(D)

CCl
4

CH3

(e)

HBr
(E)
CH 3 C CH2 Br
CCl
4

CH3

O
H O

(f)

3
(F)

(g)

(G)
racemic mixture of 2, 3
CCl

HBr

Write Mechanism

(a)

HBr

CCl4

or

(e)

MeOH

(f)

HBr

CCl4

(g)

(h)

dibromobutane.
Q.3

(d)

+ Mirror Image

Br

(c)

S
.
J
.

(A)
meso 2, 3 dibromobutane

2.

r
i
HBr

CCl4

or

or

or

H3 O

MeOH

(a) A Trans but-2-ene


(b) B cyclohexene
(c) C cyclohexene
(d) D 2-Methylpropene
(e) E can not prepared by alkene
(f) F Propyne
(g) G Cis but 2-ene

OH

H3 O

(b) PhCH2CH2OH Ph CH CH3

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16

IIT-JEE Chemistry by N.J. sir

ORGANIC chemistry

DPP NO-10

Time: 15 minutes

OZONOLYSIS:

The reaction of alkene of alkene with ozone (O3) followed by hydrolysis is known as ozonolysis.
It is two types : (I)
Reductive ozonolysis In presence of reducing agent
(II)
Oxidative ozonolysis In presence of oxidizing agent
Reducing agents:
Zn, H2O or Zn, CH3COOH or (CH3)2S or (Ph)3 P etc.
Oxidising agents:
H2O2 or R C O O H or Ag2 O etc.
||
O

R
C=C

O3
step I
70C

R
R Zn/H2O
Reductive
C = O + R C H
C
H ozonolysis R
O
O

C
R
O

Oxidative H O
2
2
ozonolysis
Example 1:

R C R + R C OH
O

Mechanism:

C
R

S
.
J
.
R

O +

C=O

RCO

R C O

RCO

O+

r
i

[SCT-Cut the double bond


and paste two oxygen atoms
and vice versa]

R
O=C

R C R + R C H

Note : In case of oxidative ozonolysis aldehyde (not ketone) further undergoes oxidation which gives acid
as product.
Q.1

Give the product of the following reaction.


[ 7 2 = 14]
(i)

(i)O

3
H2C = CH2
(ii)Zn /H O

(vii)

H2C = CH CH2 CH = CH CH3

(i)O3

(ii)Zn /H2O

(i)O

3
CH3 CH = CH2
(ii)Zn /H O
2

CH3

(iii)

Q.2

Find out the structure of reactant.


[11 2 = 22]
(i)

(i)O

(i)O

3 CH CH
X
CH
3
2
(ii)Zn /H O
2

3
CH3 C = CH2
(ii)Zn /H O
2

(iv)

(ii)

(i)O3

(ii)Zn /H2O

(v)

(iii)

(i)O

(ii)Zn /H O

(vi)

O
X

(i)O3

(ii)Zn /H2O

(i)O

3
X
(ii)Zn /H O
2

O+

O+

(i)O3

(ii)Zn /H2O

(ii)

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17

(iv)

(v)

(i)O

3
X
(ii)Zn /H O

(i)O

3
X
(ii)Zn /H O

How many species will be formed.


Q.4

(vi)

O /

Zn /H O

(iii)

(i)O3
X

(ii)Zn/H O

CH3

H 3C

C=O +

H
C=O

How many initial ozonoids are possible in given


reaction.
(i)

(i)O /

3
CH2 = CH2

(ii)Zn /H O

(vii)

(i)O

3
X
(ii)Zn /H O

(ii)

(iii)

(viii)

(i)O3
O

(ii)Zn /H2O

C10H12

+ HCHO

Q.9

(i)O

(ii)Zn /H O

C12H18
O

(x)

(i)O

(X)

(xi)

(i)O

+ HCHO

(ii)Zn/H O
2

C12H18

Q.3

Ans.

Q.21

3 C H O
C6H4
3 2 3
(ii)Zn /H O

Ans.

Give the ozonolysis product of the following.


H
O ()

3 3
(i) X
Zn
O

CH3 CH =

(ii)

N
O

3 ?

Zn /H O

How many species will be formed.

r
i

Only mole of the compound A (molecular formula


C8H12), incapable of showing stereoisomerism,
reacts with only one mole of H2 on hydrogenation
over Pd. A undergoes ozonolysis to give a
symmetrical diketone B(C8H12O2). What are the
structure of A and B?
O
(A)

(B)

O
If after complete ozonolysis of one mole of
monomer of natural polymer gives two moles of
CH3
CH2O and one mole of O = C CH = O. Identify
the monomer and draw the all-cis structure of
natural polymer.
[IIT '2005]
CH3
(a) CH2 = C CH = CH2
H
CH3
(b)
C = C
CH2)n
(CH2
OH

Q.22

(i)O /
3
CH2

(ii)Zn /H O
2

S
.
J
.

O + HCHO

O=C=O+

(ix)

(i)O /

3
CH3 CH = CH CH3

(ii)Zn /H O

H ,

(i ) O

(ii) Zn / Cl3COOH

Identify X and Y.

Ans.

O
, (Y) CH3 C (CH2)4 CH = O

(X)
CH3

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18

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO-11
O

Time: 15 minutes
CHO

(C)

Q.1

(D)

CHO
CHO

is obtained by the ozonolysis of following?

Q.5

This compound on ozonolysis gives which of the


following compounds
O

(A)

(B)

(C)

(D)

r
i
O

(I) O

(II)

OHCCCCH2CCHO
O

Q.2

O3
?
O
ZnH2O H
O

S
.
J
.
Q.6

(B)

(C)

(D)

CH3
|
H
CH3 C CH3

|
OH

O3
(A)
(P) + HCHO
Zn,H O
2

Product (P) is

Q.7

O
||
(A) CH3 CH2 CHO (B) CH3 C CH3
(C) CH CH OH (D) CH3 CHO
3
|
CH3

Q.4

The reactants that lead to product (a) and (b) on


ozonolysis are

Q.8

(A)

(B) I, III, IV
(D) I, II, IV

Which of the following will give three different


compounds on ozonolysis
Me

(A)

(B)

(C)

(D)

Me

Which one of the following compounds gives


acetone (CH3)2C=O as one of the products of its
ozonolysis?
(A)

(B)

(C)

(D)

ozonolysis

Sentene
O

Which is the correct structure of Sentene.

HCHO

CHO

(a)

OHCCCCH2CH = O

(IV)

(A) I, II, III & IV


(C) I, II, III

O
O

(A)

Q.3

(III)

Which starting material should be used to produce


the compound shown below?

(A)

(B)

(C)

(D)

(b)
(B)
Q.9

In which of following reaction product formed is


aromatic

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19

OH
Q.10
(A)

HBr

(B)

HF

KH

(C)

Propane reacts with chlorine in sunlight to give two


products. 1-chloropropane is obtained in 44% yield
and 2-chloropropane is obtained in 56% yield of the
total product. 2-Methylpropane reacts with chlorine
under same conditions to produce 1-chloro-2methylpropane 66% and 2-chloro-2-methylpropane
33% What will be the percent yield (X) of the major
product obtained when 1,3,5-trimethylclohexane is
treated with Cl2 in similar conditions. (Round
answer to nearest integer)

OH
H2SO4

(D)

HO
OH

IIT-JEE ChEmistry by N.J. sir


DPP NO-12

Time: 15 minutes

Free Radicals:
Wurtz Reaction:
Na

S
.
J
.
Cl

Cl

Mechanism: (Free radical Mechanism)


(1)
Na Na+ + e

(3)

Na

________ _
ether

Q.8

R X
R R
ether

R X + e R + X

R + R R R

(2)

Q.12

(3)


R + R X R R + X

R X + 2e R+ X

Na

_______
ether

Br

Q.11

(2)

Cl

Q.9

Q.10

(Ionic Mechanism)
(1)
Na Na+ + e

Na

Q.1

CH3 Cl
_______
ether

Q.2

Et Cl
_______
ether

Q.3

CH3 Cl + Et Cl
_______
ether

Na

Cl

Na

Na

Na
THF

Na _ _ (Wurtz fitting)
Cl + Cl CH3
THF

Cl

Q.5
Q.6
Q.7

Br

Q.16

Cl
Ag/Powder
_______
HCCl
Cl

Q.17

_______
CH2CH=CHCH2
ether

Na

Br

Br

Na

_______
Br
ether

Cl
Br
Br

Na

_______
ether

Cl
Zn
_______
CH2CH2

Br

(Ph)3 CI
_______
ether

Na

_______
ether

Na
_ _____
Cl
ether

Ph Cl
_ _ _ _ _ _ _ (fitting Reaction)

Q.13

Q.15

Na

_______
Cl
ether

Cl

Q.14

Q.4

r
i

ORGANIC chemistry

Na

_______
ether

Q.18

Na

_______
ether

Br

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20

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO-13
Q.1.

Q.2.

Q.3

Time: 15 minutes

On chlorination, an equimolar mixture of ethane and neopentane yields neopentyl chloride and ethyl chloride in
o
o
the ratio 2.3 : 1. How does the reactivity of 1 hydrogen in neopentane compare with the of a 1 hydrogen in
ethane?
Give product(s) in each of the following reactions
Br2 / hv
CH3 CH CH2 CH2 CH3
(A)
CH3
Bromination of methane is slowed down by addition of fairly large amount of HBr.
(a)
Suggest a possible explanation for this.
(b)
Account for the fact that addition of HCl does not have a similar effect upon chlorination of CH4.

r
i

Q.4.

Which of the following compounds on gentle heating, will undergo homolytic bond cleavage easily:
O
(A)
(B)
(CH3)3C OC(CH3)3
(CH3)2C O C CH3
(C)
(CH3)3C C6H5
(D)
(CH3)3C OOC(CH3)3

Q.5.

Amongst the following, the most basic compound is:


(A) C6H5NH2
(B) p-NO2C6H4NH2
(C) m-NO2C6H4NH2
Which of the following is most acidic?

Q.6

(A)

NH3

(B)

(C)

CH3 NH3

NH3

(D)

Write mechanism of following reactions?


(a)

Na

Cl

Et 2O

HC

(b)
Q.8.

S
.
J
.

NH2

Q.7.

(D) C6H5CH2NH2

Na

Ph3 CCl

Ph2 C

Et 2O

CH2

CH2

CPh2

Arrange the following in increasing order of stability.


(a)

(regarding stability of free radical)


CH3
(b)

CH2

Q.9.

CH2 , CH2

CH

CH

CH

CH2 ,

CH2

Supply the structure and type of intermediate species designated by

(a)
CH3 CH CH3 + H+ ? + H2O
(b)
CH3CH2 N N CH2CH3 ? + N2
|

OH

Q.10.

(c)

CH3CHI2 + Zn
? + ZnI2

(e)

CH3CH2Cl + AlCl3
AlCl4 + ?

(d)

CH3C CH + NaNH2
? N a + NH3

Name any organic compound which on electrolysis give H2 on both the electrodes.

Q.11. Given structure of major product formed by electrolysis of following salts.


(a)

(b)
COONa

COOK

COONa

COOK

(c)
COONa

COOK

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21

CH3

Q.12

CH3

CH3

C +

C
(Major Pr oduct)
CH3

CH3

CH3

Q.13

CH3 CH2 + CH3 CH2


(Major Pr oduct)

Q.6

(explain)

O
+

Q.14

Ph

CH = CH 2

CH3

CH 3

H / Ph

Mechanism :
(ii)

Ph

CH 3

CH 3

S
.
J
.

(Intermediate1 )

CH = CH 2 + H

r
i

(Rearrangement)

Nucleophile
Pr oduct
Intermediate3 (Intermediate2 )

HCl | CCl4

HBr
CCl4

Q.15
A

PhCH2 = CH 2

HCl
ROOR/CCl4

CH3

Q.16

CH3

CH2

HBr
(ROOR)/CCl4

Br /h

CH3

aq.KOH

2
2
A

CH3

CH3

CH2

CH3

OH

Conc. H2SO4
HBr(ROOR)
C
B
CCl4

A & C are Idenitcal / Isomers / Positon Isomers.

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22

Q.17

Ph

Ph

NaOH

OH
electrolysis

Ph

Anode

Cathode
Ph

_ _ _ _ _ _ _ _ _ e +

(I)

(ii)

Ph

Ph

Ph

2H2O + 2e _ _ _ _ _ _

(i)

Ph

CO2 +

Intermediate

Ph

(iii)

Intermediate - - - - - - - - - - -

IIT-JEE ChEmistry by N.J. sir


DPP NO- 14

S
.
J
.
COOH

Kolbe Electrolysis:

O
NaOH

RR
electrolysis

CO2 + H 2

COOH

Cathode

Anode

Mechanism:
(1)

R C OH

+ OH

R C O

+ O

Q.6

Anode:

(2)

KOH
_______

electrolysis

R C O R C O + e
O

R C O R + CO2

R + R R R

Cathode:
(1)

2H2O + 2e 2O H + H2

Q.1

electrolysis
CH3 COOK
_______

Q.2

NaOH
Et COOH
_______

electrolysis _
COONa

_ _

NaOOC

Q.8

electrolysis
COONa __ _ _ _

NaOOC

Q.7

(2)

COOH

Q.5

HOOC

(1)

Time: 15 minutes

NaOH
_______

electrolysis

Q.4

R C OH

r
i

ORGANIC chemistry

electrolysis _ _ _ _ __ _
SO3 K

KO3S

COOH

Q.9

SO3H

NaOH

electrolysis

_______

COOH

Q.10

NaOH

electrolysis

_______

COOH

SO3K
electrolysis
_ _ _ _ _ _ _

Q.11

electrolysis

NaOH
_ _ _ _
COOH

Q.3

HOOC

electrolysis

SO3K

Q.12

KO3S

electrolysis

___

SO3K

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23

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO- 15
Q.1

Time: 15 minutes

Matrix
Reactions

(A)

Number of dimerization product


(excluding stereoisomers)

Na
CH3 CH2 Cl

Dry ether

(P)

(Q)

(R)

(S)

None

Cl
Na

Dry ether

(B)

(C)

14

Na
H2C = CH CH2 Cl

Dry ether

Q.2

Cl
* 14
Na
+ CH3 Cl (H2 C CH2 )

(D)

Dry ether

Br

Identify major products.


CH2Br

(1)

+ 4 Na

AlHg

C2H5OH

(2)

Na

DE

14

(7)

I
I
I+

Cu

120260C

Cl

(4)

(6)

Br

(3)

S
.
J
.
Cl

Br

r
i

Na

DE

(5)

Br

(8)

Na

Dry ether

Na

Dry ether

(9)

Na

Dry ether

Cl

Na

DE

Br

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24

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO- 16
Q.1

Time: 15 minutes
Cl

Identify the major product:CH2 I

(12)

Na
+

Dry ether

(1)

Na

Dry ether

CH3 CH2 Cl +
Br

Br

Br

(2)

Cl

(13)
Na

Dry ether

2.

Br

Br

CH2

CH2

(1)

rxn - coordinate

Br

Se (B)
Na

(A)
Dry ether

(4)

Br

Br

Br
Br

(2)

(3)

(4)

(6)

CH2 Br

(7)

Na

(A) + (B);
Dry ether

CH2 Br

3.

Na
H2C*=CHCH2Cl
A + B + C
Dry ether

Br

Na

Dry ether

(9)

Cl

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

Cl

Na

Dry ether

(10)
Cl

Na

Dry ether

(5)
(6)

rxn - coordinate

Cl + H CH3 H Cl + CH3

Bond energy

(A) & (B) are isomer.

(11)

CH3 + CH3 CH3 CH3

Na

Naphthacene
Dry ether
Br

(8)

hv 2Cl
Cl Cl

S
.
J
.

Na

Dry ether

(5)

r
i

Which of following is correct matching of energy


profile diagram?

CH3 Cl CH3 Cl

Na

Dry ether

(3)

Na

Dry ether

rxn - coordinate

E
rxn - coordinate

KJ

KJ
H Cl 432
CH H 440

mole 3

mole

When pentane is heated to a very high temperatue,


radical reactions take palce that produce (among
other products) methane, ethane, propane, and
butane. This type of change is called thermal
cracking. Among the reactions that take place are
the following:CH3CH2CH2CH2CH3 CH3 + CH3CH2CH2CH2
CH3CH2CH2CH2CH3 CH3CH2 + CH3CH2CH2
CH3 + CH3 CH3CH3
CH3 + CH3CH2CH2CH2CH3
CH4 + CH3CH2CH2CH2CH2
CH3 + CH3CH2 CH3CH2CH3
CH3CH2 + CH3CH2 CH3CH2CH2CH3
(a)
For which of these reactions would you
expect Eact to equal zero?
(b)
To be greter than zero?
(c)
To equal H?

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25

IIT-JEE ChEmistry by N.J. sir


DPP NO-17
1.

ORGANIC chemistry
Time: 15 minutes

Compound

Number of monochloroproduct

Number of monocloroproduct
(excluding stereoisomer)

1.
2.
3.
4.
5.
6.

7.

8.

9.
CH2

2.
1.

Compound

S
.
J
.

Number of Dichloroproduct
(including stereoisomer)

1.

1-chlorobutane

2.

R-2-chlorobutane

3.

3-chloropentane

4.

R-2-chloropentane

5.

S-2-chlorobutane

6.

R & S-2-chloropentane

7.

R & S-2-chloro butane

r
i

Optically active product

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26

IIT-JEE ChEmistry by N.J. sir

ORGANIC ChemIstRy

Question bank on

r
i

GRIGNARD'S REAGENT

H
N,
RC

O
RCOR, H2

HCOOEt

SiCl
4

l2
PbC

Cl 2
Zn

H2 O
,

S,

CH

RMgX

O
+

gB
r

O
+

O
, H 2O
CH 2
CH 2

O
, H2
HO
RC

O2, H2O,

O
+

O
+

O
,H

CdCl 2

S
.
J
.
X

2
CH
H=
C
2
H
CIC
R
CICH 2O
RMgX
PhC
H2 C
l
CI
CN

Cl 2

Br2

I2

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27

GRIGNARDS REAGENT
Q.1

The order of reactivity of alkyl halide in the reaction


R X + Mg RMgX is
(B)
(A) RI > RBr > RCl
(B) RCl> RBr > RI
(C) RBr > RCl > RI
(D) RBr > RI > RCl

Q.2
Mg
BrCH2CCCH2Br
BrMgCH2CCCH2 MgBr

O
||
PhMgBr(excess) + CH3 C Cl

(C)

O
O
||
||
CH3MgBr(excess)+ CH3 C O C CH3

(D)

O
||
CH3MgBr (excess) + Cl C O Et
H

(excess)
Et 2O

Mg(1 eq.)
Et2O

Product

Cl

Q.9

The major product is


(A) Br MgCH2 C C CH2Br
(B) Cyclobutyne
(C) (CH2C C CH2)n
(D) CH2 = C = C =CH2
Q.3

Q.4

1 equivalent Mg

Br

ether

Br

(D) None of these

S
.
J
.

Which of the following reacts with Grignard reagent


to give alkane?
(A) nitro ethane
(B) acetyl acetone
(C)
acetaldehyde
(D) acetone

r
i
Y ; Y is

(B)

D
D

(C)

D O

Cl

(A)

On conversion into Grignard followed by treatment


with ethanol, how many alkyl halides (excluding Q.10
stereoisomers) would yield 2- methyl butane
(A) 2
(B) 3
(C) 4
(D) 5

Compounds are shown with the no. of RMgX


required for complete reaction, select the incorrect
option
(A) CH3COOC2H5
1
(B) CH3COCl

(C) HOCH2COOC2H5

OH

Q.5

How many litres of methane would be produced


when 0.595 g of CH3MgBr is treated with excess of
C4H9NH2
(A) 0.8 litre
(B) 0.08 litre
(C) 0.112 litre
(D) 1.12 litre

(D)

CHO
COOC2H5

Q.11

Q.6

How many litres of ethene would be produced when


2.62 g of vinyl magnesium bromide
is treated with 224 ml of ethyne at STP
(A) 0.224 litre
(B) 0.08 litre
(C) 0.448 litre
(D) 1.12 litre
MgBr

Q.7

OH

(B)

(C)

H
H

C = O (II)

CH3

(A) I > II > III > IV


(C) II > I > IV > III

C = O (III)

CH3
CH3

C = O(IV)

Me3C

C=O

Me3C

(B) IV > III> II> I


(D) III > II> I > IV

Carbonyl compound (X) + Grignard reagent (Y)


OH

OH

(A)

What will be the order of reactivity of the following


carbonyl compound with Grignards reagent?
(I)

Q.12

OPh

(D)

Ph X, Y will be-

Me
Et

O
O
||
||
Et

Ph,
MeMgBr
Me

C
Ph,Et MgBr
(A)
(B)
Q.8

(A)

In which of the following reactions 3 alcohol will be


obtained as a product.
O
||
MgBr (excess) H C Cl +
H

O
O
||
||
(D) Me C Et,Ph MgBr (D) Et C Ph,Et MgBr

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28

Q.13

(i) Mg
(R) 2Bromooctane
X; X is

C6H13
*

(A) CH3

COOH

(B) HOOC

(D) None of these

(A)

(B)

CH 2CH=O

(C)

CH=O

(D)

CHCH3
|
CH=O

Br

1. Mg/ether
Product (s)
+
2. CH3CHCH2CH 3. H3O
|
||
OH
O

(B) RMgX + C2H5OH Alkane

Select the product from the following

(C) RMgX + CH3CH2Cl Alkene

I.

(D) RMgX + Cl

Ether

The number of
consumed
per

moles
mole

of
of

COOEt

is

(A) 4

(B) 2

(C) 3

Q.20

Br

Dry Ether

O
||
CH3CCH3
NH4Cl

X
(Major)

End product of above reaction is

(A)

CH 2
||
CH2= CH CH2 C CH 3

(B) H2C CH CH C CH3


|
CH3

OH
|
H
C

CH

CH

C
CH3
(C) 2
2
|
CH3
2OH
(D) H2C = CH CH2CHCH
|

2CH3MgBr

A. Product A formed

(A) is ethyl acetate


(B) further react with CH3MgBr/H2O+ to give acetone
(C) further react with CH3Mg Br/H2O+ to give t- butyl
alcohol
(D) Can give pinacol when treated with Mg followed
by H2O
Order of rate of reaction of following compound with
phenyl magnesium bromide is
O
||
Me C Cl
I

(A) I > II > III


(C) III > I > II

Q.22

O
||
C2H5 O C OC2H5

S
.
J
.
(D) 1

Select the correct statement :


(A) 1, 4- dibromobutane react with excess of
magnesium in ether to generate di-Grignard
reagent.
(B)1, 2- dichlorocyclohexane treated with excess of
Q.21
Mg in ether produces cyclohexene.
(C) Vicinal dihalides undergo dehalogenation to
give alkene when heated with Zn dust or Mg.
(D) 1, 3- dichloropropane by treatment with Zn dust
or Mg forms cyclopropane.
Mg
2
CH3CH = CH2

r
i

II. CH 3 CHCH 2CH III. CH 3 CHCH 2CH


|
||
|
|
OH
OH
O
OH
(A) III
(B) I, III
(C) I, II
(D) II, III

grignard reagent
the
compound

Q.17

H3 O

O
||
CCH3

In which one of the following reaction products are


Q.19
not correctly matched in
(A) RMg X + CO2
Carboxylic acid
( 2) H

HO

Q.16

followed

Product

CH3

(C) A and B both

Q.15

OEt
OEt

OEt
Ethyl ortho formate

C6H13

Q.14

MgBr + H C

Q.18

(ii) CO2
(iii) H

O
||
Me C O Et
III

(B) II > III > I


(D) II > I > III

Select the correct order of decreasing reactivity of


the following compounds towards the attack of
Grignard reagent
(I) Methyl benzoate
(II) Benzaldehyde
(III) Benzoylchloride
(IV) Acetophenone
(A) II > III > I > IV
(B) I > II > III > IV
(C) III > II > IV > I
(D) II > IV > I > III
O

Q.23

CH3 MgX
NH4 Cl

(A) Enantiomer
(C) Meso
Q.24

O
||
Me C H
II

Product is
(B) Diastereisomer
(D) Achiral

Nucleophilic addition of Grignard reagent cannot


occur in
(A)

CH3

(C)

O O
O
O
|| ||
||
||
CH 3 C CCH 3
(B) CH3 C CH2CCH3
O
O
O
||
||
CH 3 C CH 2CH 2CCH 3
(D) O

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29

Q.25

CH3 CCH2CH2 CH2 Cl CH3MgBr A, A is


||
O
CH3
|
(A) CH3 CCH2CH2CH2Cl
|
OH

Q.26

Q.30

(D)

A,

(ii) H3O

HO OEt

(A) CH3CCH2CH2COCH2CH3 (B) CH3CCH2CH2CCH 3


CH3
O

OH

OH

Cl

NH4 Cl

Identify P1 & P2.

(D) CH3CCH2CH2CCH3

O
H 3C

Q.27

CH3

(A) CH4

(B)

S
.
J
.

CH CHO

Mg
2
3
PhCH3
(A)
(B)
(C)
h

NH4 Cl

ether

OH
CH2 CH

CH3

(A)
CH3

CH3

(C)

OH
CH

(B)

Q.33

CH
CH3

r
i
HO Me

(C)

(D)
O

14

Mg
NaHCO
(i) CO

(A)
(C) gas
(B)
3

(ii) H /H2 O

(i) CH ONH

3
2
2CH3MgBr

(ii) H

CH3

CH3

following

Product C is
(A) CO
(B) 14CO2
(C) CO2
14
(D) A mixtue of CO2 and CO2

CH3

OH
C

(D)

HO

Br

Q.32

CH3

the

2CH3MgX

P 1 + P2

Q.31

CH3
H 3C

RMgX (2 moles)

Deprotonation will occur from


positions:
(A) 1, 2
(B) 1, 3
(C) any two positions (D) 1, 4

A formed in this reaction is

(C)

OH

(i) CH3MgBr(one mole)

CH3

CH
(4)

OH

CH3

(2)
OH

H
(1) S

H3C

CH 3CCH 2CH2COCH 2CH 3

CH3

CH3

O (3)
H

CH3

O
CH3

HO

(D)

OH

(B) CH3 CCH


2CH2CH2CH3
||

CH3

CH3

CH3 ,

(C)

H3C

(C)

HO

(A) CH3 O NH CH3 (B) CH3 NH CH3


(C) CH3 NH2
(D) CH3 OH
OH

Q.28

Select the correct order of reactivity towards Q.34


Grignard reagent for nucleophilic attack.
O
O
||
||
(A) R C R R C H
(B) Cl CH 2 C H CH 3CH 2 C H
||
||
O
O

O
||

O
||
NO2 < CH3 C O

(C) CH3CO

Q.35

(ii) H / H2O

CH3

(A) The product is optically active


(B) The product contains plane of symmetry
(C) The product shows geometrical isomerism
(D) The product shows optical isomerism
Which of the following is incorrect.
O

O
CH3MgX

CH C OC H

(A)

O
O
||
||
(D) R C OR R C NR 2

Cl

OC2 H5

(1 eq)

OC2H5
C2H5MgX

(B) CH3 C OC2H5


CH3C OC2H5
OC2H5

(i) CH3MgBr / CuCl

(X) Major + (Y)

Q.29

(i) CH MgBr

(A)

(X) and (Y) respectively are

H3 O
(C) CH3MgX + C = S
CH3C SH

(A)

,
CH3

CH3

(ii) H2O / H

OH

(1 eq)

OH

(B)

,
CH3

CH3

OH

O
H3 O

(D) CH3MgX + C = O
CH3C OH

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30

Q.36

Which reaction gives 1 aromatic amine as major Q.41


product.
Br

(ii)NH4Cl

NH4 Cl

(A) 1ROH
(C) 3ROH

NH3
Mg/ ether

(A)

(i)CH CN

RMgX
3
RMgX
(A)
(B) will be

(B) 2ROH
(D) Alkene

Br
NH3
Mg/ ether

(B)

Q.42

F
Br

Hg(OAc )2

(D) HOCH2CH2CH2CH2 OH

CH3MgBr + CH2 = CH C H

H O

Product (1, 4

addition). It is

Q.43

OH

(A) CH2 CH

C
CH3

(A) CH4 + IMgO

OH

C CH3

(D) None

(B) CH3O

C CH3

S
.
J
.
OMgI

(i) PhMgBr

Product

Q.38

(C) CH3C

(ii) NH4 Cl

OH

CH3

Me

MgI

Produtcs in this reaction will be


(A) Stereoisomers
(B) Enantiomer
(C) Diastereomers
(D) Geometrical isomers

(D) CH3O

Q.44

CH3MgBr (1 eq.)

CCH3
r

1
+ Ph Mg Br
Ph CH2CH2OH

(i)

2
+ Ph Mg Br
Ph CH2CH2CH2OH

(ii)

The product is:

(A) r2 > r1
(C) r1 = r2

OH

(A)

Q.39

r
i

The reaction of 1 mole each of p-hydroxy


acetophenone and methyl magnesium iodide will
give

(B) CH2 CH = CH CH3

(C) CH3CH2CH2CHO

N
(B)

OH
O

(C)

Q.40

OH

CH3

NH3 /NaBH4

Q.37

(B) CH3 CHCH2CH3

CH3
CH

CHCH3
3
(C)

(D) Ph

(ii)H2O

O
(A) CH3 CHCH2OH

NH3
Mg/ ether

(C)

(i)CH3MgCl

CH3 CH CH2

Q.45

(B) r1 > r2
(D) r1 = 2r2

How many moles of Grignard reagent will be


required by one mole of given compound?
SH

HO

O
C

OEt

Cl

(D)

(i) Br

CH2

(A) 7

(ii) CH3MgBr
(2equi.)

CH3

(B)

CH3

CH3

(C)

Q.46

Cl

2
CH2= C = O
C4H8O

(A)

CH2

CH3

(B) 6

(C) 8

(D) 5

Consider the given organometallic compound.


(I) (CH3)2Hg
(II) (CH3)2Zn
(III) (CH3)2Mg
(IV) CH3Li
The correct decreasing order of ionic character is
(A) I > II > III > IV
(B) II > I > III > IV
(C) I > III > II > IV
(D) IV > III > II > I

(D) All of these

CH2

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31

(i) CH3MgBr

Q.47

CH3CH = CH C CH3

For Q. no. 48 to Q.no.50


Consider the given reaction and answer the
following questions

(ii) H3O

(i) CuI CH3MgBr


(ii) H3O+

COOCH3

MeMgBr

Products

OH

(A) P is CH3CH = CH C Me Q is CH3CH CH2 C CH3

OH

(B) P is CH3CH CH2 C CH3 Q is CH3CH = CH C Me


CH3

Me

Q.48

No. of RMgX consumed in the reaction is


(A) 4
(B) 5
(C) 6
(D) 7

Q.49

How many product will be formed in given reaction


(excluding stereo)
(A) 2
(B) 3
(C) 4
(D) 5

Q.50

Which of the following reaction will give the same


Hydrocarbon formed as one of the product in the
above reaction.
(A) EtMgBr + Me OH
(B) PhMgBr + Me OH
(C) MeMgBr + Ph OH
(D) MeMgBr + CH3 CHO

(C) P is CH3 CH=CHC(CH3)2 Q is (CH3)2CHCH2C CH3


OH

(D) P is (CH3 )2CHCH2C CH3 Q is CH3CH=CHC(CH3)2


O

CH3

Me

(excess )

OCH3
SH

OH

S
.
J
.
ANSWER KEY

R CH2 CH Me

RMgX

HO

O
+

R CH2 CH2 OH

H
N,
RC

R4Si

SiCl4

l2
PbC

HC
OO
Et

R CHO

Cl 2
Zn

PbR4

2
CH
H=
C
2

H
CIC
CICH2OR
RMgX
CIC
OO
Et
CI
CN

N
5
C
20
C,D
35
B
50
C

R2CHOH

H2
=C
CH
CH 2
R
OR
RCH2

RCOOEt

I2

Br2

RCN

R2

R C R

4
A,B
19
C
34
B,C
49
C

OH
R 3C

Cl 2

OH

3
C
18
C
33
C,D
48
C

R,
RCO

RR

Zn

R2 C= O

2
D
17
B
32
C
47
C

O
, H2
HO
RC
HO

HC

O
+

H
gB
r

RSH

O
+

R2Hg

OH
CH
2

ROH

HO
2
,

O
+

R C OH

Q.No.
1
Ans.
A
Q.No. 16
Ans. A,C,D
Q.No. 31
Ans. A,B
Q.No. 46
Ans.
D

HO
,H

R 2Cd

H
H 2O
RC

S,

RH

l
CdC 2

R C SH

RH

O2, H2O,

RSO2H
S

r
i

RCl

RBr

RI

RC

6
C
21
A
36
B

7
A
22
C
37
C

8
9
B,C,D D
23
24
A
B,D
38
39
A,C,D D

10
A
25
C
40
A

11
A
26
C
41
C

12
A,B,C
27
A,B,C
42
B

13
C
28
B
43
A

14
C
29
B
44
B

15
A
30
A
45
A

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32

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO- 01

Time: 15 minutes

Explain:

CH2N2

CH2 = CH2

CH2N2

CH CH

2.

Characteristics :
1.
The reaction is stereospecific in nature

Q.1

Simon Smith Reaction:


CH2I2
CH2 = CH2
CH2 CH 2

CH2I2

Zn

CH2

OH

Zn Zn+2 + Ze

1)

2e
I CH 2 : +
I CH2 I

1.

Zn+2

4.

OH

S
.
J
.
COH

IIT-JEE ChEmistry by N.J. sir


H

SOCl 2

3.

N +

+ HCl

S=O

Cl

OSO
+
Cl

N
:

Cl

Cl

R :O

ROSO

S=O

H
N +

Cl
:O: +

Cl
+

OSO

Cl

S=O
Cl

2.

S
O
+

Cl

O
+

R O S Cl

O
Cl R

Cl
R

+ Cl

+ HCl

Cl

Cl

R O S Cl

R Cl + SO2

Machanism:
1.

Cl

Cl

Time: 15 minutes

This reaction leads to inversion of Configuration.


Darzens Process.

Cl

(Kolbe Schmidt Reaction)

ORGANIC chemistry

+ Cl

:O: +

OH

R Cl + SO2 + HCl

Mechanism:
1.
R

O
C

DPP NO- 02

r
i
OH

CO2

NaOH
high P
high T

CH2 Zn I
(Carbenoid)

CH2I2

Zn

2.

CH2I2

Zn

3.

Zn/ Cu

Mechanism:

(No bond rotation)

CC

ZnI

N:

1.

C=C

2.

O S Cl

R Cl + Cl S

Cl

S
OH
+

O
: H

So2 + Cl

H Cl +

SO2

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33

Note:

the reaction leads to selection of configuration


Retention of configuration.
For example:
O

Q.1

H
:

CH3

C CH

SOCl2

OH

C CH = C = O

CH3

C
Ph

Ph

CH3
SOCl2

Ph

Arndt Eistert Reaction:

Q.2

CH2N2 R C CH 2 N 2
SOCl2 R C Cl
R C OH

SOCl2

C OH

Ag2O/

CH3

CH 3

R CH 2 C
OH

OH

SOCl2

RC
H

CH 3

OH

SOCl2

Nucleophilic addition elimination:


O

N:

1. SOCl 2
2. CH 2N 2

RCH = C = O

3. Ag2 O/
O
4.
H
H

S
.
J
.

(Overall)

R CH 2 C

OH

Characteristics:
1.
The reaction is known as homologation
2.
The reaction occurs with relation of configuration.

CH2N2
R C CH 2 N
R C Cl

r
i

SOCl2

Ph

O
Ph

Q.3

+ Cl

Ex.1

Mechanism:
+
CH2 = N = N:

1.

N:

Ag2O -- -
R C CH= N =N:

H
OH

---

COOH

+
R C Cl + :CH 2 N

O
+
R C CH 2 N

N:

Cl

O
+
R C CH 2 N

Wolf Rearrangement:
O

+
R C CH 2 N

Ag O/

2
N:

Mechanism:
1.

2.

N:

1. SOCl 2

2. CH 2N 2
2. Ag 2O
4. H2O

N:

+ Cl

Nucleophilic addition:

1.

OH

OH

+
R C CH N

+
Ag2O/
N: R C CH N

N:

R CH C
OH
O

OH /H O

2
R CH = C = O
R CH 2 C

1.

HOH R CH C

+OH

OH

2.

R C CH

+N

ROH/RO

R CH = C = O

NH2 / NH 3

R C CH O = C = CH R.

3.

R CH = C = O

4.

R CH = C = O

2.

+
:CH 2 N

RNH2

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34

Diazo methane
Acid-Base Reaction:
1.

O
5.

CH2N2 + HCl CH3Cl + N2

CH2N2
EtCH
- - - - - - - + - - - - - - - - ---

2.

CH3 O

R OH + CH2N2

6.

1. SOCl 2

CH3 CH2 C C OH

2. CH 2N 2
3. Ag2 O/
O
4.
H
H

3.

+ CH2N2

R C

--------

OH

7.
4.

3. Ag 2O/
COOH 4. H2 O

+ CH2N2

CH 3

8.

O
OH

Homologation Reaction:
O

S
.
J
.
H

CH3 O

O
2.

CH2N2
RCR

- - - - - - - - + - - -- - - - - - - -

CH2N2

CH2N2

DPP NO- 03
Nitrenes :
Fill in the blanks:

12.

CH2N2
EtCCH3
- - - -- - - - + - - - - - - - - ---

- - - - - - - + - - - - - - - - ---

+
R N = N = N:

(a)

ORGANIC chemistry

(d)

h
R S N = N = N:

ROCNOS
O

(e)

H N = N = N:
+

h
RC N = N = N:
+
O
- - - - - - - - - - - + - - - - - - - - - - - - - - (gas)

- - - - - - - - - - - + - - - - - - - - - - - - - - (gas)
(f)

R O C N = N = N:
+
O

- - - - - - - - + - - - - - - - - - - (gas)

+
O
- - - - - - - - - - - + - - - - - - - - - - - - - - (gas)

(c)

NO2

Time: 15 minutes

- - - - - - - - - - - + - - - - - - - - - - - - - - (gas)

- - - - - - - - - - - + - - - - - - - - - - - - - - (gas)

(b)

--------------

2. CH 2N 2
3. Ag2O/
4. OH/H 2O

CH2N2
EtCH
- - - - - - - - + - - - - - - - - - ---

IIT-JEE ChEmistry by N.J. sir


Q.1

1. SOCl 2

- - - - - - - + - - - -- - - - - -- -

11.

4.

COH

Cl

3.

10.

r
i

--------------

COOH 2. CH 2N 2
3. Ag2 O/
4. RO/H 2O

CH2N2
RCH
RCCH2 H + RCCH2

--------------

1.

1. SOCl 2

9.

1. SOCl 2

2. CH 2N 2
CH2 CCl 3. Ag2O/
4. OH/H 2O

+ CH2N2

CH3 C

--------

5.

1. SOCl 2
2. CH 2N 2

No 2

O = COH

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35

Fill in the blanks:

H N = C = O

(g)

- - - - - - - - - - - + CO _ _ _ _

KOH R NH2

Br2

RCN
D

Mechanism:
(h)

OH

R N O S Ph

1.

H
O
----------- -

R C N

HOD + R C N:
D

+ OH
D

NO2

BrBr

OH
N Cl - - - - - - - - - - - O
R C NBr
:

HOD +

RC N Cl

(j)

OH

----------- -

OH

Br + _ _ _ _ _ _ _

Hoffmann Bromanide Reaction:

NaOH
R NH2 + KBr + k2CO3

R C NH 2 + Br2

2.

S
.
J
.
RN=C=O

Mechanism:
1.
O

RCNH

R C N: +

OH

RNC

: :

OH

r
i

Wolf
Rearrangement

RN=C=O

RNC

(i)

OH

CO2 + _ _ _ _ _ _ _ _ _ _ _ _

H2 O

Br Br
OH

O + R C N:

R C N H

Br

Br

r.d.s.
RN=C=O

OH

R N=C=O

Q.1

15

(a)

RNC

R NH 2 + OH

O = C NH 2
Br2 /KOH

- - - + - -- -

(b)

Br2 /KOH

------ ---- -R C N Ph
H

Q.3
O

(a)

(iv)

RNC
H

C NH 2

OH

:
R N + CO 2

(ii)
O

Fill in the blanks:


O = C NH 2

C NH 2

CH3

(iii)

C NH 2

O
CH3

C NH 2 Cl

Q.2

Compare rate of reaction:


O

(a)

: :

:
+ Br

(i)
O

O
R C N:

+ Br

R NH 2 + OH

CH2 CH 2 C NH 2

Br2 /KOH

- - -- -

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36

(b)

O = C NH 2
Me

Et

Br2 /KOH

- - - -- - - - - - - - -

Mechanism:
1.
R

R
+

C=N

H
l

(c)

NH

C=N

OH

O
+

Br2 /KOH

------- ---- --

H
r.d.s.

R
l

Br2

------ --KOH

(d)
Ph

H
O

CONH 2
H

(e)

Br2

------ ---- -KOD/D2O

CH3

(g)

R CND 2

C=N

Ph
C=N

C NH 2

CH3

(i)

-----------

CH3

C=N

OH

OH

N
O

C=N

Q.5

C NH 2

Br2

- - - - - - - - - - NaOH

Q.6

C=N

R C NH R

(a)

Catalyst:
O

Et

OH

Ph
C=N

H2SO4
Ph C N

S Cl

Migration of R is always from anti position.

H - - - - - - - - - -

Q.7
Explain:

OH

H2SO4, SOCl2, SO3, PCl5, P2O3, PCl3, BF3,

H
CH 3

Beckmanns Rearrangement:

(Catalyst)

OH

C=N

Br

H - - - - - - -

O2 N

CH3

2
------ ---- -NH2 CNH2
NaOH

PCl5

OH

CH3

-----------

KOBr - - - - - - - - - - -

CH3

(k)

CH3 C C NH 2

(j)

PCl5

CH3

CH3

-----------

KOBr - - - - - - - - -

Q.4

Br

H2SO4

OH

CH3

Q.3

(h)

OH

S
.
J
.

Br2

------ ---- -KOH

r
i

H2SO4 Ph C NH CH 3

Ph

Q.2

Q.1

R CNH 2

+ OH

OH

O
(f)

Rl C = N

NaOCl - - - - - - - - - - -

EtCNH2

Tautomer

Rl C = N R

: :

R C = N
+

OH

Ph

(b)

C=N
HO CH2

H2SO4 PhC N+ H

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37

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

DPP NO- 04

Time: 15 minutes
Schmidt Reaction:

H2SO4
R C OH + HN3
RNH2 + CO2 +
N2.

Curtius reaction:
O
O
NaN3
RCN=N=N
R C Cl
O
NH2 NH2

R C O CH 2 CH 3
O
O

HNO2
R C NH NH 2 R C N = N = N:

+
O

Mechanism:

1. NaN3 RN=C=O OH/H2O

R NH2

R C Cl

2.

R C OH

Imp.
O

RN=C=O

N2

H OH /

R NH2 + CO2

Et O
C OH

R C N = N = N:
H

S
.
J
.
H+

H2O

_ _ _ _ _ _ _
_______

Q.2

R C N = N = N:
:

C Cl

Q.1

NaN3

_______

RC

HN = N = N:

NHR

HOH R NH + CO
R N = C = O
2
2

+H

R/ OH RNH C OR 1
R N = C = O
O
RNH2
R N = C = O
RN C
H

r
i
O

NaN3
SOCl2
_ _ _ _ _

CH3

_ _ _ _ _
_ __ __ _
_ _ _ _ _
H2O/
CH 3
Q.3

O
C

_____ R

NaN

1. NH NH
2. HNO2
H/

O
CH3 O

CH3

COH

N3H(H2SO4 )/

_ _ _ _ _ + _ _ _ _ _ _ +_ _ _ _ _ _

2
2
CH2 COC2H5

_ _ _ _ _ + _ _ _ _ _ _ +_ _ _ _ _ _

Q.2

H _____

____ H
_ __ __ _

Q.5

CH2 COH
N H(H SO )

3
_ __ __ _
Cl

O
Q.4

Q.1

Schimidt miscellaneous:

O
____

H
R C R
R C N R
N3H/
H

1. NH2 NH2 _ __

COCH 2CH 3
2. HNO2

_ _ _ _ _ H O H/ _ _ _ _ _

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38

Mechanism:
1.

+H

HN = N = N:
R

RCNOCR
H

OH

: :

OH

Mechanism:
1.

+ OH
H

O + RCN OCR

RCR
:

HN = N = N:
OH

OH
RC

N2

HN = N = N:
:

H
+

H + RCNR

Q.2

Lossens Rearrangement:
O

R C N O C R
H

+O CR

O
O
KOH _ _ _
CH2 C N O C Ph

Q.1

RCN

RCR

O
RN = C = O

: :

R NH 2+ CO 2

OH

RNH2+ R C O

C N O C
CH3

S
.
J
.

r
i
CH3

KOH

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39

IIT-JEE ChEmistry by N.J. sir

ORGANIC chemistry

r
i
S
.
J
.

Reaction

Intermediates

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40

Q.1

Q.2

EXERCISE I
2-Chloropentane on halogenation with chlorine
gives 2,3-dichloropentane. What will be the
structure of free radical species formed in the
reaction?
(A) Planar
(B) Trigonal planar
(C) Square planar
(D) Pyramidal
Decreasing order of nucleophilicity
following nucleophile is :
(1) CH3O

of

(B)
H

(C)

the

OH

(D)

(2) C N
O
S

(3)

r
i
S
.
J
.

(B) 1 > 2 > 4> 3


(D) 1 > 2 > 3 > 4

(A)

The correct order of rate of Wurtz reaction.


Na
(I)
CH2 F
CH CH
2

ether

Na

CH2 Cl

(III)

(B)

CH2 CH2

ether

Q.8

What will be the major product, when 2-methyl


butane undergoes bromination in presence of
light?
(A) 1-bromo-2-methyl butane
(B) 2- bromo-2-methyl butane
(C) 2- bromo-3-methyl butane
(D) 1-bromo-3-methyl butane

Q.9

Which can not be the possible product of the


given reaction

CH2 CH2

(A) I > II > III > IV


(B) II > I > III > IV
(C) IV > III > II > I
(D) In all rate of Wurtz reaction is same
Q.4

CH3 CH CO2K

electrolysis

(A) (Major)

CH3 CH CO2K

Major product (A) of above reaction

Q.5

(A)

(B)

(C)

(D)

Mg
H2O

P1

P2

(A) It is a spiro compound


(B) It is a Ketone
(C) It can show tautomerism
(D) It is an alkene
Q.6

Consider the following reactionO

OEt

Na/ether

FeSO4 + H2O2

liq. NH3

Fenton's
reagent

the major product P is:


O

(A)

OH

CCl4,

Product (s)

N
H

Br2

CH3 CH2 C OAg

(A) CH3 CH2 Br


(B) CH3 CH2 C O CH2 CH3

Which of the following is not correct about P2.


O

(C)

(D) None of these

Na

Na
ether

CH2 I

CH2 CH2

ether

CH2 Br

(IV)

(X)

X is :

(A) 4 > 3 > 2 > 1


(C) 2 > 1 > 3 > 4

(II)

Na/ether

CCl4. Peroxide

Q.3

NBS

Q.7

(4) CH3 C O 2

(C) CH3 CH2 CH2 CH3


(D) CH3 CH2 CH3

Q.10

Pick the correct statement for monochlorination of


R-secbutyl Bromide.
Me
H

Br

Cl2
300C

Et
P

(A) There are five possible product; four are


optically active one is optically inactive
(B) There are five possible product; three are
optically inactive & two are optically active
(C) There are five possible product; two are
optically inactive & three are optically active
(D) None of these

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41

Q.11

Correct order of rate of photochlorination for Q.16


following compounds is

(A) I is more soluble than bromocyclopropane


(B) I gives pale yellow ppt. on addition with
AgNO3
(C) I is having lower dipole moment than
bromocyclopropane
Br
(D) I is more ionic than

CH3
C

CD3 CD3 CH3

CH3 CH3

CH3

CH3

(I)
(A) II < I < III
(C) III < I < II
Q.12

(II)

(III)
(B) I < II < III
(D) II < III < I

Which one of the following carbocation would you


expect to rearrange.

KNH2

(A)

(A)

(C)

(D)

r
i
S
.
J
.
NH2

(B)

(C)

Q.18

How many, 1,2-Shifts are involved during the


course of following reaction:
OH

(D) (B) and (C) both

conc. H2 SO4

Which of the following carbocation is most stable?


CH3

(A) 1

(B) 2

(C) 3

(D) 4

CH3

+
C

CH3

H3C

+
C

(B)

CH3

CH3
+
C

CH3

(D)

CH3

Q.19

(X)

OH

Product (X) is:

CH3

OH

CH3

HO

CH3

CH3

H3C

OH

(C)

(B)

CH3

NH2

NH2

(A)

CH3

CH3

Cl
NH3

Q.13

Q.17

Product can be

, which is not the correct statement

Br

(A)

(B)

CH3

Q.14

Which carbocation is least likely to form as an


intermediate?

(A) (C 6H5 )3 C

(B)

(C)

Q.20

(C)

Q.15

(D) CH2 CH

For the reactions


(I)

Cl

(II)

Cl

(III)
(IV)

(D)

(I)

OH

(III)

OH

+ Cl , H1

(A) I < II < III < IV


(C) I < III < IV < II

+ Cl , H2

Among the given


dehydration order is:

compounds,

the

(II)

OH

(IV)

OH

correct

(B) II < III < IV < I


(D) I < II < III = IV

OH

CH2Cl

CH2 + Cl , H3

Cl

+ Cl , H4

The correct decreasing order of enthalpies of


reaction for producing carbocation is:
(A) H1 > H2 > H3 > H4
(B) H4 > H1 > H2 > H3
(C) H3 > H2> H1 > H4
(D) H2> H1> H4 > H3

Q.21

P. The product P is

5C

(A)

(B)

(C)

(D)

OH

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42

Q.22

Rate of dehydration when given compounds are


treated with conc. H2SO4.
Q.26

OH

H+

OH

CH2OH

(P)

CH3

(Q)

(A)

(B)

(C)

(D)

OH

OH
CH3

CH3

(R)

(S)

(A) P > Q > R > S


(C) R > Q > P > S

(B) Q > P > R > S


(D) R > Q > S > P

Me

Q.27

Conc.H2SO4

Me

OH
H2SO4

Q.23

OH

OH

Product 'A' is-

r
i
S
.
J
.
(A)

Me (B)

Me

Me

Me

'X' is

Me

OH

OH

(A)

(C)

(B)

C Me

Me

(D)

Me

Q.28

OH

(C)

How many products are obtained in the given


reaction:
Et

(D)

Ph

HO

OH

OH

Et

OH

Q.24

CH3 H+
CH3
O

Q.29

(B) O

Q.25

CH3

N
(D) OH

CH2
O
CH3

CH3

Ph

(B) 2

H2SO4

OH

Ph

(C) 3

H3O

CH3 CH C CH2 NH2

CH3

CH3

HO

HO

(D) 4

CH3

(A)

(C)

Ph

CH3

CH3

CH3

(A) 1

major product is

CH3

HNO2

(X)

CH3 CH3

(major)
Major product of above reaction is:

CH3

CH3

(A)

CH3

CH3

CH C CH2 OH

CH3

A, A is

(B)

OH

CH3

(C)

(D)
OH

OH

OH

HO

(A)

Q.30

Which will dehydrate at fastest rate by H3PO4 :


(A) 2-methyl butane-2-ol (B) 3-methyl butane-2-ol
(C) Butane-1-ol
(D) 2-methyl butane-1-ol

Q.31

What is the order of reactivity with HBr.

(B)

CH3
OH

CH3
OH

OH

OH

(C)

(a)

(D)
OH

OH

(b)

(c)

CH3O

CH3O

OH

(A) a > b > c


(C) c > b > a

(B) b > a > c


(D) b > c > a

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43

CH2 = CH3

Q.32

HBr
CCl4

Cl

Q.38

Stability order of following singlet halocarbene is


(A) CF2 > CCl2 > CBr2 > CI2
(B) Cl2 > CBr2 > CCl2 > CF2
(C) CCl2 > CF2 > CBr2 > CI2
(D) CF2 > CI2 > CCl 2 > CBr2

Q.39

Trans-Butene-2 3 Product

CH3

What is stereochemistry of product?


(A) Racemic mixture
(B) Optically inactive
(C) Diastereomers
(D) Meso product
Q.33

CHCl / KOH
Solvent

In the given reaction :

Cl

H
Br2

(A) CH3

[X]

[X] is :
H
N
Br

(A)
Br

(C)

Br

Br2

Products

Cl3C CH = CH2

(A)

(C)

H3C CH = CH2

The order of rate of reaction of following towards


carbylamine reaction:
O CH3

Q.37

CH2 = CH CH3
Mg / ether

NH2

NaOH

(i) CHCl / KOH

CaO /

(ii) H3O

Y.

X 3

COOH

(D) None of these

OMe

OMe

(A)

NBS

14

NH2

OMe

O
1

NH2

(iv)

Identify X and Y :

(B) CH3 C CBr3

(C) CH3 CH2 C CI3

(iii)

NH2

(ii)

NO2

CH3

(A) (ii) > (i) > (iii) > (iv) (B) (ii) > (iii) > (i) > (ii)
(C) (iv) > (i) > (iii) > (ii) (D) None

(A) CH3 C CCl3

(D)

(i)

Which of the following compounds yield most


Q.42
stable carbanion after rupture of (C1 C2) bond:
O

(B)

Cl

(I)
(II)
In addition of HOBr to (I) and (II)
(A) Br is at C2 in both cases
(B) Br is at C2 in II and at C1 in I
(C) Br is at C1 in II and C2 in I
(D) Br is at C1 in both cases
Q.36

CHCl Br

2
Product

Br

Q.41

Q.35

Br

(A) it is optically active (B) it is racemic mixture


(C) it is a resolvable mixture
(D) it is a mixture of erythro compounds
1

(D) Both (A) and (B)

Cl

CCl 4

CH3

Product is :

Br

Select the incorrect statement about the product


mixture in the following reaction:

Cl

KOH

Br

Q.34

CH3

Q.40

(D)

r
i
S
.
J
.
(C)

(B)

Cl

(B) CH3

CH3

Br

Cl

Cl

CHO

CCl4 / Peroxide

CHO

CH3

OMe

D O

2 Product(s)
Product(s) is/are :
14
14
(A) CH2 = CHCH2D (B) CH2 = CH CH2 D
(C) Both of these
(D) None of these

OMe

(B)
COONa

OMe

OMe

OMe

OMe

(C)

(D)
CHO

CHO

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44

OH

MgBr

(i) CH MgBr
CHBr3
P1
P3
P2 3

Q.43

KOH

(ii)H /

HN

P. Identify P.

Q.47

H2SO4

OMe

P1, P2 and P3 are


OMe

OMe

(A)

OMe

NH

(A)

(B)

O
R

CHOH

OH

(C)

Me
OMe

OMe

(B)

OMe

Me2CH
Me

CHO

CHOH

conc .H SO

2
4

r
i
S
.
J
.
(A) Me2CH NH C Me

OMe

OMe

OH
C=N

Major product of this reaction is

Me
OMe

(D) Both (A) and (C)

O
NH

Q.48
OH

NH

(C)

OMe

OMe

(B) Me NH C CHMe2

CH= CH2

CHO

OH

OMe

(D)

Me

CHO

(C) Me C CH = N Me

CH= CH2

OH

(C) CH2 = C CH = N Me

h /

Q.44


P.

Me

N3

'P' is:
(A)

OH

(B)

Q.49

N=N

(C)

Chloride

(D)

N=N

P Toluene sulphonyl

P. 'P' is

(A)

N=N

(B)

NH

NH

NH2

Q.45

NH

Br

(C)

KOH

CH3CH2CH2NH2. Compound (X) is


O

(A)

CH3

(B)

(C)

OH
Cl

Q.46

(D)

Cl

COOD

Q.50

product is

OD

(A)

(B)
C2H5

C NH2

C2H5

OD

(B)

CH2OD

(C)

(C) Me C NH Me

HN

C2H5

CHO

NH

C Cl

Which of the following can not give Hoffmann's


bromamide reaction:

(A) Me C NH Br

(D)

CH3

Cl

3
2
(X) C4H7OCl
C4H9ON

(D)
C2H5

(D)

C2H5

NH
O

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45

Q.1

EXERCISE II
Match the column :
Column-I
Column-II
(A) Electrophile (P) CH3 CH = CH CH3
(B) Nucleophile (Q) :CHCl

CH3

(C) Lewis acid (R) CH3 CH2


(D) Lewis base (S) Guanidine

(A)

Select the correct statements :


(A) Protonation increases electrophilic nature of
carbonyl group

(B) CF3SO3 is better leaving group than CH3SO3


(C) Benzyl carbocation is stabilized by resonance

(B)

CH3
H3C CH CH CH = CH2
CH3

(C)

H3C CH CH2 CH = CH CH3


CH3

(D) H3C CH CH = CH CH2 CH3

is unstable

r
i
S
.
J
.
CH3

OH

Q.3

CH3
H3C CH = CH CH
CH3

OH

(D) CCl3CH

Which of the following can be produced by Wurtz


reaction in good yield.
(A)
(B)

Q.8

Select correct statement about the product (P) of


the reaction :
H

Me

(C)

Q.5

(D)

Select true statement(s) :


(A) Instead of radical substitution, cyclopropane
undergoes electrophilic addition reactions in
sun light.
(B) In general, bromination is more selective than
chlorination
Q.9
(C) The2,4,6-tri-tert, butylphenoxy radical is
resistant to dimerization
(D) The radical-catalysed chlorination, ArCH3
ArCH2Cl, occurs faster when Ar= phenyl than
when Ar= p-nitrophenyl.
Q.10
Choose all alkane that give only one monochloro
derivative upon reaction with chlorine in sun light.
(A)

(B)

(C)

(D)

NBS

Q.6

(A) P is optically inactive due to internal


compensation
(B) P is optically inactive due to the presence of
plane of symmetry in the molecule
(C) The structure of P can have three optical
isomers possible
(D) P can have four possible optical isomers.
Products formed when HCl adds to 2,4-hexadiene
is:
(A) 4-chloro-2-hexene (B) 2-chloro-3-hexene
(C) 2-chloro-4-hexene (D) 1-chloro-2-hexene
HBr
In the given reaction C7H12 (A)

as major product

(B)

CH3

(D)

Which

of

following

reaction

CCl4

(B)

Br

Br

Br

(D)
Br

Q.7

Br

H3C CH2 CH2 CH2


OH

conc . H SO

4
2
X+ Y

(i) NaCN

(ii) H

CH3

(C)

(C)

are

CHO

Br2

CH3

(A)

(B)

Br

product

diastereomer of each other.

Br

(A)

CH2

CH =CH2
CH3

Q.11

CH3
Br

(A) can be

(C)

HBr

Br

(A)

(X)+(Y) enantiomeric pair.


CCl4 / h

Br / CCl

4
2
P

Me

Q.4

Product(s)

Product(s) are :

Q.2

(CH3 CH)2CuLi

NBS

CCl4 / peroxide

CH3

CH3
H

HBr

C=C

CCl4

(D) CH3 CH CH = CH Ph

HCl

peroxide

Et

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46

Q.12

Which of the following can be formed during this Q.16

Which of the following will give cyclic products

reaction?

upon being heated or being treated by an acid?


O

H3O

(A)

OH

OH

OH
OH

(B)
(A)

OH

(B)
OH

OH

OH

(C)
(C)

(D)

r
i
S
.
J
.
O

(ii) ROH

(iii) RNH2

P1, P2 and P3 are :


(A) MeO
NH2

(B) MeO

Q.17

(C)

(D)

Which of the following reaction is not representing Q.18


major product.
O

OH
+

CH3

C NH CH3

CH3
H

(B)

14

Cl
CH3

(C) Ph C NH
2
O

(D)

14

PhLi

C= C

3-hydroxy propanoic acid forms Lactide on


heating

NH C NHR

C= N

succinic acid forms succinic anhydride on


heating

N= C = O

MeO

(A)

Select the correct statements.

(B)

Q.15

P3

propanoic acid on heating

NH C OR

(C) MeO

Q.14

OH

P2

(A) methyl malonic acid is converted into

(D)

P1

NaN3

C Cl

MeO

OH

(D)

(i) H2O

Q.13

OH

OH

CC

N
Br2

CH3 C CH2COOH

forms acetone on heating


Soda lim e

C5H8O4(A) C4H8O2(B) (C)

C is a hydrocarbon occupying 0.509 litre per g at


NTP approximately. Hence A and B are:
(A) methyl malonic acid, propanoic acid
(B) succinic acid, succinic anhydride
(C) Dimethylmalonic acid, 2-Methylpropanoic acid
(D) Ethyl Malonic acid, Butanoic acid

CH3

Q.19

Which of the following reaction is not incorrectly


formulated.
SO Cl

2
(A) CH2=CHCH3 2

CH2ClCHCl CH3

UV light

CH

Ph NH2

KOH

(B) HC CH + CH2N2 HC

HN3
H2 SO4

In which of following compound chiral center is

HC

NH2

N
H
photo

(C) (CH3)3CH+Cl2
(CH3)3CCl
ha log enation

as major product

not affected on heating.


(A)

CH3 CH COOH
OH

(B)

O
HOOC CH3

HCl

(D) CH3 C C H CH3 CH CH2


Cl

Cl

(C) CH3 CH CH2 COOH (D) CH3 CHCOOH


OH

CH2COOH

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47

KNH

Q.20

Cl

Q.21

NH3 ,33C

Cl

KNH

liq. NH3

NH2

(A)

H2N

(B)

NH2

(A)

(B)

NH2
NH2

NH2

(C)

NH2

(C)

(D)

(D)
D

NH2

Q.22

This question consist of two statements, printed as assertion and reason, while answering this question you
are required to choose any one of the following responses.
(A) If assertion is true but the reason is false.
(B) If assertion is false but the reason is true.
(C) If both assertion and reason are true and the reason is a correct explanation of assertion
(D) If both assertion and reason are true but reason is not a correct explanation of assertion
NO2

Assertion :

r
i
S
.
J
.

PCl5

C= N
OH
OMe

O2N

C NH

OMe

OMe

Reason :

Migratory aptitude of

group is greater than migratory aptitude of

group during

NO2

cation rearrangements.
Q.23

Each of the compounds in Column A is subjected to further chlorination. Match the following for them.
Column-A
Column-B
(A) CHCl2 CH2 CH3
(P)
Optically active original compound
(B) CH2Cl CHCl CH3
(Q)
Only one trichloro product
(C) CH2Cl CH2 CH2Cl
(R)
Three trichloro product
(D) CH3 CCl2 CH3
(S)
Four trichloro product
Cl Cl

(E) CH3 C C CH3

CH3 CH3

Q.24

(T)

Atleast one of the trichloro product is optically active

(U)

Two trichloro products

Column-I and Column-II contains four entries each. Entries of column-I are to be matched with some entries
of column-II. One or more than one entries of column-I may have the matching with the same entries of
column-II and one entry of column-I may have one or more than one matching with entries of column-II.
Column-I
Column-II
(Reaction)
(Type of intermediate formed)
HO

(A) PhCHCl 2 (A)

(P)

Carbocation

(Q)

Carbanion

(R)

Free- radical

(S)

Carbene

Na

(B) R Br

dry ether

O
(i) Mg / H O

(C) CH C CH 2

3
3
(ii) H SO
2

CH3 OH

(D)

4,

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48

Q.25

Column-I

Column-II
O

(A) Caprolactum formation take place in

HN

(P)

H2SO 4

N OH

(B) Beckmann rearrangement is

(Q)

OH

(C) Schmidt reaction is

(i) CHCl / HO

(R)

(ii) H

OH

r
i
S
.
J
.
Ph

(D) Reaction in which number of carbon increases

PCl

C= N

(S)

CH3

EXERCISE III
Q.1

(ii) Ph CH = CH2 + N2

Identify P1 to P8.
CH3 CH = CH CH2

CH3

CH2
D

HBr

CH3

CH3 CH = CH CH2 CH CH2

HBr

Q.5

P1 + P2 + P3 + P4

CH3 CH = CH CH2 CH CH2 CH CH3


D

P1 + P2 + P3 + P4 + P5 + P6 + P7 + P8

HBr

Compare the rate of decarboxylation in sodalime Q.6


process for the following.
(i) (a) HC C COOH (b) CH2 = CH COOH
(c) CH3 CH2 COOH
(ii) (a) CH2 CH2 COOH (b) FCH2 CH2 COOH

(c)

(a)

Formulate the reactions between but-1-ene


in presence of small amount of benzoyl
peroxide and (i) CCl4
(ii)
CBrCl3
Give your reasons.
(b) The dichlorocarbene reacts with phenol in
base where as it doesn't reacts with
benzene explain.
Give the product of the following reaction.
O

Mg

(i)

A
H2O

(ii)

CH = O

Mg

CH = O

(c) Cl CH2CH2 COOH


(iii) (a) CH3 CH COOH (b) CH3 CH COOH

H2O

(iii)

Cl

Mg

Me C Et

H2O

(iv)

Which compound is more stable explain.

Q.7

(a) CH3 C CH = N = N and CH3 CH = N =

Ph C Me

MeOCH Cl
BuLi

CHBr

3

?
t

BuOK

H SO

Br

H SO

2
4
(B) 2

(D) = ?
(C)

CCl 4

Give product and suggest mechanism for these


reactions.
(i) ? 2

Mg

H2O

2
D

Identify missing products in the given reaction


sequence.
Br2 / h
aq. KOH
(a) CH3 CH2 CH3
(A)

Q.4

CH3 CH COOH

H SO

2
C

CH3

Q.3

B. Find

CH2 CH2

out A & B.

(iii) Cl3C C OH + Na A

P1 + P2

NO2

Zn

Q.2

CO2Et ?

O
C Cl

(b)

NaN

Ag O

3
2

(P)
(Q)

H2O

NaNO 2

(R) (S)
HCl

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49

Q.8

Find out the total number of products (including


stereo) in the given reaction:

OH
CH3

CH3

NBS,CCl

4

Products.

X CH2 CH2 XCH2 C H2 + H X

heat

CH3

XCH2 CH3 + X

conc .

+ H2O

H2SO 4

HCl
HBr
HI

67
25.1
+46

Q.10

Addition of small amount of (C2H5)4 Pb to a


mixture of methane and chlorine, starts the
Q.16
reaction at 140C instead of the usual minimum
250C. Why?

Q.12

1,2-Dimethylcyclohexene
Isopropylidenecyclopentane

(a) Write a reasonable and detailed mechanism


for the following transformation.

Q.11

C(CH3)2

2,2-Dimethylcyclohexanol

With the help of following data show HBr exhibits


Q.15
the peroxide effect.
1
1
H1/ kJ mol
H2/kJ mol

H X X + CH2 = CH2

CH3

Peroxide ,

Q.9

CH3

+ 12.6
50.2
117.1

OH

(b)

HO

OH

H / HOH

r
i
S
.
J
.

On chlorination, an equimolar mixture of ethane


and neopentane yields neopentyl chloride and
ethyl chloride in the ratio 2.3 : 1. How does the
reactivity of 1 hydrogen in neopentane compare
with that of a 1 hydrogen in ethane?

It required 0.7 g of a hydrocarbon (A) to react


completely with Br2(2.0 g) and form a non
resolvable product. On treatment of (A) with HBr it Q.17
yielded monobromo alkane (B). The same
compound (B) was obtained when (A) was treated
with HBr in presence of peroxide. Write down the
structure formula of (A) and (B) and explain the
reactions involved.

- Terpeniol

Geraniol

Assuming that cation stability governs the barrier


for protonation in HX additions, predict which
compound in each of the pairs in parts (a) and (b)
will be more rapidly hydrochlorinated in a polar
solvent.
(I)
(II)
(a)
CH2 = CH2
or
(b)

or

Choose the member of the following pairs of


unsaturated hydrocarbons that is more reactive
towards acid-catalysed hydration and predict the
regiochemistry of the alcohols formed from this
compound.
(a)
or

Q.13

Give product(s) in each of the following reactions.

Br / h
(a) CH3 CH CH2 CH2 CH3 2 (A)(major)

CH3

(C H CO) O

+ NBS 65 2 (B)
S

(b)

or

(i)

CH3

(b)

CH3

(c)

or

CH3

(ii)

Give product in the following reaction.


(i)
NaNO
2

CH3 C O Cl /

(d)C6H5CH2CH2CH3

(ii)

(i)

(c) CH3CH2CH=CH2+Me3COCl
(C) + (D) Q.18

Q.14

(ii)

(i)

NH2

(E)(major)

We saw that acid-catalyzed dehydration of 2,2dimethyl-cyclohexanol


afforded
1,2dimethylcyclohexene. To explain this product we
must write a mechanism for the reaction in which
a methyl shift transforms a secondary carbocation
to a tertiary one. Another product of the
dehydration of 2,2-dimethylcyclohexanol is
isopropylidenecyclopentane. Write a mechanism
to rationalize its formation.

(ii)

HCl

NH2

NaNO2
HCl

NH2

CH2NH2

(iii)

NaNO2
HCl

(v)

NaNO2

OH NH2

HCl

(iv)

NaNO2
HCl

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50

Q.19

What are the products of the following reactions?


(B) CH3CH2CHBr

(a) PhCH = CHCH3 + HBr A


H3C

(b)

CH3
C=C

H3C

+ HI B

Peroxide

(c)

Q.5

CH3

+ HCl D
CH2CH3

Complete following reaction:


HCl

Br2
CCl4

(b)

CH2

CH3
CS2

Reaction of RCO NH2 with a mixture of Br2 and


KOH gives R NH2 as the main product. The
intermediates involved in this reaction are :
Q.8
[JEE 1992]
(A) R CO NHBr
(B) RNHBr
(C) R N = C = O
(D) R.CO.NBr2
Which one of the following has the smallest heat
Q.9
of hydrogenation per mole?
[JEE 1993]
(A) 1-Butene
(B) trans-2-Butene
(C) cis-2-Butene
(D) 1,3-Butadiene
In the following compounds :
OH

N
OH

The reaction of CH3CH=CH


HBr gives :
(A) CH3CHBrCH2

OD

The correct order of basicities of the following


compounds is:
[JEE 2001]
NH

CH3CH2NH2

NH2

(1)

(2)

(CH3)2NH

CH3CNH2

(3)

(4)

(B) 1 > 3 > 2 > 4


(D) 1 > 2 > 3 > 4

Q.10

Left to right sp , sp , sp, sp hybridization is


present in :
[JEE 2003]
(A) H2C = CH C N (B) H2C = C = CH CH3
(C) HC C C CH (D) HC C CH = CH2

Q.11

Maximum dipole moment will be of: [JEE 2003]


(A) CCl4
(B) CHCl3 (C) CH2Cl 2 (D) CH3Cl

OH with

[JEE 1998]
OH

Amongst the following, the most basic compound


is
:
[JEE 2000]
(A) C6H5NH2
(B) p-NO2C6H4NH2
(C) m-NO2C6H4NH2
(D) C6H5CH2NH2

(A) 2 > 1 > 3 > 4


(C) 3 > 1 > 2 > 4

NO2

(D) CD2 = C CD3

A solution of (+) 1-chloro-1-phenylethane in


toluene racemizes slowly in the presence of small
amount of SbCl5 due to formation of:
[JEE 1999]
(A) carbanion
(B) carbene
(C) free radical
(D) carbocation

OH

(I)
(II)
(III)
(IV)
The order of acidity is :
(A) III > IV > I > II
(B) I > IV > III > II
(C) II > I > III > IV
(D) IV > III > I > II
Q.4

(B) CH3 C CH3

CH3 C = CH2

CH3 C

[JEE 1996]

NO2

CH3

[JEE 1999]

The enol form of acetone, after Prolonged


treatment with D2O, gives:
[JEE 1999]
O
OD

(C) CH2 = C CH2D

EXERCISE IV (A)

OH

An aromatic molecule will:


(A) have 4n electrons
(B) have (4n +2) electrons
(C) be planar
(D) be cyclic

(A)

Total number of products obtained in this reaction


Q.7
is?

Q.3

Br

OH

Cl2

(c)

Q.2

(D) CH3CH2CHBr

r
i
S
.
J
.
Q.6

CH3

Q.1

Br

+ HBr
C

(d)

(a)

(C) CH3CHBrCH2

CH3

Q.20

OH

OH

COOH

Q.12
H
O 2N
M

OH

when X is made to react with 2 eq. of NaNH2 the


product formed will be :
[JEE 2003]

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51

Q.18
OOC

OH

(A)

OOC

(B)
H

OH

O2N
M

OH

O 2N
M

OOC

(D)

CH3

OH

O2N
M

Ph MgBr +CH3 C OH

r
i
S
.
J
.
CH3

(A)

[JEE 2004]

(B) CH3 C OPh


CH3

COOH
x

Correct order of acidic strength is:


(A) x > y > z
(B) z > y > x
(C) y > z > x
(D) x > z > y

OH

CH3

(C)

(D) CH3 C Ph

Order of rate of reaction of following compound


with phenyl magnesium bromide is: [JEE 2004]
Ph C Ph

Me C H

O
(I)

(II)

(III)

(A) I > II > III


(C) III > I > II
Q.15

Q.19

CH3

NH3

H3N
z
M

O2N
M

Q.14

HOOC

OH

(C)

Q.13

For 1-methoxy-1,3- butadiene, which of the


following resonating structure is the least stable?
[JEE 2005]

(A)
H2 C CH CH CH O CH3

(B) H C CH CH CH
O CH3
2

(C)
H 2 C CH CH CH O CH3

(D) H C CH CH CH
O CH3
2

Me C Me

(B) II > III > I


(D) II > I > III

CH3

Q.20

When benzene sulfonic acid and p-nitrophenol


are treated with NaHCO3, the gases released
respectively are
[JEE 2006]
(A) SO2, NO2
(B) SO2, NO
(C) SO2, CO2
(D) CO2, CO2

Q.21

(I) 1,2-dihydroxy benzene


(II) 1,3-dihydroxy benzene
(III) 1,4-dihydroxy benzene
(IV) Hydroxy benzene
[JEE 2006]
The increasing order of boiling points of above
mentioned alcohols is
(A) I < II < III < IV
(B) I < II < IV < III
(C) IV < I < II < III
(D) IV < II < I < III

Q.22

CH3NH2 + CHCl3 + KOH Nitrogen containing


compound + KCl + H2O. Nitrogen containing
compound is
[JEE 2006]
(A) CH3 C N
(B) CH3 NH CH3

1-Bromo-3-chloro cyclobutane on reaction with 2equivalent of sodium in ether gives [JEE 2005]
Cl

Br

(A)

(B)

(C)

(D)

SO3H

CH3COONa(excess)

Q.16

(aq. solution)

Me

[JEE 2005]

(D) CH3N C

(C) CH3N C

SO2COOCH3

(A)

(B)

Me
SO3Na

(C)

Question No. 23 to 25 (3 questions)


Comprehension I
RCONH2 is converted into RNH2 by means of
Hofmann bromamide degradation.

COONa

+ CH3COOH

(D)

+ H2SO4

Cl

Cl

NH2

Me

Q.17

Me

Conversion of cyclohexanol into cyclohexene is


most effective in:
[JEE 2005]
(A) concentrated H3PO4 (B) concentrated HCl
(C) concentrated HCl/ZnCl 2
(D) concentrated HBr

Cl
(ii)

(i)

(iii)

OM

O
C

O
H2N

NBr

NHBr

Cl

Cl

Cl

H
(vi)

(v)

(iv)

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52

In this reaction, RCONHBr is formed from which


this reaction has derived its name. Electron
donating group at phenyl activates the reaction.
Hofmann degradation reaction is an
Intramolecular reaction.

Q.28

The structure of the intermediate I is: [JEE 2007]

ONa

CH2Cl

CHCl2

(A)

(B)
CH3

Q.23

Q.24

Q.25

How can the conversion of (i) to (ii) be brought


about?
[JEE 2006]
(A) KBr
(B) KBr + CH3ONa
(C) KBr + KOH
(D) Br2 + KOH

15

CH2OH
2

CCl3

(C)

(D)
CH3

CH3

Q.29

Hyperconjugation involves overlap of the following


orbitals:
[JEE 2008]
(A) (B) p (C) p p (D)

r
i
S
.
J
.

The correct stability order for the following


species is:
[JEE 2008]

(I)

(ii)

(i)

ONa

ONa

What are the constituent amines formed when the


mixture of (i) and (ii) undergoes Hofmann
Q.30
bromamide degradation?
CONH2

CH3

Which is the rate determining step in Hofmann


bromamide degradation?
[JEE 2006]
(A) Formation of (i)
(B) Formation of (ii)
(C) Formation of (iii)
(D) Formation of (iv)

CONH2

ONa

(II)

NH2

NH2

NH2

NH2

NH2

(C)
(D)

15

NH2

NH2

15

NHD

Q.31

15

NH2

(III)
(IV)
(A) (II) > (IV) > (I) > (III) (B) (I) > (II) > (III) > (IV)
(C) (II) > (I) > (IV) > (III) (D) (I) > (III) > (II) > (IV)

15

(B)

15

15

(A)

In the following carbocation , H/CH3 that is most


likely to migrate to the positively charged carbon
is
[JEE 2009]

[JEE 2006]

HO

4 5

H3C C 3C C CH3

Paragraph for Question Nos. 26 to 28 (3 questions)


Riemer-Tiemann reaction introduces an aldehyde
group, on to the aromatic ring of phenol, ortho to
the hydroxyl group. This reaction involves
electrophilic aromatic substitution. This is a
general method for the synthesis of substituted
salicylaldehydes as depicted below.

ONa

OH

CHO

(I)
(Intermediate)
CH3
(I)

Q.26

Q.27

(B) H at C-4
(D) H at C-2

EXERCISE IV (B)

Q.1

OH

Complete the following, giving the structures of


the principal organic products: [JEE 1997]
(a)

CHO

Ph

+ KNH2

aq.HCl

CH3
(II)

CH3

(A) CH3 at C-4


(C) CH3 at C-2

Ph

(b)

CH3
(III)

Br

+ CHBr3 + t- BuOK

Q.2
Write the intermediate steps for each of the
Which one of the following reagents is used in the
following reaction.
[JEE 1998]
above reaction?
[JEE 2007]

H
O
3
(A) aq. NaOH + CH3Cl (B) aq. NaOH + CH2Cl2
(i) C6H5CH(OH) C CH
C6H5CH = CH CHO
(C) aq. NaOH + CHCl 3 (D) aq. NaOH + CCl 4
The electrophile in this reaction is [JEE 2007]
(A) : CHCl
(B) +CHCl2
(C) :CCl2
(D) CCl 3

(ii)

OH

CH3

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53

Q.3

Out of anhydrous AlCl3 and hydrous AlCl3 which


is more soluble in diethyl ether?
Explain with reason.
[JEE 2003]

Q.4

Match Ka values with suitable acid: [JEE 2003]

(i)

Ka
5
3.3 10

(ii)

4.2 10

(iii)

6.3 10

(iv)

6.4 10

(v)

Acid
(a)

NH3

NH3

COOH
COOH

MeO

(e)

OH
Which of the following is more acidic and why?
[JEE 2004]

COOH

Cl

(d)

Give resonating structures of the following


compound.
[JEE 2003]

Me

(c)

30.6 10

Q.6
COOH

(b)

Q.5

r
i
S
.
J
.
F

COOH

O2N

ANSWER KEY
EXERCISE-1

Q.No.
Ans.
Q.No.
Ans.
Q.No.
Ans.
Q.No.
Ans.

1
B
16
C
31
B
46
C

2
B
17
B
32
C
47
D

3
C
18
C
33
D
48
B

4
C
19
A
34
A
49
C

5
D
20
A
35
C
50
A

6
B
21
D
36
A

7
C
22
C
37
C

8
B
23
D
38
A

9
D
24
C
39
B

10
D
25
B
40
C

11
A
26
D
41
B

12
D
27
D
42
C

13
C
28
B
43
D

14
C
29
C
44
B

15
B
30
A
45
A

EXERCISE-II

Q.No.
Ans.
Q.No.
Ans.
Q.No.
Ans.
Q.No.
Ans.

1
8
A,B,C
19
A,C,D
24

Q.1

A
Q,R
9
A,B
20
B,C
A
Q,S

B
P,S
10
A,B,C
21
A,C
B
Q,R

C
Q
11
A,B,D
22
B
C
P,R

N
H

P1 = CH3C CH2 C CH2 C CH3


Br

P3 = CH3C CH2 C CH2 C CH3


Br

D
P,S
12
A,B,D
23

2
A,B,C
13
A,B,D
A
S,T

D
P

25

3
B,D
14
A,B,D
B
P,S,T
A
P,Q

4
B,C,D
15
A,B,D
C
U
B
Q,S

5
A,B,D
16
A,B,C
D
Q
C
P

6
B,D
17
A,B,D
E
T,U
D
R

7
B,C
18
C,D

EXERCISE-III
Br

P2 = CH3C CH2 C CH2 C CH3


H
Br

D
D

T
H

P4 = CH3C CH2 C CH2 C CH3


H

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Br

Br

Q.2

P8 = CH3 C CH2 C CH2 C CH3

P7 = CH3C CH2 C CH2 C CH3


H

P6 = CH3C CH2 C CH2 C CH3

P5 = CH3C CH2 C CH2 C CH3


Br

Br

(i) a > b > c; (ii) a > b > c ; (iii) b > a > c Q.3

(a) Due to Resonance

Br

Q.4

(i)

OMe (ii)

&
Br

(iii) A : CCl2

B:
Cl

Q.5

(a) Free radical mechanism

(a)

CH3 CH2 CH3

(b) Due to more electron density

Br2/h

Br2
CCl4

CH2 CH CH3

aq.KOH

CH3 CH CH3
(B)

CH2 = CH CH3
(C)

Br
(D)

C Cl

C N3

(b)

OH

CH3 CH CH3
(A)

Br

r
i
S
.
J
.

Cl

Br

Q.7

COOEt

Ph

NaN3

OH

N=C=O

Ag2O

NH2

NaNO2

H 2O

+HCl

CH3

CH2 Br

CH2
Br

Q.8

and its enantiomer,

CH3

and its enantiomer,

Br

CH3

Br

and its enantiomer,

Q.11

1.15 times more reaction

Q.13

(a) A :

Br

CH3

Br

Q.12 A =

Br
CH3 C CH2CH2CH3

(c) C: CH3 CH CH = CH2


Cl

CH3

D: CH3 CH = CHCH2Cl

CH2Br

(b)B :
S

(d) E:

Ph CH Et
Cl

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55

OH

Q.15

(b)

HOH/H

OH

Q.16

(a) II, (b) I

Q.19

(a)

Q.17 (a) II, (b) I, (c) II


(b) Me2C(I) Et,

Ph CH Et

(c)
Br

Br

CH3

Q.20

(a)

Cl

r
i
S
.
J
.

CH3

CH3

CH3
Br

Br

(b)

(diastereoisomers)

+
Br

Br

Me

Me

Me
Et

Et

(diastereoisomers)

+
Cl

(c) H
H

Cl

(d)

Me
H
H

Cl + Cl
Cl Cl

(Enantiomers)

Et

EXERCISE IV(A)

Q.No.
Ans.
Q.No.
Ans.
Q.No.
Ans.

1
C
16
C
31
D

2
D
17
A

3
D
18
C

4
B
19
A

5
B,C,D
20
D

N
Br

Q.1

7
D
22
D

8
D
23
D

9
B
24
D

10
A
25
B

11
D
26
C

12
C
27
C

13
D
28
B

14
B
29
B

15
C
30
D

EXERCISE IV(B)

(A) PhC CPh, (B)

C6H5CH C CH

Q.2

6
D
21
C

OH

C6H5CH C CH

H2O

C6H5CH C CH
+

OH2

OH2

C6H5CH =C = CH

H2O

C6H5CH =C = CH

C6H5CH =C = CH
+

tautomerism

C6H5CH =CH CHO

OH2

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+
H

(ii)

OH

OH

H +
+

O|

CH3

CH3

Q.3

Anhydrous AlCl 3 is more stable then hydrous AlCl3 because it is having vacant 3p orbital of Al which can
accept lone pair of electrons from oxygen of diethylether.

Q.4

(i)-(d), (ii)- (b), (iii) (a), (iv) (c), (v)-(e) Q.5

r
i
S
.
J
.

OH

NH3

Q.6

is more acidic as overall effect of F is electron withdrawing so loss of portion is easier from this

compound.

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