RM

i r
REACTION
MECHANISM
.S
. J
N
1
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IIT-JEE ChEmistry by N.J. sir ORGANIC chemistry
DPP NO-01 Time: 15 minutes
Q.1
CH3
(a) CH3—CH2—CH2  _____ (o) CH3— C — C = O: _ _ _ _ _ _ _ _ _
:
(b)  _ _ _ _ _ _ _ H
CH—OH
2
(c)  _____
(p)  _______ _
CH3
(d)  _ _ _ _ _ CH2
CH3—CH2—CH2—C—CH2
(q)   _________
r
CH3
CH2
i
(e)   ________
(r)  _________
(f)  _________

(s)  ________
S
`
(g)  _ _ _ _ (t)   _________
Ph—CH2—CH2
.
CH3
(h)  ___
CH3—CH—CH2—CH2
(u)  _______ _
J
Ph Me
(i) Ph—C— CH—CH2—CH2  ____
.
D
Ph
(j) CH3–O C—CH2—CH2—CH2
 _ _ _
Ph
(v)   _________
(k)  _ __ _ _ _ _ _
N
OH
(w)  _ _ _ _ _ _ _ _ _
(l) CH3—CH—CH2—OH  _ _ _ _ _ _

OH
OH
(x)  ________
(m)  _________
`
CH3 Me
(n) CH3—C— C—et _ _ _ _ _ _ _ _ _
OH
2
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Dehydration of Alcohol H /   _ _ _ _ _ _ _
Conc.H2SO4 CH3—CH=CH2 Q.11 OH 
Q.1 CH3—CH2—CH2—OH  
170C
Mechanism:– Q.8 3, 3–Dimethyl–butan–2–ol loses a molecule of

 water in the presence of concentrated sulphuric
(1) CH3 — CH2 — CH2 — O
 — H + H+ CH 3 — CH2 — CH2 —
acid to give tetramethylethylene as a major product.
rds Suggest a suitable mechanism.
Electrophilic addition:–

CH—CH—CH   CH3 — CH2 — CH2  +  ENu 
3 3
C=C  C—C
r
H E Nu

(2) CH3 — CH — CH3 + :O: CH3—CH=CH2+ H3O+
i
H Mechanism:–
Energy profile diagram:—
C=C + E  —C — C—
E 
E
S
:
Nu
Reaction
Nu
.
Q.1 H /   _ _ _ _ _ _ _ —C — C—
OH 
H /   _ _ _ _ _ _ _ E
Q.2  Q.1 Compare rate of electrophilic addition on alkenes:–
OH
J
(a)
Q.3 H
/ _ _ _ _ _ _ _ (i) (ii) (iii) (iv)

OH
.

H / _ _ _ _ _ _ _ (b) CH = CH2 CH = CH2 CH = CH2
Q.4 OH 
Conc.H2SO4
Q.5  _ _ _ _ _ _ _
OH 
Conc.H2SO4 NO2
Q.6  _ _ _ _ _ _ _ CN
 (i) (ii) (iii)
OH
N
OH CH = CH2 CH = CH2
Q.7
H  _ _ _ _ _ _ _


OH Conc.H2SO4
Q.8  _ _ _ _ _ _ _
 O – Me NH2
(iv) (v)
OH
Q.9 H /   _ _ _ _ _ _ _
 COOH
(c)
(i) (ii) (iii) (iv) (v)
OH (d) Ph — CH = CH2 PH — CH = CH — Ph
Q.10 H /   _ _ _ _ _ _ _
 (i) (ii)
3
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Q.1
HI
CH2 = CH2  _ _ _ _ _ _ _ _ _ _ Q.15 HCl(2eq.)
CH3 — C  CH   __________
Q.16 HCl  _ _ _ _ _ _ _ _ _ _

Q.2 KBr
CH2 = CH2  __________
Q.17 dil.H2SO4
HI   __________
Q.3  __________
KBr
H /H2O
Q.18   __________
Q.4 HI __________
C = CH2 
KBr
Q.19 H /R–OH  _ _ _ _ _ _ _ _ _ _

Q.5
Q.6
HI  _ _ _ _ _ _ _ _ _ _

KF
HI  _ _ _ _ _ _ _ _ _ _

Q.20
Q.21
H
Me
D
H /H2O

i r
 __________
HCl  _ _ _ _ _ _ _ _ _ _

S
CH = CH2
.
Q.22 D /D2O
Q.7 HCl  __________   __________

O
J
O
H+ H
Q.23 __________
.
Q.8 HI  _ _ _ _ _ _ _ _ _ _

Q.24 HBr
 __________
Q.9 HI  _ _ _ _ _ _ _ _ _
(Ph)2 CH—CH—CH=CH2  HCl  _ _ _ _ _ _ _
Q.25 CH  C — CH2 — CH = CH2 
Me
N
Q.26 CH  C — CH = CH2 HCl 
 __________
Q.10 HBr __________
C = CH—Ph 
Q.27 H
HO—CH2—CH2—CH2—CH = CH2  ___
MeOH
Q.11 HCl  _ _ _ _ _ _ _ _ _ _
 OH

H /MeOH  _ _ _ _ _ _
Q.28 CH2= CH—CH—CH=CH2 
Q.12 HBr
 __________ H  _ _ _ _ _ _ _ _ _ _
Q.29 
O
H
Q.13 HCl  _ _ _ _ _ _ _ _ _ _
CH2 = CH — Cl 
Q.14 HCl(2eq.)
CH  CH   __________
4
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Q.1 OH OH
O H H H 
CH3—CH—CH—CH3 H 

Q.3 

 CH3—CH2—C—CH3
OH OH
OH OH
Mechanism:– CH3 CH 3
(1)
+ Q.4
H 

CH3 —CH—CH—CH 3 +H
+
 H2 O + CH 3—CH—CH—CH 3

:
:O–H O–H O–H
r
OH OH
Q.5
H 

CHO
3 C—C— 
i
H H
+ OH OH
s  CH3 — CH 2—C—CH 3  CH3 — CH 2—C—CH 3
:
O—H Q.6
H 

+ O—H 
CH3 CH 3 OH OH
S
H  H 
Q.1 Et — C — C —Et 
 Q.7 

.
OH OH
Ph
H  Diazotization of primary amine:–
Q.2 Ph— C — CH 2 

 NaNO2
OH OH R — NH2   R — N  N :  
 R  N2
HCl
J
Mechanism:–
.
(1) NaNO2 + HCl  H—O—N=O + NaCl
:
(2) H — O — N = O + H H2O + N=O

+
H H H
:
:
:
(3) R—N: + N = O  R—N — N = O  R—N—N = O—H

:
N
H H
H
: :
R—N= N—O—H
 H H
:
:
N2  R  R — N  N :  R—N = N + O  R—N = N—O: 

H H
5
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Demjanov Reaction:–
OH NH2 O OH NH2
Q.4 NaNO2
NaNO2
CH3 — CH—CH—CH3   CH 3 — C—CH 2—CH3 CH3 — CH —CH—   _______
HCl HCl
Q.5 SbCl5 __________

Mechanism:– 
 
(1) Cl O—H
OH NH2 OH
NaNO2 OH
CH3 — CH—CH—CH3 
HCl
 CH3 — CH—CH—CH3 + N2
Br
 Q.6 AlBr3 __________

 
O OH
H + CH3 — C—CH2—CH3  CH3 — C—CH2—CH3 
r
OH NH2
NaNO2 AgI
Q.1   __ Q.7 
  __________
CH — CH — —OCH3 HCl
I O—H
i
NH2
Q.2 NaNO2 __________
  OH
HCl aq.AgNO3
OH Q.8   __________

NH 2 OH I
Q.3 NaNO2
  __________
HCl
IIT-JEE ChEmistry by N.J. sir

DPP NO-04
Non Classical Carbocation:–
.S Q.4
Br2

ORGANIC chemistry
Time: 15 minutes
_ _ _ _ _ _ _
J
Nu CCl4
E—Nu 

C=C —C — C—
Q.5 ICl  _ _ _ _ _ _ _
CH3 — CH = CH2 
.
E
Mechanism:– Q.6 HOCl  _ _ _ _ _ _ _
CH3 — CH = CH2 
(1)  —C — C— Cl2

:
C=C + Nu Q.7  _ _ _ _ _ _ _

CCl4
E
E
Nu
N
Br2
Q.8  _ _ _ _ _ _ _ _ _
CCl4
Nu
Q.9 Br2 /H2O
—C — C—   _______
E
Br2
Q.10  _______
2 Br H2O
Q.1 CH2 = CH2   _______
Q.2 CH2 = CH2 Br2 _ _ _ _ _ _ _ Br2 /CCl4
O Q.11  _______
(1eq.)
H H
Br2
Q.3  _ _ _ _ _ _ _
CCl4
6
----------------------------------------------------------------------------------------------------
H Diel’s Alder Reaction:–
N Br2 (CCl4 )
Q.12   _______ + ||  
(1eq.)
Q.13 HCl  _ _ _ _ _ _
CH3 — CH = CH2  COOH
Q.1 + 
CH3Cl / AlCl3
COOH
CH3Cl COOH
Q.2 + 
H H–O CH3
Q.14 ______ HOOC
Q.3 + 
r
NO2
Q.15 HCl  _ _ _ _ _ _

CH3 O—
Q.4 + 
i
Q.13 The reaction of propene with HOCl proceeds via
the addition of [IIT '2001]
(A) H+ in first step Q.5 + 
+
(B) Cl in first step
(C) OH– in first step
(D) Cl+ and OH– in single step Q.6 + 
S
Ans. B
.
OH
H  x
Br2
Q.18 
   5 compounds of
(mixture)
H 2O Q.7 + 
molecular formula C4H8Br2 [IIT '2003]
Number of compounds in X will be :
(A) 2 (B) 3 (C) 4 (D) 5
J
Ans. B
Q.8 + 
Q.23 CH3 – CH = CH2 + NOCl  P [IIT '2006]
.
Identify the adduct.
(A) CH3 – CH – CH2 (B) CH3 – CH – CH2
Cl NO NO Cl
NO Q.9 + 
(C) CH3 – CH2 – CH (D) CH2 – CH2 – CH2
N
Cl NO Cl O
Ans. A
Q.10 + O

Q.26 The number of stereoisomers obtained by
bromination of trans-2-butene is [IIT '2007]
(A) 1 (B) 2 (C) 3 (D) 4 O
Ans. A
Q.11 + 
Q.5 Write down the structures of the stereoismers
formed when cis-2-butene is reacted with bromine.
[IIT '1995]
Me Me
Q.12 O + 
H Br + Br H
Ans. Br H H Br
Me Me
7
----------------------------------------------------------------------------------------------------
DPP NO- 05 Time: 15 minutes
Fill in the blanks:–
O
CH3

Q.1 OH H


OH
H
Mechanism :–
CH3 O
OH
(i) + H+  H H  
OH
H Intermediatecarbocation 
r
Rearrargemet
(ii)    
Intermediatecarbocation  Re arrangedcarbocation
i
O
+
(iii)   H +
Re arrangedcarbocation
(iv) [H ] = - - - - - - - - - - - - - - -
t
S
(v) Name of Reaction is - - - - - - - - - - - - - - - -
OH OH
.

H
Q.2 CH3 — O C C CH3 

Product
H
Mechanism : –
J
OH OH
CH3 — O C C CH3 + H  Intermediate Carbocation
.
H 
Intermediate Carbocation  rearrangedCarbocation

(i)  
RearrangedCarbocation  H+
N
(ii) Pr oduct


NH2 OH
NaNO2 |HCl.
Q.3 PH C C CH3   Pr oduct
H H 
Mechanism : –
NH2 OH
NaNO2 |HCl.
(i)
PH C C CH3
  ---- ---------
H H
Rearrangement
H+ + - - - - - - - - - - -  - - - - - - - - - - - -
None of Reaction - - - - - - - - - - - - - -
8
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CH3 CH3
Q.4            Q.5 CH3 — C°H2 + CH3 — C°H2           
CH3 C° + CH3 C°
(Major Pr oduct) (Major Pr oduct)
CH3 CH3
H H
O
+
Q.6 C + C Ph C C CH = CH 2  H / Ph H
      Q.7
(explain) CH 3 CH3
Mechanism : –
H H  
(i) +H 
Ph C C CH = CH2
(Intermediate1 )
CH 3 CH 3
r
(Rearrangement)
Nucleophile 
Pr oduct   Intermediate3  (Intermediate2 )
i
  
HCl | CCl 4 HBr
A B
CCl4
Q.8 Ph—CH= CH 2
S
D C
HCl HBr
R–O–O–R/CCl 4 (R–O–O–R)/CCl 4
.
CH3 CH3
Br /h aq.KOH
Q.9 CH3   A 

2 2
CH3 C CH2 CH3 C CH2 CH3
H OH
J
Conc. H2SO4
.
HBr(R–O–O–R)
C   B
CCl4
A & C are Idenitcal / Isomers / Positon Isomers.
   
Ph O
Q.10 NaOH
N
Ph C C OH 
electrolysis
Ph
Anode Cathode
Ph O
(I) _ _ _ _ _ _ _ _ _ e— + Ph C C O° (i) 2H2O + 2e— _ _ _ _ _ _
Ph
Ph O
(ii) Ph C C O° CO2 +        
Ph Intermediate
(iii) Intermediate - - - - - - - - - - - -

9
----------------------------------------------------------------------------------------------------
1. Which of following carbocation will undergo Ph — CH — Ph
rearrangement? CH2 — CH2 — OH
+ + H 
CH2 CH2 3. 

(a) (b) (c) (d) (A) , Major product (A) is

+
+ (major)
+ Ph — C — Ph
+
+
+ CH2 — CH3
(e) (f) (g) (h) (A)
r
O
Ph — CH — Ph
i
Ph
+ CH — CH3
(i) CH2 — O — CH2 — CH2 — CH2
+ (B)
(j)
Ph — CH — Ph
S
+ CH — CH2
CH2
+ + (C)
.
(k) (l) (m) CH3
Ph
+
Ph — C — OH
Ph
+ CH2 — CH3
J
+
(n) CH2 — CH2 — CH2 (o) (p) CH2 — C =O (D)
CH3 — CH2 — O
.
+
(q) CH OH
4. Reaction-1
H 

  (A)
(r) CH3CH2CH2+ (s) (CH3)2 CH CHCH3 (major)
N

(t) (CH3)3 C CHCH3 (u) (CH3CH2)3CCH2+
CH2—OH Reaction-2 H 

 (A)
H  (A)

2.
 OH (major)
(A) an heating isomerizes to (B). What is the H 

structure of (B). Reaction-3 
 (A)
CH3 OH OH
(major)
(A) (B) (C) (D) Sum of -hydrogen (A + B + C) is.
5. (A) H  (x)


OH
10
----------------------------------------------------------------------------------------------------
H  (y) OH
(B) 

OH H  (B)
Reaction-2 

OH
(C)
H  (z)

 OH
H  (p) Reaction-3
H  (C)

(D) 
 
OH
Total number of products obtained in above OH

reactions including minor products is (include
stereoisomer)
Reaction-4
H  (D)

x y z p 
r
6. In which of following reaction rearrangement take
Sum of -hydrogen is A+B+C+D=
i
place with change is carbon skeleton.
CH3
8. In which of following reaction resonance stabilized
(A) CH — C — CH + (B) CH3 — CH2 CH2  product will form.
3 2
CH2—OH
(A) H 

CH3 
(C) +
S
CH3 — CH — CH2 — CH2 OH
(B) H 

CH3 
.
(D) CH3 — CH  — CH3
CH3
7. Sum of -hydrogen in major product of the (C)
H 

OH 
reaction.
OH
(D) All
J
Reaction-1
H  (A)


.
N
11
----------------------------------------------------------------------------------------------------
Q.1 Compare rate of dehydration (acid-catalyzed) OH
OH OH (h) H
 A+B


H
(i) H H 

A+B
(a) CH3 OH
CH3
OH OH (j) H


A+B

(b) OH
r
OH OH OH KHSO4
(k) 
170 C

i
OH
(c) (d) OH H2 SO4
OH (l) 
OH
OH (m)
H2 SO4

OH 
CH3
S
(e) OH
H2 SO4
(n) 
.
Q.2 Predict the major product of acid-catalyzed OH 
H
dehydration of alcohols (o) 

(A) 2-pentanol
CD3
(B) 1-methyl cyclopentanol OH
(C) 2-methyl cyclohexanol
J

(D) 2, 2-dimethyl-1-propanol (p) H


Q.3 Identify-Product
.
OH
H2 SO4
CH3
(a)  
D D
H
OH (q) D D 

CH3 CH3
H SO
(b) CH3—CH2—C — CH—CH3 
2

4
Cl

H
OH (r) 

N
— CH2 — OH OH
H3PO4 H3PO4
(c) 
 (s) 

OH
OH
H PO Q.4 Write – Mechanism
(d) — CH — CH2 — CH3 
3 4


H
OH (a) OH 



H
(e) 
 H2 SO4
(b) 
CH3
H OH
(f) CH3—CH2—CH — C —CH3 
 (c)
OH CH3 H
 18
OH 
H  CH2 — CH — CH2 — CH2 — CH2 

 + H2 O 
(g)  OH OH CH 3 O
18
12
----------------------------------------------------------------------------------------------------
Me Me
Q.5 Predict Major Product
HCl
(a)  
CH2
(i)
HCl
(b) 

HCl (j)
(c)  
HCl
(d) 2-methyl propene  

Hl
(e) 1-methyl cyclohexene   (k)
OH
OH
r
(l) (m)
Ans.1 (a)
i
OH OH (n) (o)
(b) CD3
OH D D
OH
(p) (q) D
S
(c)
.
(r) (s)
(d) OH
OH
OH Cl
OH Cl
J
(e)
Ans.5 (a) (b)
C
.
Ans.2 (A) (B) (C) (D) C—C=C—C
(c) (d)
Cl
Cl
I
Ans.3 (a) (b) (c) (d)
(e)
N
(e) (f) (g)
(h) +
13
----------------------------------------------------------------------------------------------------
Q.1 Identify major products: H H H3 O 
CH3 (d) C=C  

HgSO4
(a)   Ph Ph
CH3 — C — C CH H2 SO4
HBr
CH3 (e) 
CCl4

HgSO
(b) CH3 — C  CH 
H SO
4
 2 4 (f) D–Cl (x)
D3O+
(c) CH3 CC
HgSO4
  (y)
H2 SO4
Q.3 What will be major – product obtained from
r
C CH addition of HBr to each of the following
HgSO4
(d) 
H2 SO4
 compounds.
(a) CH3 — CH2 — CH = CH2
i
C CH CH3 CH2

H3 O
(e)  (b) (c)
CH3
HgSO4
(f) CH3 — C  CH 
 (d) CH3 — CH = C — CH3
S
H2 SO4
C CH CH3

H3 O
(g)  (e) H2C = C — CH2 — CH3
(h)
(i)
(j) HBr
 
H3 O
l-phenyl cyclohexene 
H3 O
l-methyl cyclopetene 




J. (f)
(g)
(h)
CH3 — CH = CH — CH3
HO CH = CH2
CH3 — CH — CH2 — CH = CH2
.
CH3
HBr
(k) Ph — CH2 — CH = CH2 
CCl
 4
CH3
Q.2 Find total product in following reaction ? (including

(i) (j)
stereoisomer)

H
(a)   (x) products (k)
N
OH 
Br2 Ans.
(z) (products)
CCl4 O
HBr O

 (y) (products) (Markonikoff products)
CCl4 1. (a) (b)
O
OH
H  HBr
(c) Me
(b) 

 (A) 
CCl4
 (B)
Br2
(C)
CCl4
OH 
H
(c) 


14
----------------------------------------------------------------------------------------------------
O O
*
3. (a) M. I. (b) Br
(d) (e) Br
O Br
(c) (d)
O
Br
(f) (g) CHD2
*
(e) (f)
OH Br Br
OH
(h) Ph (i) M. I. (g) HO * M. I.
Br Br
Br Br
r
(h) * M. I. (i) Br
(j) (k)
2. (a) x  3 ; y 2 ; z 5

(b)
(c) 3
(e) 4
A 1 ; B 1 ; C 2
(d) 2
(f) x 4 ; y 4
S
(j)
(k)
HO
Br
i Me
Br
M. I.
J.
.
N
15
----------------------------------------------------------------------------------------------------
Q.1 How will prepare following compound using alkene Ans.
as the starting material ?
OH H3 O 
1. (a)  
(a) (b)
OH
H3 O 
Br (b) or  
(c) (d)
or
Br
CH3 Br
r
(e) CH3 — O — C — CH3
(f)
HBr
(c) or 
CCl4

CH3
i
OCH3
OH (i) or
(g)
Q.2 Identify reactant in following reaction
S
Br2
(a) (A) 
 meso – 2, 3 – dibromobutane
CCl4 HBr
(d)  
Br or CCl4
.
Br
(b) (B) 2
CCl
 + Mirror Image
4
Br
Br MeOH
(c)
HBr
(C)   (e) 
CCl 4
J
HBr
HBr Br (f) 
CCl4

(d) (D) 
CCl
 4
.
CH3

H3 O
(e)
HBr
(E)   CH 3 — C — CH2 — Br (g) or or  
CCl 4
CH3
O
H O MeOH
(f) (F) 
3
 (h) 
N
HBr
(g) (G) 
CCl
 racemic mixture of 2, 3 –
4
dibromobutane. 2. (a) A  Trans but-2-ene

(b) B cyclohexene
Q.3 Write – Mechanism (c) C  cyclohexene
(d) D 2-Methylpropene
(e) E can not prepared by alkene
H  (f) F Propyne
(a)  
 (g) G Cis but 2-ene
OH
H3 O
(b) Ph—CH2—CH2—OH  Ph — CH — CH3
16
----------------------------------------------------------------------------------------------------
IIT-JEE Chemistry by N.J. sir ORGANIC chemistry
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 R’ O3 R O R’ Zn/H2O R
C=C step I C C Reductive C = O + R’– C – H
R H –70°C R H ozonolysis R
r
O
O O
Oxidative H O
i
ozonolysis
2 2 [SCT-Cut the double bond
and paste two oxygen atoms
Example 1: and vice versa]
R – C – R + R’ – C – OH
O O
S
Mechanism:
R R R
R R’
O O
.
C R—C—O
C O + C=O
+ O+ O +
R H
C R’ — C — O
R’ H O
H
R
J
R R—C—O
O
C O O
.
R + O
R’ C R – C – R + R’ – C – H
O=C R’
H H O O
Note : In case of oxidative ozonolysis aldehyde (not ketone) further undergoes oxidation which gives acid
as product.
N
Q.1 Give the product of the following reaction. (vii) H2C = CH — CH2 – CH = CH – CH3
[ 7 × 2 = 14] (i)O3
(i)O 
(ii)Zn /H2O

(i) H2C = CH2  3 
(ii)Zn /H O 2
3  (i)O Q.2 Find out the structure of reactant.
(ii) CH3 — CH = CH2 
(ii)Zn /H O [11 × 2 = 22]
2
CH3 (i)O
3  CH – CH –
(i) X 
(ii)Zn /H O 3 2 C–H
(i)O
3  2
(iii) CH3 – C = CH2 
(ii)Zn /H O 2 O
(i)O3
(iv) 
(ii)Zn /H2O
 H
(i)O3
(ii) X 
(ii)Zn /H2O
 O+ O
(i)O3 H H
(v) 
(ii)Zn /H2O
 (i)O
(iii) X  3  O
(i)O
(ii)Zn /H O 2 O+
(vi)  3 
(ii)Zn /H O 2
H
17
----------------------------------------------------------------------------------------------------
KJhalawar Road, Kota, Rajasthan (324005)
O O
(i)O
3 
(iv) X  + O /
(ii)Zn /H O (iii) 3 
2 Zn /H O
H H 2
(i)O
3 
(v) X 
(ii)Zn /H O O
2 How many species will be formed.
O Q.4 How many initial ozonoids are possible in given

CH3 H reaction.
(i)O3
(vi) X  + C=O + (i)O / 
(ii)Zn/H O
 C=O
(i) CH2 = CH2  3 
2 H 3C H (ii)Zn /H O
2
O
O
(i)O (i)O / 
3  (ii) CH3 – CH = CH – CH3  3 
(vii) X 
(ii)Zn /H O (ii)Zn /H O
2 2
(i)O / 
CH2  3 
r
O (iii) CH3 – CH = (ii)Zn /H O
2
(i)O3 O
(viii) X 
(ii)Zn /H2O
 + HCHO Q.9 Only mole of the compound A (molecular formula
O
C8H12), incapable of showing stereoisomerism,
i
C10H12 O reacts with only one mole of H2 on hydrogenation
O over Pd. A undergoes ozonolysis to give a
(i)O symmetrical diketone B(C8H12O2). What are the
(ix)  3  +
X (ii)Zn /H O structure of A and B?
2
C12H18 O
S
O + HCHO Ans. (A) (B)
O=C=O+
O O
.
Q.21 If after complete ozonolysis of one mole of
(i)O
(x) C6H4  3 C H O
3 2 3
monomer of natural polymer gives two moles of
(ii)Zn /H O 2 CH3
(X)
O O
CH2O and one mole of O = C – CH = O. Identify
(i)O the monomer and draw the all-cis structure of
J
(xi) X  3
(ii)Zn/H O
+ HCHO natural polymer. [IIT '2005]
2
C12H18 CH3
O
.
Ans. (a) CH2 = C – CH = CH2
CH3 H
Q.3 Give the ozonolysis product of the following.
H (b) C = C
O () (CH2 CH2)n
3  3
(i) X 
Zn O C H OH
H , (i ) O
Q.22  X 3
  Y
(ii) Zn / Cl3COOH
N
O
O
Identify X and Y.
(ii)  3 ?
Zn /H O
2
O
How many species will be formed. Ans. (X) , (Y) CH3 – C – (CH2)4 – CH = O
CH3
18
----------------------------------------------------------------------------------------------------
O CHO
(C) (D)
Q.1
CHO
CHO O Q.5 This compound on ozonolysis gives which of the
is obtained by the ozonolysis of following? following compounds
O
(A) (B)
(C) (D)
(I) O
(III)
O
O
O
O
O
(II)
(IV)
i r O
O
O
OHC—C—C—CH2—C—CHO
O
S
Q.2 Which starting material should be used to produce OHC—C—C—CH2—CH = O
the compound shown below?
H O
.
O3 (A) I, II, III & IV (B) I, III, IV
?   O O
ZnH2O H (C) I, II, III (D) I, II, IV
O
O
Q.6 Which of the following will give three different
(A) (B) compounds on ozonolysis
J
Me Me
(A) (B)
.
(C) (D)
(C) (D)
CH3
| H  O3
Q.3 CH3 — C — CH3  (A)   (P) + HCHO Q.7 Which one of the following compounds gives
|  Zn,H O 2
OH acetone (CH3)2C=O as one of the products of its
ozonolysis?
N
Product (P) is
O (A) (B)
||
(A) CH3 — CH2 — CHO (B) CH3 — C — CH3
(C) CH — CH — OH (D) CH3 — CHO (C) (D)
3
|
CH3
ozonolysis
Q.8 Sentene 
Q.4 The reactants that lead to product (a) and (b) on
ozonolysis are O O
O O
Which is the correct structure of Sentene.
HCHO
(A) (B)
CHO
(a) (b)
(A) (B) (C) (D)
Q.9 In which of following reaction product formed is

aromatic
19
----------------------------------------------------------------------------------------------------
OH
Q.10 Propane reacts with chlorine in sunlight to give two
HBr products. 1-chloropropane is obtained in 44% yield
(A) 
 and 2-chloropropane is obtained in 56% yield of the
total product. 2-Methylpropane reacts with chlorine
under same conditions to produce 1-chloro-2-
(B)
HF 

methylpropane 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
KH  treated with Cl2 in similar conditions. (Round
(C) 
 answer to nearest integer)
OH
H2SO4
(D) 

HO
r
OH
i
Free Radicals:– Q.8
Na
 ________ _
S
Wurtz Reaction:– ether
Na Cl Cl
R — X 
ether R— R
Cl
.
Na
Q.9 
ether _______
Mechanism:– (Free radical Mechanism)
(1) Na Na+ + e– Br

R — X + e–  R + X
:
(2) Na
  Q.10 Cl Cl 
ether _______
J
(3) R + R R — R
Cl Na
(Ionic Mechanism)
Q.11 Cl 
ether _ _____
.
(1) Na Na+ + e– Q.12 Ph — Cl 
Na
 _ _ _ _ _ _ _ (fitting Reaction)
THF
:
(2) R — X + 2e–  R+ X Na  _ _ (Wurtz fitting)

Q.13 Cl + Cl — CH3 
  THF
:
(3) R + R — X R — R + X Cl
Na
Q.14 
ether _______
Na
N
Q.1 CH3 — Cl 
ether _______ Cl
Na Q.15 Zn  _______
Q.2 Et — Cl  _______ CH2—CH2 
ether
Q.3 CH3 — Cl + Et — Cl 
Na
_______ Br Br
ether Cl
Q.16 Ag/Powder
H—C—Cl   _______
Na
Q.4 (Ph)3 CI 
ether _______ Cl
Na
Na
Q.17 CH2—CH=CH—CH2 
ether _______
Q.5 I 
ether _______
Br Br
I
Na
Q.6 Cl Br 
ether _______ Na
Q.18 
ether _______
Br Na
Q.7 
ether _______
Br
Br
20
----------------------------------------------------------------------------------------------------
Q.1. 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?
Q.2. Give product(s) in each of the following reactions
Br2 / hv
CH3 CH CH2 CH2 CH3  (A)
CH3
Q.3 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
Q.4. Which of the following compounds on gentle heating, will undergo homolytic bond cleavage easily:
O
(A) (B) (CH3)3C ─ OC(CH3)3
i
(CH3)2C O C CH3
(C) (CH3)3C ─ C6H5 (D) (CH3)3C ─O─O─C(CH3)3
Q.5. Amongst the following, the most basic compound is:

(A) C6H5NH2 (B) p-NO2─C6H4NH2 (C) m-NO2─C6H4NH2 (D) C6H5CH2NH2
Q.6 Which of the following is most acidic?
S
NH2  
NH3 NH3

(A) (B) CH3 NH3 (C) (D)
Q.7. Write mechanism of following reactions?
(a)
(b)
HC
-
Ph3 C─Cl 

Na
Et 2O
Cl 
Na
Et 2O
Ph2 C
J. CH2 CH2
CPh2
.
Q.8. Arrange the following in increasing order of stability.
(a) , ,
, ,
(regarding stability of free radical)
N
CH3
(b) CH2
CH2 CH
2
CH2 , CH2 CH
2
CH CH2 , ,
Q.9. Supply the structure and type of intermediate species designated by

 
(a) CH3 CH ─CH3 + H+  ? + H2O (b) CH3CH2 ─ N ═ N ─ CH2CH3  ? + N2
|
OH

(c) CH3CHI2 + Zn 
 ? + ZnI2 (d)  ? N a + NH3
CH3C ≡ CH + NaNH2 
(e)  AlCl4– + ?
CH3CH2Cl + AlCl3 
Q.10. 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.

COOK COONa COOK
(a) (b) (c)
COONa COONa COOK
21
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CH3 CH3
Q.12 CH3 C° + CH3 C°           

(Major Pr oduct)
CH3 CH3
Q.13 CH3 — C°H2 + CH3 — C°H2           

(Major Pr oduct)
Q.6 C + C  

(explain)
Q.14 Ph
H
CH3
H
CH 3
CH = CH 2  H / Ph
+
O
H
i r
S
Mechanism : –
H H
          
.
(ii) Ph C C CH = CH 2 + H
(Intermediate1 )
CH 3 CH 3
(Rearrangement)
J
Nucleophile 
Pr oduct   Intermediate3  (Intermediate2 )
.
  
Q.15
HCl | CCl4 HBr
A B
CCl4
N
Ph—CH2 = CH 2
D C
HCl HBr
R–O–O–R/CCl4 (R–O–O–R)/CCl4
CH3 CH3
Br /h aq.KOH
Q.16 CH3   A 

2 2
CH3 C CH2 CH3 C CH2 CH3
H OH
Conc. H2SO4
HBr(R–O–O–R)
C   B
CCl4
A & C are Idenitcal / Isomers / Positon Isomers.
   
22
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Ph O
NaOH
Q.17 Ph C C OH 
electrolysis
Ph
Anode Cathode
Ph O
(I) _ _ _ _ _ _ _ _ _ e— + (i) 2H2O + 2e— _ _ _ _ _ _
Ph C C O°
Ph
Ph O
(ii) CO2 +        
Ph C C O°
Intermediate
Ph
(iii) Intermediate - - - - - - - - - - - -
r

IIT-JEE ChEmistry by N.J. sir

DPP NO- 14
Kolbe Electrolysis:–
O
S Q.4
COOH
NaOH

electrolysis
i
ORGANIC chemistry
Time: 15 minutes
_______
.
R — C —OH NaOH

electrolysis R—R + CO2 + H 2 COOH
COOH
Anode Cathode Q.5 KOH _______

electrolysis
Mechanism:– HOOC
J
(1)
O Q.6 electrolysis
O H NaOOC COONa  __ _ _ _

+ OH   R — C —O— + O electrolysis _
.
R — C —O—H Q.7 COONa  _ _
H NaOOC
Anode:–
Q.8 electrolysis _ _ _ _ __ _
O KO3S SO3 K 
O
–  COOH
(1) R — C —O—  R — C — O + e Q.9 NaOH
 _______
electrolysis
O SO3H
N
 
(2) R — C — O  R + CO2  COOH
  Q.10 NaOH _______
(2) R + R R — R 
electrolysis
Cathode:–
(1) 2H2O + 2e— 2O H + H2 COOH
SO3K
Q.1 electrolysis
CH3 COOK  _______
Q.11 electrolysis
Q.2 NaOH
Et — COOH  _______  _ _ _ _ _ _ _
electrolysis
Q.3 NaOH
COOH  _ _ _ _ SO3K
electrolysis
HOOC Q.12 KO3S electrolysis ___
C C 
SO3K
23
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Q.1 Matrix
Reactions Number of dimerization product
(excluding stereoisomers)
(A) Na
CH3 — CH2 — Cl 
 (P) 1
Dry ether
Cl
(B) Na
  (Q) 3
Dry ether
r
14
(C) Na
H2C = CH — CH2 — Cl   (R) 6
i
Dry ether
(D) * Cl 
Na * 14
 + CH3 — Cl (H2 C  CH2 ) (S) None
Dry ether
Q.2 Identify major products. Br
S
CH2Br (5) Na 

(1) + 4 Na  DE
Cl
.
Br
(2) AlHg (6) 14 Na 


  DE
C2H5OH
Br
O
J
I (7) Na 

DE
(3) I Cu
I+  Br
.
120260C
Cl Na
I (8)  
Dry ether
Cl Na
(9)  
Dry ether
Na Br
(4)  
Dry ether
N
24
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Q.1 Identify the major product:- Cl
CH2 — I
(12) CH3 — CH2 — Cl + Na

 
(1) Na
+   Dry ether
Dry ether
Br
Br Br Cl
(13) Na
 
Dry ether
(2) + Na
 
Dry ether
r
2. Which of following is correct matching of energy
Br Br
profile diagram?
i
CH2 CH2  
(1) CH3  Cl  CH3 — Cl
E
(3) Na
 
Dry ether
rxn - coordinate
Br
Se  (B) (2) hv  2Cl
Cl — Cl 
Na
S
(4)   (A) 
Dry ether E
rxn - coordinate
.
Br
Br
(3) CH3  + CH3   CH3 — CH3
(5) Na
  E
Dry ether
J
Br rxn - coordinate
Br
(4) Cl  + H — CH3  H — Cl +  CH3
.
E
(6) Na
  Naphthacene
Dry ether
rxn - coordinate
Br  KJ   KJ 
CH2 — Br Bond energy  H  Cl  432   CH  H  440 
(7) Na  mole   3 mole 
  (A) + (B);
Dry ether
CH2 — Br 3. When pentane is heated to a very high temperatue,
(A) & (B) are isomer.
N
radical reactions take palce that produce (among
other products) methane, ethane, propane, and
(8) H2C*=CH—CH2—Cl 
Na A + B + C butane. This type of change is called thermal
Dry ether
Br
cracking. Among the reactions that take place are
the following:-
(9) Na
  (1) CH3CH2CH2CH2CH3  CH3  + CH3CH2CH2CH2 
Dry ether
(2) CH3CH2CH2CH2CH3  CH3CH2  + CH3CH2CH2 
(3) CH3  + CH3   CH3CH3
Cl (4) CH3  + CH3CH2CH2CH2CH3 
Cl CH4 + CH3CH2CH2CH2CH2 
(10) Na
 
(5) CH3  + CH3CH2   CH3CH2CH3
Dry ether (6) CH3CH2  + CH3CH2   CH3CH2CH2CH3
Cl (a) For which of these reactions would you
expect Eact to equal zero?
Na (b) To be greter than zero?
(11)  
Dry ether (c) To equal H°?
25
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1. Compound Number of monochloroproduct Number of monocloroproduct
(excluding stereoisomer)
1.
2.
3.
4.
5.
r
6.
7.
8.
S i
.
9.
CH2
J
2.
1. Compound Number of Dichloroproduct Optically active product
(including stereoisomer)
.
1. 1-chlorobutane
2. R-2-chlorobutane
3. 3-chloropentane
N
4. R-2-chloropentane
5. S-2-chlorobutane
6. R & S-2-chloropentane
7. R & S-2-chloro butane
26
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IIT-JEE ChEmistry by N.J. sir ORGANIC ChemIstRy
Question bank on
GRIGNARD'S REAGENT
i r
.S
J
,
O2, H2O,
CdCl 2
H2 O
O 2
,H
.
O
+ H
S,
gB –X
O
CH
2
O
+ O
CH
r H=R
, H2 –C
HO
2
H
O
+
RC SiCl H 2
4
CIC
R
R–Mg–X RCOR, H2
O R–Mg–X CICH 2O
l2
O , H 2O O
+ HCOOEt PbC PhC
H2 C
– CH 2 l
CH 2 O Cl 2
H 3
Zn CI–
N,
CN
RC Cl 2
Br2 I2
N ?
27
----------------------------------------------------------------------------------------------------
GRIGNARD’S REAGENT
Q.1 The order of reactivity of alkyl halide in the reaction O

R – X + Mg  RMgX is ||
(A) RI > RBr > RCl (B) RCl> RBr > RI (B) PhMgBr(excess) + CH3 – C – Cl  
H
(C) RBr > RCl > RI (D) RBr > RI > RCl
O O
|| ||
Q.2 (C) CH3MgBr(excess)+ CH3 – C – O  C  CH3  
Mg H
Br–CH2–CC–CH2–Br  BrMg–CH2–CC–CH2 –MgBr
(excess) O
Et 2O ||
(D) CH3MgBr (excess) + Cl  C  O  Et  
H
Mg(1 eq.)
Product Cl
r
Et2O Q.9 1 equivalent Mg X D O Y ; Y is
 2 

The major product is ether
Br
(A) Br –Mg–CH2 –C  C –CH2–Br
i
Cl D
(B) Cyclobutyne (A) (B)
(C) –(CH2–C  C –CH2)n – D Br
(D) CH2 = C = C =CH2 D
(C) (D) None of these
D
Q.3 On conversion into Grignard followed by treatment
S
with ethanol, how many alkyl halides (excluding Q.10 Compounds are shown with the no. of RMgX
stereoisomers) would yield 2- methyl butane required for complete reaction, select the incorrect
(A) 2 (B) 3 (C) 4 (D) 5 option
.
(A) CH3COOC2H5 1
Q.4 Which of the following reacts with Grignard reagent
to give alkane? (B) CH3COCl 2
(A) nitro ethane (B) acetyl acetone (C) (C) HOCH2COOC2H5 3
acetaldehyde (D) acetone
J
OH
Q.5 How many litres of methane would be produced
when 0.595 g of CH3MgBr is treated with excess of (D) 4
.
C4H9NH2 CHO
(A) 0.8 litre (B) 0.08 litre COOC2H5
(C) 0.112 litre (D) 1.12 litre
Q.11 What will be the order of reactivity of the following
Q.6 How many litres of ethene would be produced when carbonyl compound with Grignard’s reagent?
2.62 g of vinyl magnesium bromide H H CH3 Me3C
is treated with 224 ml of ethyne at STP (I) C = O (II) C = O (III) C = O(IV) C=O
N
H CH3 CH3 Me3C
(A) 0.224 litre (B) 0.08 litre
(C) 0.448 litre (D) 1.12 litre (A) I > II > III > IV (B) IV > III> II> I
(C) II > I > IV > III (D) III > II> I > IV
MgBr OH
Q.12 Carbonyl compound (X) + Grignard reagent (Y) 

Q.7 + A OH
OH Me Ph X, Y will be-
O–Ph
(A) (B) (C) (D) Et

O O
|| ||
(A) Et – C – Ph, MeMgBr (B) Me – C – Ph,Et MgBr
Q.8 In which of the following reactions 3º alcohol will be O O
obtained as a product. || ||
O (D) Me – C – Et,Ph MgBr (D) Et – C – Ph,Et MgBr
||
(A) MgBr (excess) H – C – Cl +  
H
28
----------------------------------------------------------------------------------------------------
(i) Mg OEt
Q.13 (R) – 2–Bromooctane   X; X is followed
(ii) CO2 Q.18 MgBr + H –C OEt  
(iii) H H3 O
OEt
C6H13 C6H13 Ethyl ortho formate
Product
(A) CH3 * COOH (B) HOOC * CH3 O
||
H H
(A) C–CH3 (B) CH 2CH=O
CH–CH3
(C) A and B both (D) None of these (C) CH=O (D) |
CH=O
Q.14 In which one of the following reaction products are Br 1. Mg/ether

not correctly matched in Q.19 + Product (s)
2. CH3CHCH2CH 3. H3O
(A) RMg X + CO2   Carboxylic acid | ||
( 2) H
OH O
(B) RMgX + C2H5OH  Alkane Select the product from the following
r
(C) RMgX + CH3CH2Cl  Alkene I. II. CH 3 CHCH 2CH III. CH 3 CHCH 2CH
| || | |
i
(D) RMgX + Cl O Ether
OH O OH OH
(A) III (B) I, III
Q.15 The number of moles of grignard reagent (C) I, II (D) II, III
consumed per mole of the compound O
HO COOEt ||
2CH3MgBr
is Q.20 C2H5 O – C – OC2H5  A. Product A formed
S
O
(A) is ethyl acetate
(A) 4 (B) 2 (C) 3 (D) 1 (B) further react with CH3MgBr/H2O+ to give acetone
Q.16 Select the correct statement : (C) further react with CH3Mg Br/H2O+ to give t- butyl
.
(A) 1, 4- dibromobutane react with excess of alcohol
magnesium in ether to generate di-Grignard (D) Can give pinacol when treated with Mg followed
reagent. by H2O
(B)1, 2- dichlorocyclohexane treated with excess of
Mg in ether produces cyclohexene. Q.21 Order of rate of reaction of following compound with
J
phenyl magnesium bromide is
(C) Vicinal dihalides undergo dehalogenation to O O O
give alkene when heated with Zn dust or Mg. || || ||
.
(D) 1, 3- dichloropropane by treatment with Zn dust Me – C – Cl Me – C – H Me – C – O – Et
I II III
or Mg forms cyclopropane.
(A) I > II > III (B) II > III > I
Mg Br (C) III > I > II (D) II > I > III
Q.17 CH3–CH = CH2 
2
 
 Dry Ether
O Q.22 Select the correct order of decreasing reactivity of
|| X
N
CH3–C–CH3  the following compounds towards the attack of
H (Major)
 Grignard reagent
NH4Cl 
(I) Methyl benzoate (II) Benzaldehyde
End product of above reaction is (III) Benzoylchloride (IV) Acetophenone
(A) II > III > I > IV (B) I > II > III > IV
CH 2
|| (C) III > II > IV > I (D) II > IV > I > III
(A) CH2= CH – CH2– C – CH 3
(B) H2C  CH – CH  C – CH3 Q.23 O

CH3 MgX
Product is
| NH4 Cl
CH3 (A) Enantiomer (B) Diastereisomer
OH (C) Meso (D) Achiral
|
H
(C) 2 C  CH – CH2 – C – CH3 Q.24 Nucleophilic addition of Grignard reagent cannot
| occur in
O O O O
CH3 || || || ||
(A) CH 3– C– C–CH 3 (B) CH3– C– CH2–C–CH3
(D) H2C = CH– CH2–CH–CH
|
2–OH
O O
CH3 || || O
(C) CH 3– C– CH 2–CH 2–C–CH 3 (D) O
29
----------------------------------------------------------------------------------------------------
O
Q.25 CH3 CCH2CH2 CH2 Cl CH3MgBr A, A is O HO CH3 HO CH3
(C) CH3 , (D) , CH3
||
O
OH CH3 CH3 OH
CH3
|
(A) CH3 CCH2CH2CH2Cl (B) CH3 CCH
||
2CH2CH2CH3
O
(2)
| OH
C
OH O
H3C CH3 O (3) RMgX (2 moles)
Q.30 H 
H
CH3 (1) S
(C) (D) C
O
O CH3
H3C CH
(4)
O O Deprotonation will occur from the following
Q.26 CH 3CCH 2CH2COCH 2CH 3
(i) CH3MgBr(one mole)
 A, positions:

(ii) H3O (A) 1, 2 (B) 1, 3
r
A formed in this reaction is (C) any two positions (D) 1, 4
OH O O O
(A) CH3CCH2CH2COCH2CH3 (B) CH3CCH2CH 2CCH 3 HO OEt
i
2CH3MgX
CH3
Q.31   P 1 + P2
NH4 Cl
CH3 CH3
H 3C O Identify P1 & P2.
(C) O (D) CH3CCH2CH2CCH3 O
H 3C HO Me
OH OH
(A) CH4 (B) (C) (D)
S
O
MgCl CH CHO
Q.27 PhCH3 
2
 (A)  (B) 
3
 (C)
h ether NH4 Cl
Br Mg 14
.
OH (i) CO NaHCO
Q.32  (A)   (B)   (C) gas 2 3
(ii) H /H2 O
OH
CH2 CH CH3 CH3
Product C is
(A) (B) CH CH3 (A) CO (B) 14CO2 (C) CO2
(D) A mixtue of CO2 and CO2
14
J
CH3 OH (i) CH ONH
CH3 Q.33 2CH3MgBr 
3 2


C CH3 (ii) H
(C) (D)
(A) CH3 – O – NH – CH3 (B) CH3 – NH – CH3
.
CH3
(C) CH3 – NH2 (D) CH3 – OH
CH
HO CH3 OH
O
Q.28 Select the correct order of reactivity towards Q.34 
3 (i) CH MgBr
 (A)
Grignard reagent for nucleophilic attack. 
(ii) H / H2O
O O CH3
N
|| || (A) The product is optically active
(A) R  C  R  R  C  H
(B) The product contains plane of symmetry
(B) Cl – CH 2  C – H  CH 3CH 2 – C  H (C) The product shows geometrical isomerism
|| ||
(D) The product shows optical isomerism
O O
O O
|| || Q.35 Which of the following is incorrect.
(C) CH3–C–O NO2 < CH3 – C – O O O
CH3MgX
O O (A) C 
 CH –C – OC H 3 2 5
|| || Cl OC2 H5
(1 eq)
(D) R  C  OR  R  C  NR 2
OC2H5 O
C2H5MgX
O (B) CH3– C – OC2H5  CH3–C – OC2H5
(1 eq)
OC2H5
(i) CH3MgBr / CuCl
Q.29 

 (X) Major + (Y) S S
(ii) H2O / H

(X) and (Y) respectively are H3 O
(C) CH3MgX + C = S   CH3–C – SH
OH O
CH3 OH CH3 OH O O
(A) , (B) , H3 O
(D) CH3MgX + C = O  CH3–C – OH
CH3 CH3
30
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Q.36 Which reaction gives 1° aromatic amine as major Q.41 RMgX 
3 (i)CH CN
RMgX
 (A)   (B) will be
product. (ii)NH4Cl NH4 Cl
Br (A) 1°ROH (B) 2°ROH
Mg/ ether NH3
(A)     (C) 3°ROH (D) Alkene
Br
Mg/ ether NH3
(B)     Q.42 CH3 – CH – CH2
(i)CH3MgCl
 
(ii)H2O
F
Br O
Mg/ ether NH3 (A) CH3– CH–CH2OH (B) CH3– CH–CH2–CH3
(C)    
CH3 OH
F CH – CH–CH3
Hg(OAc )2
(C) 3
(D) Ph  
NH3 /NaBH4 CH3
O (D) HO–CH2–CH2–CH2–CH2– OH
CH3MgBr + CH2 = CH – C – H H O
Q.37  Product (1, 4
r
3
Q.43 The reaction of 1 mole each of p-hydroxy
addition). It is acetophenone and methyl magnesium iodide will
OH
give
i
(A) CH2 CH C H (B) CH2 CH = CH – CH3 O
CH3 OH (A) CH4 + IMgO C– CH3

(C) CH3CH2CH2CHO (D) None O
O (B) CH3–O C– CH3
S
OMgI
(i) PhMgBr
Q.38   Product
(ii) NH4 Cl (C) CH3–C OH
.
Me CH3
Produtcs in this reaction will be MgI
O
(A) Stereoisomers (B) Enantiomer
(C) Diastereomers (D) Geometrical isomers (D) CH3O C–CH3
J
r
Q.44 (i) + Ph Mg Br 
1
 Ph CH2CH2OH
O
O O
.
CH3MgBr (1 eq.)
Q.39 O  ? r
(ii) + Ph Mg Br 
2
 Ph CH2CH2CH2OH
O
The product is: (A) r2 > r1 (B) r1 > r2
(C) r1 = r2 (D) r1 = 2r2
OH O
O O
N
(A) (B) Q.45 How many moles of Grignard reagent will be
O required by one mole of given compound?
O
SH
OH O HO C OEt
O O
(C) (D)
C Cl
CH2 CH2
O
Cl
(i) Br (A) 7 (B) 6 (C) 8 (D) 5
Q.40 CH2= C = O 
2
 C4H8O
(ii) CH3MgBr
(2equi.) Q.46 Consider the given organometallic compound.
O (I) (CH3)2Hg (II) (CH3)2Zn
O
(A) CH3 (B) (III) (CH3)2Mg (IV) CH3Li
CH3 CH3
The correct decreasing order of ionic character is
CH3
(A) I > II > III > IV (B) II > I > III > IV
(C) I > III > II > IV (D) IV > III > II > I
(C) O
(D) All of these
CH2
31
----------------------------------------------------------------------------------------------------
O (i) CH3MgBr For Q. no. 48 to Q.no.50
P
(ii) H3O
+
Consider the given reaction and answer the
Q.47 CH3CH = CH –C –CH3 following questions
(i) CuI CH3MgBr
Q COOCH3
(ii) H3O+
MeMgBr
OH O   Products
(excess )
O OCH3
(A) P is CH3CH = CH –C –Me Q is CH3CH – CH2 –C –CH3 O SH
O
Me CH3
Q.48 No. of RMgX consumed in the reaction is
O OH (A) 4 (B) 5 (C) 6 (D) 7
(B) P is CH3CH– CH2 –C –CH3 Q is CH3CH = CH –C –Me
Q.49 How many product will be formed in given reaction
CH3 Me
(excluding stereo)
(A) 2 (B) 3 (C) 4 (D) 5
(C) P is CH3 CH=CH–C(CH3)2 Q is (CH3)2CHCH2C –CH3
r
OH O Q.50 Which of the following reaction will give the same
Hydrocarbon formed as one of the product in the
i
(D) P is (CH3 )2CHCH2C –CH3 Q is CH3CH=CH–C(CH3)2 above reaction.
(A) EtMgBr + Me – OH 
O OH
(B) PhMgBr + Me – OH 
(C) MeMgBr + Ph – OH 
(D) MeMgBr + CH3 – CHO 
.S
ANSWER KEY
RH R–OH
J
RSO2H RH RSH
S H R 2Cd
H 2O
R – C– SH RC R2Hg
R–R
H2
,
OH =C
O2, H2O,
CdC 2
CH
HO
CH
O
CH 2
2
O R R–
2
,H
2
l
O
+ H
S,
gB –X
HO
CH
2
R – C– OH O r R H=
.
O
+ , H2
HC
R4Si –C
HO OH
2
O
+
RC R 3C SiCl4
CIC
H 2
RCH2
OR
R, HO 2
R – CH2 – CH – Me R–Mg–X RCO R–Mg–X CICH2OR
l2
HC
OO PbC CIC
OO
HO O O
+ Et Et
PbR4 Cl 2
O R – CHO Zn CI–
CN R–COOEt
H 3
R – CH2 – CH2 –OH N, Cl 2 I2
RC Br2
Zn R–CN
R2
R2– C= O
OH
R2CHOH R–I
O RCl RBr
R – C– R
R–C
R
R
Q.No.
Ans.
1
A
Q.No. 16
Ans. A,C,D
Q.No. 31
2
D
17
B
32
3
C
18
C
33
N 4
A,B
19
C
34
5
C
20
C,D
35
6
C
21
A
36
7
A
22
C
37
8
B,C,D D
23
A
38
9
24
B,D
39
10
A
25
C
40
11
A
26
C
41
12
A,B,C
27
A,B,C
42
13
C
28
B
43
14
C
29
B
44
15
A
30
A
45
Ans. A,B C C,D B,C B B C A,C,D D A C B A B A
Q.No. 46 47 48 49 50
Ans. D C C C C
32
----------------------------------------------------------------------------------------------------
Explain:
2. C=C  C—C (No bond rotation)
I
CH2N2 Zn–I
1. CH2 = CH2  C C
N:
N H H H H
:
CH2N2 Characteristics :–
2. CH  CH 
N 1. The reaction is stereospecific in nature
H CH2I2 CH2I2
Q.1   2.  
Simon Smith Reaction:– Zn Zn
r
CH2I2
CH2 = CH2   CH2 — CH 2 CH2I2
Zn/ Cu 3.  
Zn
CH2
i
OH OH O
Mechanism:– 1) Zn  Zn+2 + Ze— CO2 C
4.  OH
NaOH
2e– –
1. I — CH2 — I  I — CH 2 : – + I high P
high T
OH
S
Zn+2
I
+ (Kolbe’ Schmidt Reaction)
.
CH2 — Zn I
(Carbenoid) C—OH
O
J
SOCl 2 H
.
R R — Cl + SO2  + HCl  3. N +
:
:
O N –
N
H + Cl + HCl
Mechanism: – This reaction leads to inversion of Configuration.

1. Darzen’s Process.
Cl
R Cl R Cl
:
N
— R — :O + S=O  R— Cl + SO2 + HCl
:O: + S=O O—S—O  
+ H Cl
H Cl H Cl Machanism:–
:
N 1.
R Cl R Cl
+
H :O: + S=O O—S—O
—
Cl N + H Cl H Cl
—
R—O—S—O +
Cl
Cl R —
S O
O O Cl
– +
R — O — S — Cl + Cl H
2. O O
—
O O R – Cl + Cl — S Cl + S
– : O–H
– O
: —H +
Cl + R — O — S — Cl Cl – R + O — S — Cl
–
So2 + Cl
H— Cl + SO2
 
33
----------------------------------------------------------------------------------------------------
Note: the reaction leads to selection of configuration
Retention of configuration. For example:—
O H
CH3
:
H C — CH C — CH = C = O
Q.1 SOCl2
H OH A
C CH3
Ph Ph
CH3
SOCl2
B Ph
:
N
Arndt Eistert Reaction:–
O O O
H CH2N2 R — C — CH 2 – N 2
SOCl2 R — C — Cl
R — C — OH  
SOCl2
Q.2 C — OH A  Ag2O/
r
CH3 O O
Ph H H
:
N
R — CH 2 – C R—CH = C = O
SOCl2
i
B OH
CH 3 OH 1. SOCl 2
Q.3 SOCl2 O O
A 2. CH 2N 2 (Overall)
R—C R — CH 2 – C
Ph H H CH 3 3. Ag2 O/
OH OH
:
N
4. O
S
SOCl2 H H
B
Characteristics:—
.
Nucleophilic addition elimination:—
O O 1. The reaction is known as homologation
+ – 2. The reaction occurs with relation of configuration.
CH2N2
R — C — Cl  R — C — CH 2 — N N: + Cl
Ex.1
Mechanism:— O
O
J
+ – + Ag2O -- -- H H
:CH 2 —N N: 1. ---
CH2 = N = N: R — C — CH= N =N: 


–
:
+ – OH
.
COOH
1.
O –O 2.
– + + 1. SOCl 2
R — C — Cl + :CH 2— N N: R — C — CH 2 — N N:
2. CH 2N 2
Cl 2. Ag 2O 
4. H2O
O
+ –
R — C — CH 2— N N: + Cl Nucleophilic addition:—
N
Wolf Rearrangement:—
O O
+ 2 Ag O/  OH /H O
R — C — CH 2 — N N:  1. R — CH = C = O 
2
R — CH 2 – C
H OH
Mechanism:— – – O
OH
:
1. R — CH – C
O O
+ Ag2O/  + OH
R — C — CH — N N:  R — C — CH — –N N: O
:
– H—OH  R — CH – C –
H  2 +OH
 OH
O ROH/RO —
2. R — CH = C = O
:
R — C — CH +N 2 –
O NH2 / NH 3
3. R — CH = C = O
:
2. R — C — CH  O = C = CH — R.
4. R — CH = C = O
:
R—NH2
34
----------------------------------------------------------------------------------------------------
Diazo methane
Acid-Base Reaction:– O
CH2N2
Et—C—H 
1. CH2N2 + HCl CH3Cl + N2 5. - - - - - - - + - - - - - - - - ---

CH3 O
2. R — OH + CH2N2  1. SOCl 2
6. CH3 — CH2 — C — C — OH --------
2. CH 2N 2
O 3. Ag2 O/
3. R— C + CH2N2  4. O
H H
O—H
1. SOCl 2
O = C—OH No 2 2. CH 2N 2
7. --------
3. Ag 2O/
4. + CH2N2  COOH 4. H2 O
r
CH 3 1. SOCl 2
O 8. O --------------
2. CH 2N 2
i
5. CH3 — C
+ CH2N2 
CH2 —C—Cl 3. Ag2O/
OH 4. OH/H 2O
Homologation Reaction:– 9. 1. SOCl 2 --------------

O O
O COOH 2. CH 2N 2
CH2N2 S
R—C—H  3. Ag2 O/
S
1. R—C—CH2 — H + R—C—CH2
4. RO/H 2O
H
.
O CH3 O
10. 1. SOCl 2 --------------
CH2N2
R—C—R  H C—OH
2. - - - - - - - - + - - -- - - - - - - - 2. CH 2N 2
Cl 3. Ag2O/
O
4. OH/H 2O
J
CH2N2 O
3.  - - - - - - - + - - - -- - - - - -- -
CH2N2
Et—C—H 
11. - - - - - - - - + - - - - - - - - - ---
.
O O
CH2N2
12. Et—C—CH3  - - - -- - - - + - - - - - - - - ---
CH2N2
4.  - - - - - - - + - - - - - - - - ---

DPP NO- 03
Nitrenes :–
Q.1 Fill in the blanks:–

+
N h  (d) R—O—C—N—O—S—
Time: 15 minutes
- - - - - - - - - - - + - - - - - - - - - - - - - - (gas)
O
NO2
:
(a) – 
:
R — N = N = N:  O H O
B
:
- - - - - - - - - - - + - - - - - - - - - - - - - - (gas) - - - - - - - - + - - - - - - - - - - (gas)
O h 
h  (e) H— N = N = N: – 
R — S – N = N = N: – 
:
(b)
+
:

+ - - - - - - - - - - - + - - - - - - - - - - - - - - (gas)
O
- - - - - - - - - - - + - - - - - - - - - - - - - - (gas)
– h 
(f) R—C— N = N = N: 
+
:
– h  O
:
(c) R — O — C – N = N = N: 
 - - - - - - - - - - - + - - - - - - - - - - - - - - (gas)
+
:
O
35
----------------------------------------------------------------------------------------------------
h Fill in the blanks:–
(g) H — N = C = O 
 O D
- - - - - - - - - - - + CO _ _ _ _ KOH  R — NH2

R—C—N Br2
D
Mechanism:–
O –
(h) OH 1.
R — N — O — S —Ph
H O O D O
----------- - –
:
R— C — N + OH H–O–D + R — C — N: –
D D
NO2
OH Br—Br
(i) N — Cl  - - - - - - - - - - - -
H O –
OH
r
:
H–O–D + R — C — N—Br
OH 
:–
(j) R—C— N — Cl  ----------- -
i
O H
– Wolf
Br + _ _ _ _ _ _ _ R—N=C=O
Hoffmann Bromanide Reaction:– Rearrangement
O
NaOH
 R – NH2 + KBr + k2CO3 2.
R — C — NH 2 + Br2
S
– – O H O
OH
: :
R—N=C=O R—N—C R—N—C
:
Mechanism:– OH O
—
.
1. 
O O
– H
:
R—C—N—H + OH R — C — N: – + O CO2 + _ _ _ _ _ _ _ _ _ _ _ _
H H H
H2 O
Br —Br –
J
R — NH 2 + OH
O – O
H OH –
:
O + R — C — N: – R— C — N— H + Br Q.1 Compare rate of reaction:–
.
H Br Br O O
(a) O C — NH 2
CH3 C — NH 2
CH3
O (i) (ii)
– O O
:
R — C — N: + Br
C — NH 2 Cl C — NH 2
N
r.d.s. (iii) (iv)
R—N=C=O
2 Q.2 Fill in the blanks:–

15
O = C — NH 2 O = C — NH 2
– O Br2 /KOH
OH (a) +   - - - + - -- -
: :
R— N=C=O R—N—C
D
O—H O Br2 /KOH
(b) R — C — N — Ph
  ------ ---- --
O
H
:

:
R — N + CO 2 R—N—C
— Q.3
H H O
O
Br2 /KOH
O (a)   - - -- -
CH2 — CH 2 — C — NH 2
H H
–
R — NH 2 + OH
36
----------------------------------------------------------------------------------------------------
O = C — NH 2 Mechanism:–
Br2 /KOH
(b)   - - - -- - - - - - - - - 1.
Et Me
R R
+
C=N H C=N
H
l l
H
O R OH R O
Br2 /KOH + r.d.s.
(c)   ------- ---- -- H
N–H
R
l
O R —C = N
+
: :
Br2 O
(d)   ------ --- H H
KOH
Ph CONH 2 O R
Tautomer –
H
Rl —C = N — R Rl —C = N + OH
O
r
NaOCl  - - - - - - - - - - - - H OH
(e) Et—C—NH2  O
CH3 H2SO4 Ph — C —NH — CH 3
Q.1
i

C=N
O
Br2 Ph OH
(f) R —C—NH 2   ------ ---- --
KOD/D2O
Ph H2SO4
Q.2 C=N  -----------
S
O
Br2 CH3 OH
(g) R —C—ND 2   ------ ---- --
KOH
.
CH3 PCl5
Q.3 C   -----------
S
O
N
CH3 C —NH 2 KOBr  - - - - - - - - - -
(h)  OH
J
CH3 PCl5
Q.4  -----------
C=N  
.
CH3 OH
Br O O
(i) CH3 —C — C —NH 2 KOBr  - - - - - - - - - - - -
 C
OH
CH3 CH3
Q.5 C=N H  - - - - - - - -

O
N
(j) C —NH 2 Br2
 - - - - - - - - - - -
NaOH
O2 N
N CH3 OH
O C=N
Br H  - - - - - - - - - - -
(k) 2
NH2 —C—NH2  ------ ---- -- Q.6 
NaOH H C 
CH 3 Et
Beckmann’s Rearrangement:—
O
R Q.7
H l
C=N 
(Catalyst)
 R —C — NH —R Explain:–
l
R OH
Ph OH
H2SO4
Catalyst:– (a)  Ph – C  N
C=N 
O
H2SO4, SOCl2, SO3, PCl5, P2O3, PCl3, BF3, H
S — Cl O
O Ph OH C
Migration of R is always from anti position. (b) C=N H2SO4 Ph–C  N+ H H


HO— CH2
37
----------------------------------------------------------------------------------------------------
Curtius reaction:–
O O Schmidt Reaction:–
NaN3
R — C — Cl   R—C—N=N=N O
O
NH2 –NH2
H2SO4
R — C — O—H + HN3  R—NH2 + CO2 +
R — C — O CH 2 — CH 3  
O O
HNO2 – N2.
R — C — NH — NH 2  R — C — N = N = N:
:
+
O Mechanism:–
r
1. NaN3 R—N=C=O OH/H2O O
R — C — Cl   
  R— NH2 O
2. 
R — C — OH +H R—C + H H
Imp.
i
O O
R/ —OH  R—NH — C —OR 1
:
R — N = C = O  H—N = N = N:
:
R—NH2 O
R — N = C = O   R—N— C O O
NH–R
:
H R — C — N = N = N: R — C — N = N = N:
S
–H+
:
HOH  R — NH + CO
:
R — N = C = O  2 2 H

.

O NaN3 
Q.1   _______
— C — Cl R—N=C=O + N2
O
H2O H H OH / 
J
 _ _ _ _ _ _ _  _______
 
Et O R —NH2 + CO2
.
SOCl2 NaN3
Q.2  _ _ _ _ _  
H C — OH
O
CH3 Q.1 CH2— C—OH 
N H(H SO )

 _ _ _ _ _ 
_ __ __ _  _ _ _ _ _ 3 2 4
H2O/  _ _ _ _ _ + _ _ _ _ _ _ +_ _ _ _ _ _
N
O
CH 3
C 3
NaN 
Q.3 Cl   _ __ __ _  O
Q.2 CH3— C—OH  
O N3H(H2SO4 )/ 
_____ R H _____
_ _ _ _ _ + _ _ _ _ _ _ +_ _ _ _ _ _
O
1. NH NH
Q.4 CH2 — C—OC2H5 
2 2
 Schimidt miscellaneous:–
2. HNO2
O O
 ____ H
_ __ __ _  H/ ____ O
H
R — C — R 
N3H/  R — C — N —R
O H
Q.5 1. NH2 –NH2 _ __
CH3 —O— C—OCH 2CH 3 
2. HNO2

 _ _ _ _ _ H O H/ _ _ _ _ _

38
----------------------------------------------------------------------------------------------------
Mechanism:– Mechanism:–
1. 1.
O OH O O
:
O O
:
H—N = N = N: H
–
: :
:
C + C R—C—N—O—C—R + OH O + R—C—N— O—C—R
R R +H R R OH –
H H
R—C—R
H—N = N = N:
:
– O O
: :
—
OH R — NH 2+ CO 2 R—N = C = O R—C—N +O —C—R
OH
R—C + N2 R—C—R
N H—N = N = N: O O
KOH  _ _ _
:
:
Q.1 CH2 — C— N — O — C — Ph 

H R

H
r
O
+
H + R—C—N—R O O
KOH 
i
H Q.2 C— N — O — C — CH3 

Lossen’s Rearrangement:–
H
– O
O O OH CH3
R—NH2+ R — C — O—
R — C — N — O — C— R
H
.S
. J
N
39
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Reaction i r
Intermediates
.S
. J
N
40
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F-106, Road No. 2, Indraprastha Industrial Area, End of Evergreen Motors (Mahindra Showroom), BSNL Office
Lane, Jhalawar Road, Kota, Rajasthan (324005)
EXERCISE – I O O
Q.1 2-Chloropentane on halogenation with chlorine
gives 2,3-dichloropentane. What will be the
(B)
structure of free radical species formed in the
H
reaction? O
(A) Planar (B) Trigonal planar O
(C)
(C) Square planar (D) Pyramidal
Q.2 Decreasing order of nucleophilicity of the H

O
following nucleophile is : OH
 (D)

(1) CH3O (2) C N
O
 NBS Na/ether
(3) S O (4) CH3 C O 2  Q.7 (X)
CCl4. Peroxide
O X is :
r
(A) 4 > 3 > 2 > 1 (B) 1 > 2 > 4> 3
(C) 2 > 1 > 3 > 4 (D) 1 > 2 > 3 > 4 (A)
i
Q.3 The correct order of rate of Wurtz reaction.
(I) CH2– F
Na
CH – CH (B) (C)
2 2
ether
(II) CH2– Cl
Na
CH2 – CH2
ether
(D) None of these
S
(III) CH2– Br
Na
CH2 – CH2
ether
Q.8 What will be the major product, when 2-methyl
(IV) CH2– I
Na
CH2 – CH2 butane undergoes bromination in presence of
.
ether
light?
(A) I > II > III > IV (B) II > I > III > IV (A) 1-bromo-2-methyl butane
(C) IV > III > II > I (B) 2- bromo-2-methyl butane
(D) In all rate of Wurtz reaction is same (C) 2- bromo-3-methyl butane
(D) 1-bromo-3-methyl butane
J
CH3 – CH –CO2K
Q.4 electrolysis
(A) (Major) Q.9 Which can not be the possible product of the
CH3 – CH –CO2K given reaction
.
Major product (A) of above reaction Br2
CH3 – CH2 – C – OAg Product (s)
CCl4, 
(A) (B)
O
(C) (D) (A) CH3 – CH2 – Br
Q.5 Which of the following is not correct about P2. (B) CH3 – CH2 –C– O – CH2 – CH3
N
O O
Mg H
(C) CH3 – CH2 – CH2 – CH3
H2O
P1

P2 (D) CH3 – CH2 – CH3
(A) It is a spiro compound Q.10 Pick the correct statement for monochlorination of
(B) It is a Ketone R-secbutyl Bromide.
(C) It can show tautomerism Me
(D) It is an alkene
Cl2
Br H
Q.6 Consider the following reaction- 300°C
O
Et
Na/ether FeSO4 + H2O2
P
liq. NH3 Fenton's
OEt reagent
(A) There are five possible product; four are
the major product P is: optically active one is optically inactive
(B) There are five possible product; three are
O OH
optically inactive & two are optically active
(C) There are five possible product; two are
(A)
optically inactive & three are optically active
(D) None of these
41
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Q.11 Correct order of rate of photochlorination for Q.16 Br , which is not the correct statement
following compounds is
CH3 (A) I is more soluble than bromocyclopropane
(B) I gives pale yellow ppt. on addition with
C CH3 AgNO3
CH3 – CH3 CD3 – CD3 CH3
(C) I is having lower dipole moment than
bromocyclopropane
CH3 Br
(D) I is more ionic than
(I) (II) (III)
(A) II < I < III (B) I < II < III
(C) III < I < II (D) II < III < I Q.17 Which one of the following carbocation would you
expect to rearrange.
Q.12 Product can be CH3 CH3
 CH3
Cl 
* KNH2 (A) (B) 
(C) (D)
?
r
NH3 
NH2 NH2
NH2 Q.18 How many, 1,2-Shifts are involved during the
i
* course of following reaction:
(A) (B) * (C) OH
*
(D) (B) and (C) both conc. H2 SO4
Q.13 Which of the following carbocation is most stable? (A) 1 (B) 2 (C) 3 (D) 4
S
CH3 CH3
+ CH3 + CH3
(A) C (B) C CH3
.
+
H3C H
H3C CH3 (X)
Q.19 
OH
OH
CH3
CH3 Product (X) is:
(C) +
(D) C CH3
C CH3 
CH3 OH
J
HO (A) (B)
CH3
Q.14 Which carbocation is least likely to form as an
.
intermediate? (C) (D)

(A) (C 6H5 )3 C (B) 
Q.20 Among the given compounds, the correct
 dehydration order is:

(C) (D) CH2  CH (I) (II) OH
OH
N
Q.15 For the reactions (III) (IV)
OH OH

(I) Cl + Cl , H1°
(A) I < II < III < IV (B) II < III < IV < I
(C) I < III < IV < II (D) I < II < III = IV

(II) Cl + Cl , H2°
OH
 
Q.21 H
+ P. The product P is
(III) CH2Cl CH2 + Cl , H3° 5°C
(IV) Cl + Cl , H4°

(A) (B)
The correct decreasing order of enthalpies of
reaction for producing carbocation is:
(A) H1º > H2º > H3º > H4º OH
(B) H4º > H1º > H2º > H3º (C) (D)
(C) H3º > H2º> H1º > H4º
(D) H2º> H1º> H4º > H3º
42
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Q.22 Rate of dehydration when given compounds are
treated with conc. H2SO4. OH
Q.26 H+
OH 
CH2OH CH3
(P) (Q)
(A) (B)
OH OH
CH3 CH3
(R) (S) (C) (D)
(A) P > Q > R > S (B) Q > P > R > S Me

(C) R > Q > P > S (D) R > Q > S > P
Q.27 Me
Conc.H2SO4
A

OH OH OH
Product 'A' is-
r
Q.23 H2SO4
X

(A) Me (B) Me
i
O O Me Me
'X' is
Me
OH OH
(C) (D) Me
C –Me
Me
(A) (B) O
S
O
O OH Q.28 How many products are obtained in the given
reaction:
.
Et Ph CH3 Ph
(C) (D)
H2SO4
HO OH + HO OH

OH
Et Ph CH3 Ph
J
OH
O (A) 1 (B) 2 (C) 3 (D) 4
Q.24 CH3 H+ major product is
.
CH3
CH3
CH3 CH3
O
Q.29 CH3 – CH – C – CH2 – NH2 HNO2 (X)
(A) (B) O CH3
CH3 CH3 CH3
CH3 (major)
CH3
N
CH3 Major product of above reaction is:
CH3
(C) (D) OH CH3 (A) CH3
(B)
CH –C –CH2 – OH
HO
CH3
CH3 OH
CH2 +
Q.25 H3O A, A is
O (C) (D)
CH3 OH OH
OH
HO Q.30 Which will dehydrate at fastest rate by H3PO4 :
(A) (B) (A) 2-methyl butane-2-ol (B) 3-methyl butane-2-ol
CH3 (C) Butane-1-ol (D) 2-methyl butane-1-ol
CH3
OH OH
Q.31 What is the order of reactivity with HBr.
OH OH
(C) (D) (a) (b) (c)
CH3O
OH OH CH3O
OH
(A) a > b > c (B) b > a > c
(C) c > b > a (D) b > c > a
43
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CH2 = CH3
Q.38 Stability order of following singlet halocarbene is
Q.32 HBr
H Cl
CCl4
(A) CF2 > CCl2 > CBr2 > CI2
(B) Cl2 > CBr2 > CCl2 > CF2
CH3
(C) CCl2 > CF2 > CBr2 > CI2
What is stereochemistry of product? (D) CF2 > CI2 > CCl 2 > CBr2
(A) Racemic mixture (B) Optically inactive
(C) Diastereomers (D) Meso product CHCl / KOH
Q.39 Trans-Butene-2  3  Product
Solvent
Q.33 In the given reaction :
Cl Cl Cl Cl
H
N Br2 H
[X] (A) CH3 CH3 (B) CH3
[X] is :
H H H CH3
H Br
r
N N (C) CH3 Cl (D) Both (A) and (B)
Br
(A) (B)
H
i
Br H
H CHCl Br
N Q.40  2
 Product
(C) N (D) KOH
Br
Br
Br Product is :
Q.34 Select the incorrect statement about the product Br
Br
S
mixture in the following reaction:
(A) (B)
Br2
 Products

.
CCl 4
Cl
Cl
(A) it is optically active (B) it is racemic mixture (C) (D)
(C) it is a resolvable mixture
(D) it is a mixture of erythro compounds
J
Q.41 The order of rate of reaction of following towards
3 2 1 3 2 1 carbylamine reaction:
Q.35 Cl3C –CH = CH2 H3C – CH = CH2
O – CH3 CH3 NO2
.
(I) (II)
In addition of HOBr to (I) and (II) (i) (ii) (iii) (iv)
(A) Br is at C2 in both cases
(B) Br is at C2 in II and at C1 in I
NH2 NH2 NH2 NH2
(C) Br is at C1 in II and C2 in I
(D) Br is at C1 in both cases (A) (ii) > (i) > (iii) > (iv) (B) (ii) > (iii) > (i) > (ii)
(C) (iv) > (i) > (iii) > (ii) (D) None
N
Q.36 Which of the following compounds yield most
stable carbanion after rupture of (C1 – C2) bond: Q.42 Identify X and Y :
O OMe
O
NaOH (i) CHCl / KOH
(A) CH3 – C – CCl3 (B) CH3 – C – CBr3  X   3 
   Y.
1 2 1 2 CaO /  (ii) H3O 
O COOH
(C) CH3 – CH2 – C– CI3 (D) None of these OMe OMe OMe OMe
1 2 (A) (B)
14 NBS COONa CHO CH3

Q.37 CH2 = CH – CH3  CHO
CCl4 / Peroxide
OMe OMe
Mg / ether D O OMe OMe
   2 Product(s) (C) (D)
Product(s) is/are :
14 14
(A) CH2 = CH–CH2–D (B) CH2 = CH – CH2 –D
(C) Both of these (D) None of these CHO CHO
44
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OH R
MgBr O
Q.43 CHBr3
P1  (i) CH MgBr HN
 P2  3   P3 Q.47 3
  P. Identify P.
KOH 
(ii)H /  H2SO4
OMe
R R
P1, P2 and P3 are
OMe N–H O
(A) OMe OMe (A) (B)
O
NH
CHOH R
OH
(C) (D) Both (A) and (C)
Me O
NH
OMe OMe OMe
(B)
Me2CH OH conc .H SO
2 4
Q.48 C=N     A
Me 
r
OH CHO CHOH
Major product of this reaction is
Me
(A) Me2CH – NH – C – Me
i
OMe OMe OMe
(C) O
(B) Me – NH – C – CHMe2
OH CHO CH= CH2
OMe O
OMe OMe
S
(D) Me
(C) Me – C – CH = N – Me
.
CHO CH= CH2
OH
h /  (C) CH2 = C –CH = N –Me
Q.44  P.
 
Me
N3
J
'P' is:
OH
(A) (B) Q.49 O N
P  Toluene sulphonyl
      P. 'P' is
.
•• Chloride
N
N=N
H
O O
O
(C) N=N (D) N=N (A) NH (B) O
NH
NH2
O O
NH Br O
N
3 2
Q.45 (X) C4H7OCl   C4H9ON 
  (C) O (D)
KOH NH
HN
CH3CH2CH2NH2. Compound (X) is
O
O CH3
O
(A) (B) C – Cl COOD 
Cl CH3 Q.50  product is
(C) OH (D) CHO
C2H5
Cl
Cl
OD O
Q.46 Which of the following can not give Hoffmann's
(A) (B)
bromamide reaction:
C2H5 C2H5
O
O C – NH2 O
OD
(A) Me – C – NH – Br (B) CH2OD
O
(C) (D)
O
C2H5 C2H5
(C) Me – C – NH – Me (D) N–H
45
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EXERCISE – II CH3
Q.1 Match the column :
(CH3 –CH)2CuLi
Column-I Column-II 
NBS
Product(s)
(A) Electrophile (P) CH3 – CH = CH – CH3 CCl4 / peroxide
(B) Nucleophile (Q) :CHCl Product(s) are :
 CH3
(C) Lewis acid (R) CH3 – CH2 (A) H3C –CH = CH – CH
(D) Lewis base (S) Guanidine CH3
CH3
Q.2 Select the correct statements : (B)
H3C –CH – CH –CH = CH2
(A) Protonation increases electrophilic nature of
CH3
carbonyl group
– – (C) H3C –CH –CH2 –CH = CH – CH3
(B) CF3SO3 is better leaving group than CH3SO3
(C) Benzyl carbocation is stabilized by resonance CH3
OH (D) H3C –CH –CH = CH – CH2 – CH3
r
(D) CCl3CH is unstable
CH3
OH
i
Q.8 Select correct statement about the product (P) of
Q.3 Which of the following can be produced by Wurtz the reaction :
reaction in good yield. H Me
Br / CCl
(A) (B) 2 
4
P
Me H
S
(C) (D) (A) P is optically inactive due to internal
compensation
(B) P is optically inactive due to the presence of
.
Q.4 Select true statement(s) : plane of symmetry in the molecule
(A) Instead of radical substitution, cyclopropane (C) The structure of P can have three optical
undergoes electrophilic addition reactions in isomers possible
sun light. (D) P can have four possible optical isomers.
(B) In general, bromination is more selective than
chlorination
J
Q.9 Products formed when HCl adds to 2,4-hexadiene
(C) The2,4,6-tri-tert, butylphenoxy radical is is:
resistant to dimerization (A) 4-chloro-2-hexene (B) 2-chloro-3-hexene
.
(D) The radical-catalysed chlorination, ArCH3  (C) 2-chloro-4-hexene (D) 1-chloro-2-hexene
ArCH2Cl, occurs faster when Ar= phenyl than
when Ar= p-nitrophenyl. CH3
HBr
Q.10 In the given reaction C7H12 (A)  Br
Q.5 Choose all alkane that give only one monochloro as major product
derivative upon reaction with chlorine in sun light. (A) can be
CH2
(A) (B)
N
(A) CH =CH2 (B)
(C) (D) CH3 CH3

(C) (D)
NBS HBr Q.11 Which of following reaction product are

Q.6   (X)+(Y) enantiomeric pair.
CCl4 / h diastereomer of each other.
Br CHO
Br
Br2 (i) NaCN
(A) CH3   (B) D H  

(A) (B) CCl4 (ii) H
Br CH3
Br CH3 CH3
(C) HBr
C=C 
Br Br CCl4
H H
(C) (D) (D) CH3 –CH – CH = CH –Ph 

HCl
Br Br peroxide
conc . H SO Et
Q.7 H3C –CH2 –CH2 –CH2   2
4
X+ Y

OH
46
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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
OH O
(B)
(A) (B)
OH
OH OH
O
(C)
OH
(C) (D) OH
r
O O
OH O
(i) H2O (D)
O P1
NaN3  (ii) ROH
i
OH
Q.13 MeO C – Cl  A
  P2
(iii) RNH2
P3
Q.17 Select the correct statements.
P1, P2 and P3 are :
(A) methyl malonic acid is converted into
(A) MeO NH2 propanoic acid on heating
S
O (B) succinic acid forms succinic anhydride on
(B) MeO NH – C – OR heating
.
(C) 3-hydroxy propanoic acid forms Lactide on
(C) MeO N= C = O
heating
O O
(D) (D) CH3 – C –CH2COOH forms acetone on heating
MeO NH – C – NHR
J
 Soda lim e
Q.14 Which of the following reaction is not representing Q.18 C5H8O4(A)  C4H8O2(B)    (C)

.
major product. C is a hydrocarbon occupying 0.509 litre per g at
OH O
(A) +
NTP approximately. Hence A and B are:
H
C= N
•• 
CH3 C – NH – CH3 (A) methyl malonic acid, propanoic acid
CH3 (B) succinic acid, succinic anhydride
(C) Dimethylmalonic acid, 2-Methylpropanoic acid
(B) H
14 14
(D) Ethyl Malonic acid, Butanoic acid
Ph–Li
C= C CC CH3
N
Cl Q.19 Which of the following reaction is not incorrectly
formulated.
CH3
 SO Cl
(A) CH2=CH–CH3  2
2
 CH2Cl–CHCl– CH3
O UV light
(C) Ph – C – NH Br2
Ph –NH2 CH
2
KOH
(B) HC  CH + CH2N2  HC
N
O NH2 HC
N
HN3 H
(D)
H2 SO4 photo
(C) (CH3)3CH+Cl2  
 (CH3)3C–Cl
ha log enation
Q.15 In which of following compound chiral center is
as major product
not affected on heating.
HCl
(A) CH3 – CH – COOH (B) O (D) CH3 – C  C – H  CH3 – CH – CH2
OH
HOOC CH3 Cl Cl
(C) CH3 – CH – CH2 – COOH (D) CH3 – CHCOOH

OH CH2COOH
47
----------------------------------------------------------------------------------------------------
D
2KNH
Q.20  
 ? Q.21 Cl KNH
 
2
?
NH3 ,33C
liq. NH3
D
Cl
D NH2
H2N NH2
(A) (B) (A) (B)
NH2
NH2
NH2 NH2
D D
(C) (D)
(C) (D)
D
NH2
Q.22 This question consist of two statements, printed as assertion and reason, while answering this question you
r
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.
i
(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 : PCl5
C= N O2N C– NH OMe

S
OH O
OMe
.
OMe
Reason : Migratory aptitude of group is greater than migratory aptitude of group during
NO2
J
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 – CH2–Cl (R) Three trichloro product
(D) CH3 – CCl2 – CH3 (S) Four trichloro product
Cl Cl
(E) CH3 – C – C – CH3 (T) Atleast one of the trichloro product is optically active
N
CH3 CH3
(U) Two trichloro products
Q.24 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) Ph–CHCl 2  (A) (P) Carbocation

Na
(B) R – Br 
 (Q) Carbanion
dry ether
O
(i) Mg / H O
(C) CH –C –CH   2  (R) Free- radical
3 3
(ii) H SO  2 4,
CH3 OH
H
(D) 
 (S) Carbene

48
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Q.25 Column-I Column-II
O
3 HN
(A) Caprolactum formation take place in (P)  
H2SO 4
N – OH
H
(B) Beckmann rearrangement is (Q) 


OH
(i) CHCl / HO 
(C) Schmidt reaction is (R)   3 
(ii) H
OH
r
Ph
5 PCl
(D) Reaction in which number of carbon increases (S) C= N  
CH3
EXERCISE – III
i

(ii) Ph –CH = CH2 + N2 CO2Et  ?
Zn
Q.1 Identify P1 to P8. O

H H 
(iii) Cl3C – C – OH + Na  A  B. Find
S
HBr
CH3 – CH = CH – CH2 CH2 CH3   P1 + P2 CH2 CH2
D T out A & B.
.
H
HBr Q.5 (a) Formulate the reactions between but-1-ene
CH3 – CH = CH – CH2 – CH – CH2 CH3  
in presence of small amount of benzoyl
D T
peroxide and (i) CCl4 (ii)
P1 + P2 + P3 + P4 CBrCl3
HBr Give your reasons.
 
J
CH3 – CH = CH – CH2 – CH – CH2 – CH –CH3
(b) The dichlorocarbene reacts with phenol in
D T base where as it doesn't reacts with
benzene explain.
.
P1 + P2 + P3 + P4 + P5 + P6 + P7 + P8
Q.2 Compare the rate of decarboxylation in sodalime Q.6 Give the product of the following reaction.
process for the following. O
Mg
(i) (a) HC  C – COOH (b) CH2 = CH –COOH (i)  A

(c) CH3 – CH2 – COOH H2O
(ii) (a) CH2 – CH2 – COOH (b) F–CH2 –CH2 – COOH (ii) CH = O
Mg
 B

N
NO2 CH = O H2O
(c) Cl – CH2CH2 –COOH O

Mg H SO
(iii) (a) CH3 – CH – COOH (b) CH3 – CH – COOH (iii) Me –C –Et  2 
 4
C
H2O 
F Cl
O
CH3 – CH – COOH Mg H SO
(c) (iv) Ph –C –Me  2 
 4
 D
H2O 
CH3
Q.3 Which compound is more stable explain. Q.7 Identify missing products in the given reaction
O sequence.
    Br2 / h aq. KOH
(a) CH3 – C – CH = N = N and CH3 – CH = N = (a) CH3 – CH2 – CH3   (A)   
N H SO 2 Br
(B) 2 
4
 (C) 
  (D) = ?
 CCl 4
Q.4 Give product and suggest mechanism for these
O
reactions.
C – Cl NaN Ag O
3 2
MeOCH Cl CHBr (b)  
  (P)   (Q)
(i) ?   2  3
  ? 
BuLi t
BuOK H2O NaNO 2
 (R)   (S)
HCl
49
----------------------------------------------------------------------------------------------------
Q.8 Find out the total number of products (including CH3
H
stereo) in the given reaction: H C(CH3)2
OH 
 +
CH3 CH3 heat
NBS,CCl
4
CH3
    Products. CH3
Peroxide , 
2,2-Dimethylcyclohexanol 1,2-Dimethylcyclohexene
Isopropylidenecyclopentane
Q.9 With the help of following data show HBr exhibits
Q.15 (a) Write a reasonable and detailed mechanism
the peroxide effect.
–1 –1 for the following transformation.
H1°/ kJ mol H2°/kJ mol
• • • • conc .
H – X X + CH2 = CH2 X CH2 – CH2 XCH2 – C H2 + H –X XCH2 CH3 + X  
 + H2O
 H2SO 4
HCl –67 + 12.6 OH
HBr –25.1 – 50.2 HO
OH
H  / HOH
HI +46 –117.1 (b)   

r
Q.10 Addition of small amount of (C2H5)4 Pb to a Geraniol
- Terpeniol
mixture of methane and chlorine, starts the

Q.16 Assuming that cation stability governs the barrier
i
reaction at 140°C instead of the usual minimum
for protonation in H–X additions, predict which
250°C. Why?
compound in each of the pairs in parts (a) and (b)
will be more rapidly hydrochlorinated in a polar
Q.11 On chlorination, an equimolar mixture of ethane
solvent.
and neopentane yields neopentyl chloride and
(I) (II)
ethyl chloride in the ratio 2.3 : 1. How does the
(a) CH2 = CH2 or
S
reactivity of 1° hydrogen in neopentane compare
with that of a 1° hydrogen in ethane?
(b) or
.
Q.12 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 Choose the member of the following pairs of
yielded monobromo alkane (B). The same unsaturated hydrocarbons that is more reactive
compound (B) was obtained when (A) was treated towards acid-catalysed hydration and predict the
regiochemistry of the alcohols formed from this
J
with HBr in presence of peroxide. Write down the
structure formula of (A) and (B) and explain the compound.
reactions involved. (a)
.
or
Q.13 Give product(s) in each of the following reactions.
(i) (ii)
Br / h
(a) CH3 –CH – CH2 – CH2 – CH3 2 (A)(major)
(b)
CH3 or
CH3 (i) (ii)

(C H CO) O (c)
+ NBS 65 2 (B)
N
(b) or
S (i) (ii)
h
(c) CH3–CH2–CH=CH2+Me3COCl 
 (C) + (D) Q.18 Give product in the following reaction.
CH3
(i) NaNO 2
CH3 – C – O –Cl / A
HCl
NH2
CH3
(d)C6H5–CH2–CH2–CH3 (E)(major) (ii) NaNO2
B
NH2 HCl
Q.14 We saw that acid-catalyzed dehydration of 2,2-
dimethyl-cyclohexanol afforded 1,2- CH2NH2 NH2
dimethylcyclohexene. To explain this product we (iii) NaNO2 (iv) NaNO2
must write a mechanism for the reaction in which C D
HCl HCl
a methyl shift transforms a secondary carbocation
to a tertiary one. Another product of the
(v)
dehydration of 2,2-dimethylcyclohexanol is NaNO2
E
isopropylidenecyclopentane. Write a mechanism HCl
OH NH2
to rationalize its formation.
50
----------------------------------------------------------------------------------------------------
Q.19 What are the products of the following reactions?
(B) CH3CH2CHBr OH
(a) PhCH = CHCH3 + HBr  A
H3C CH3
(b) C=C + HI  B (C) CH3CHBrCH2 Br
H3C H
CH3
(D) CH3CH2CHBr Br
Peroxide
(c) + HBr   
 C
CH3 Q.5 An aromatic molecule will: [JEE 1999]

(d) + HCl  D (A) have 4n  electrons
(B) have (4n +2)  electrons
(C) be planar
CH2CH3
(D) be cyclic
r
Q.20 Complete following reaction: Q.6 The enol form of acetone, after Prolonged
HCl treatment with D2O, gives: [JEE 1999]
(a) H (b) Br2
CH2
CCl4 O
i
OD
CH3 CH3 (A) CH3 – C = CH2 (B) CH3 – C – CH3
(c) Cl2 OH OD
CS2
(C) CH2 = C – CH2D (D) CD2 = C – CD3
S
Total number of products obtained in this reaction
is? Q.7 A solution of (+) 1-chloro-1-phenylethane in
toluene racemizes slowly in the presence of small
.
EXERCISE – IV (A) amount of SbCl5 due to formation of:
[JEE 1999]
Q.1 Reaction of R–CO – NH2 with a mixture of Br2 and (A) carbanion (B) carbene
KOH gives R – NH2 as the main product. The (C) free radical (D) carbocation
intermediates involved in this reaction are :
Q.8 Amongst the following, the most basic compound
J
[JEE 1992]
(A) R –CO –NHBr (B) RNHBr is : [JEE 2000]
(C) R – N = C = O (D) R.CO.NBr2 (A) C6H5NH2 (B) p-NO2–C6H4NH2
.
(C) m-NO2–C6H4NH2 (D) C6H5CH2NH2
Q.2 Which one of the following has the smallest heat
of hydrogenation per mole? [JEE 1993] Q.9 The correct order of basicities of the following
(A) 1-Butene (B) trans-2-Butene compounds is: [JEE 2001]
(C) cis-2-Butene (D) 1,3-Butadiene NH O
CH3 – C (CH3)2NH
Q.3 In the following compounds : [JEE 1996] CH3CH2NH2 CH3CNH2
NH2
N
OH OH OH
OH (1) (2) (3) (4)
(A) 2 > 1 > 3 > 4 (B) 1 > 3 > 2 > 4
(C) 3 > 1 > 2 > 4 (D) 1 > 2 > 3 > 4
NO2 Q.10
2 2
Left to right sp , sp , sp, sp hybridization is
CH3 NO2
present in : [JEE 2003]
(I) (II) (III) (IV) (A) H2C = CH – C  N (B) H2C = C = CH –CH3
The order of acidity is : (C) HC  C – C  CH (D) HC  C – CH = CH2
(A) III > IV > I > II (B) I > IV > III > II
(C) II > I > III > IV (D) IV > III > I > II Q.11 Maximum dipole moment will be of: [JEE 2003]
(A) CCl4 (B) CHCl3 (C) CH2Cl 2 (D) CH3Cl
Q.4 The reaction of CH3–CH=CH OH with OH
COOH
HBr gives : [JEE 1998] Q.12
H
(A) CH3CHBrCH2 OH
O 2N OH
M
when X is made to react with 2 eq. of NaNH2 the

product formed will be : [JEE 2003]
51
----------------------------------------------------------------------------------------------------
Q.18 For 1-methoxy-1,3- butadiene, which of the
 OOC OH 
OOC O
 following resonating structure is the least stable?
[JEE 2005]
(A) (B) (A)  
H2 C – CH – CH  CH – O – CH3
 H

O2N OH O 2N OH (B) H C – CH  CH – CH   O – CH3
M M 2
(C)  
HOOC
O H 2 C  CH – CH  CH – O – CH3
 OOC OH

(D) H C  CH  CH – CH   O – CH3
2
(C) (D)
CH3
H 
OH Q.19
O2N O O2N Ph – MgBr +CH3 –C – OH A
M M
CH3
r
  CH3
H3N NH3
z y
(A) (B) CH3 – C – OPh
i
Q.13 M [JEE 2004]
COOH
x
CH3
Correct order of acidic strength is: OH

(A) x > y > z (B) z > y > x CH3
(C) y > z > x (D) x > z > y (C) (D) CH3 – C – Ph
S
Q.14 Order of rate of reaction of following compound CH3
with phenyl magnesium bromide is: [JEE 2004]
.
Ph – C – Ph Me – C – H Me – C – Me Q.20 When benzene sulfonic acid and p-nitrophenol
O O O are treated with NaHCO3, the gases released
respectively are [JEE 2006]
(I) (II) (III)
(A) SO2, NO2 (B) SO2, NO
(A) I > II > III (B) II > III > I (C) SO2, CO2 (D) CO2, CO2
J
(C) III > I > II (D) II > I > III
Q.21 (I) 1,2-dihydroxy benzene
Q.15 1-Bromo-3-chloro cyclobutane on reaction with 2- (II) 1,3-dihydroxy benzene
.
equivalent of sodium in ether gives [JEE 2005] (III) 1,4-dihydroxy benzene
Br Cl (IV) Hydroxy benzene [JEE 2006]
The increasing order of boiling points of above
(A) (B) mentioned alcohols is
(A) I < II < III < IV (B) I < II < IV < III
(C) (D) (C) IV < I < II < III (D) IV < II < I < III
N
Q.22 CH3NH2 + CHCl3 + KOH  Nitrogen containing
SO3H compound + KCl + H2O. Nitrogen containing
compound is [JEE 2006]
CH3COONa(excess)
(A) CH3 – C  N (B) CH3 – NH –CH3
Q.16 (aq. solution) [JEE 2005] + + –
–
Me (C) CH3–N  C (D) CH3N  C
SO2COOCH3
Question No. 23 to 25 (3 questions)
(A) (B)
Me Comprehension I
SO3Na COONa
RCONH2 is converted into RNH2 by means of
Hofmann bromamide degradation.
(C) + CH3COOH (D) + H2SO4
O O O
Cl Cl Cl
NH2 –
NH–Br N–Br
Me Me (ii)
••
(i) (iii)
– +
Q.17 Conversion of cyclohexanol into cyclohexene is OM O
C
most effective in: [JEE 2005] H2N Cl
O
Cl
N N Cl
(A) concentrated H3PO4 (B) concentrated HCl
H
(C) concentrated HCl/ZnCl 2 (vi) (v) (iv)
(D) concentrated HBr
52
----------------------------------------------------------------------------------------------------
In this reaction, RCONHBr is formed from which Q.28 The structure of the intermediate I is: [JEE 2007]
 
this reaction has derived its name. Electron 
ONa
 
ONa

donating group at phenyl activates the reaction. CH2Cl CHCl2

Hofmann degradation reaction is an (A) (B)
Intramolecular reaction.
CH3 CH3
Q.23 How can the conversion of (i) to (ii) be brought 





ONa ONa
about? [JEE 2006]
(A) KBr (B) KBr + CH3ONa CCl3 CH2OH
2
(C) KBr + KOH (D) Br2 + KOH (C) (D)
Q.24 Which is the rate determining step in Hofmann CH3 CH3

bromamide degradation? [JEE 2006]
(A) Formation of (i) (B) Formation of (ii) Q.29 Hyperconjugation involves overlap of the following
(C) Formation of (iii) (D) Formation of (iv) orbitals: [JEE 2008]
r
(A)  –  (B)  – p (C) p – p (D)  –
Q.25 What are the constituent amines formed when the
mixture of (i) and (ii) undergoes Hofmann Q.30 The correct stability order for the following
i
bromamide degradation? species is: [JEE 2008]
15
CONH2 CONH2 



O
D
(i) (ii) (I) (II)
S

15 15 
NH2
(A) NH2
, NH2
,
NH2
,
O 

D
.
D
(III) (IV)
(B) NH2
15 (A) (II) > (IV) > (I) > (III) (B) (I) > (II) > (III) > (IV)
, NH2
(C) (II) > (I) > (IV) > (III) (D) (I) > (III) > (II) > (IV)
D
15 15
Q.31 In the following carbocation , H/CH3 that is most
(C) NH2 NH2 likely to migrate to the positively charged carbon
J
,
is [JEE 2009]
15
(D) NHD [JEE 2006] H H
,
.
1 2 + 4 5
H3C – C – 3C – C –CH3
HO H CH3
Paragraph for Question Nos. 26 to 28 (3 questions)
Riemer-Tiemann reaction introduces an aldehyde (A) CH3 at C-4 (B) H at C-4
group, on to the aromatic ring of phenol, ortho to (C) CH3 at C-2 (D) H at C-2
the hydroxyl group. This reaction involves
electrophilic aromatic substitution. This is a EXERCISE – IV (B)
N
general method for the synthesis of substituted
salicylaldehydes as depicted below. Q.1 Complete the following, giving the structures of

  the principal organic products: [JEE 1997]
OH ONa OH
Ph H
CHO CHO (a)
aq.HCl + KNH2 A
(I) Ph Br
(Intermediate)
CH3 CH3 CH3 (b) + CHBr3 + t- BuOK B

(I) (II) (III)
Q.2 Write the intermediate steps for each of the

Q.26 Which one of the following reagents is used in the
following reaction. [JEE 1998]
above reaction? [JEE 2007] 
(A) aq. NaOH + CH3Cl (B) aq. NaOH + CH2Cl2 H3 O
(i) C6H5CH(OH) C  CH    C6H5CH = CH –CHO
(C) aq. NaOH + CHCl 3 (D) aq. NaOH + CCl 4
Q.27 The electrophile in this reaction is [JEE 2007] (ii) 

H
(A) : CHCl (B) +CHCl2
(C) :CCl2 (D) •CCl 3 OH CH3
O
53
----------------------------------------------------------------------------------------------------
Q.3 Out of anhydrous AlCl3 and hydrous AlCl3 which Q.5 Give resonating structures of the following
is more soluble in diethyl ether? compound. [JEE 2003]
Explain with reason. [JEE 2003]
Q.4 Match Ka values with suitable acid: [JEE 2003]

OH
Ka Acid Q.6 Which of the following is more acidic and why?
–5
(i) 3.3 × 10 (a) COOH [JEE 2004]
–5
(ii) 4.2 × 10 (b) Me COOH 

NH3
NH3
–5
(iii) 6.3 × 10 (c) Cl COOH
–5
(iv) 6.4 × 10 (d) MeO COOH
r
F
–5
(v) 30.6 × 10 (e) O2N COOH
Q.No. 1 2 3 4 5 6
SiANSWER KEY
EXERCISE-1
7 8 9 10 11 12 13 14 15
.
Ans. B B C C D B C B D D A D C C B
Q.No. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans. C B C A A D C D C B D D B C A
Q.No. 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
Ans. B C D A C A C A B C B C D B A
J
Q.No. 46 47 48 49 50
Ans. C D B C A
Q.No.
Ans.
Q.No. 8
1
A
Q,R
9
B
P,S
10
C
Q
11
. EXERCISE-II
D
P,S
12
2
A,B,C
13
3
B,D
14
4
B,C,D
15
5
A,B,D
16
6
B,D
17
7
B,C
18
N
Ans. A,B,C A,B A,B,C A,B,D A,B,D A,B,D A,B,D A,B,D A,B,C A,B,D C,D
Q.No. 19 20 21 22 A B C D E
23
Ans. A,C,D B,C A,C B S,T P,S,T U Q T,U
Q.No. A B C D A B C D
24 25
Ans. Q,S Q,R P,R P P,Q Q,S P R
EXERCISE-III
H H H Br H H
Q.1 P1 = CH3–C –CH2 –C –CH2 –C –CH3 P2 = CH3–C –CH2 –C –CH2 –C –CH3
Br D T H D T
H D H Br D H
P3 = CH3–C –CH2 –C –CH2 –C –CH3 P4 = CH3–C –CH2 –C –CH2 –C –CH3
Br H T H H T
54
----------------------------------------------------------------------------------------------------
H D T Br D T
P5 = CH3–C –CH2 –C –CH2 –C –CH3 P6 = CH3–C –CH2 –C –CH2 –C –CH3
Br H H H H H
Br H T H H T
P7 = CH3–C –CH2 –C –CH2 –C –CH3 P8 = CH3– C –CH2 –C –CH2 –C –CH3
H D H Br D H
Q.2 (i) a > b > c; (ii) a > b > c ; (iii) b > a > c Q.3 (a) Due to Resonance
Br
Q.4 (i) & OMe (ii) Ph COOEt
r
Br
i
•
(iii) A : • CCl2 B:
Cl Cl
Q.5 (a) Free radical mechanism (b) Due to more electron density
Br OH
S
Br2/h aq.KOH
CH3– CH2 – CH3 CH3– CH – CH3 CH3– CH – CH3
Q.7 (a)
(A) (B)
.
Br2
CH2 – CH – CH3 CH2 = CH – CH3
CCl4
Br Br (C)
(D)
J
O O
C – Cl OH O
C – N3 N=C=O
.
(b) NH2 NaNO2
NaN3 Ag2O
 H 2O
+HCl
CH3
CH2 – Br CH2
Br
Q.8 and its enantiomer, and its enantiomer,
,
N
Br
CH3 CH3 CH3

Br
Br Br
and its enantiomer,
,
Q.11 1.15 times more reaction Q.12 A =
Br CH2Br
Q.13 (a) A : (b)B : (c) C: CH3 – CH –CH = CH2
CH3 – C – CH2CH2CH3
Cl
CH3
S
D: CH3– CH = CH–CH2Cl (d) E: Ph – CH –Et

Cl
55
----------------------------------------------------------------------------------------------------
 OH
+  +
Q.15 (b) H HOH/H
OH
Q.16 (a) II, (b) I Q.17 (a) II, (b) I, (c) II
Cl
Q.19 (a) (b) Me2C(I) –Et, (c) (d)
Ph –CH – Et
Br
Br Et
r
CH3 Cl
Q.20 (a) H + H (diastereoisomers)
i
Cl CH3
CH3 CH3
Br Br
S
(b) + (diastereoisomers)
Br Br
.
Me Me
Me Me
(c) H Cl + Cl H (Enantiomers)
J
H Cl Cl H
Et Et
EXERCISE –IV(A)
.
Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C D D B B,C,D D D D B A D C D B C
Q.No. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans. C A C A D C D D D B C C B B D
Q.No. 31
N
Ans. D
EXERCISE –IV(B)
Br
Q.1 (A) PhC  CPh, (B)
H –H2O
C6H5–CH –C  CH C6H5–CH –C  CH C6H5–CH –C  CH
+

Q.2 OH OH2
H2O +
C6H5–CH =C = CH C6H5–CH =C = CH
+ –H
+
OH2
tautomerism
C6H5–CH =C = CH C6H5–CH =CH – CHO
OH2
56
----------------------------------------------------------------------------------------------------
+
(ii) +
H
OH ••
OH
••
–H +
+
O| CH3 O CH3
H
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


OH
i

NH3
Q.6 is more acidic as overall effect of –F is electron withdrawing so loss of portion is easier from this
S
F
compound.
J.
.
N
57
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i r

(f)  _________

(l) CH3—CH—CH2—OH  _ _ _ _ _ _

Mechanism:– Q.8 3, 3–Dimethyl–butan–2–ol loses a molecule of

(2) H — O — N = O + H H2O + N=O

(3) R—N: + N = O  R—N — N = O  R—N—N = O—H

N2  R  R — N  N :  R—N = N + O  R—N = N—O: 

Q.5 SbCl5 __________

IIT-JEE ChEmistry by N.J. sir

(1)  —C — C— Cl2

C=C + Nu Q.7  _ _ _ _ _ _ _

(C) CH3 – CH2 – CH (D) CH2 – CH2 – CH2

CH3 — O C C CH3 + H  Intermediate Carbocation

Intermediate Carbocation  rearrangedCarbocation

(a) (b) (c) (d) (A) , Major product (A) is

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

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

Total number of products obtained in above OH

CH3 (d) C=C  

Q.3 What will be major – product obtained from

CH3 — CH — CH2 — CH = CH2

Q.2 Find total product in following reaction ? (including

2. (a) x  3 ; y 2 ; z 5

Q.2 Identify reactant in following reaction

dibromobutane. 2. (a) A  Trans but-2-ene

O Q.4 How many initial ozonoids are possible in given

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

Q.9 In which of following reaction product formed is

(2) R — X + 2e–  R+ X Na  _ _ (Wurtz fitting)

Q.5. Amongst the following, the most basic compound is:

Q.7. Write mechanism of following reactions?

Ph3 C─Cl 

(regarding stability of free radical)

Q.9. Supply the structure and type of intermediate species designated by

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

Q.12 CH3 C° + CH3 C°           

Q.13 CH3 — C°H2 + CH3 — C°H2           

Q.6 C + C  

IIT-JEE ChEmistry by N.J. sir

Q.2 Identify major products. Br

(2) AlHg (6) 14 Na 

(12) CH3 — CH2 — Cl + Na

7. R & S-2-chloro butane

Q.1 The order of reactivity of alkyl halide in the reaction O

Q.12 Carbonyl compound (X) + Grignard reagent (Y) 

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

Q.14 In which one of the following reaction products are Br 1. Mg/ether

(B) H2C  CH – CH  C – CH3 Q.23 O

CH3 OH (A) CH4 + IMgO C– CH3

O (B) CH3–O C– CH3

IIT-JEE ChEmistry by N.J. sir ORGANIC chemistry

Mechanism: – This reaction leads to inversion of Configuration.

Homologation Reaction:– 9. 1. SOCl 2 --------------

IIT-JEE ChEmistry by N.J. sir ORGANIC chemistry

Q.1 Fill in the blanks:–

O + R — C — N: – R— C — N— H + Br Q.1 Compare rate of reaction:–

2 Q.2 Fill in the blanks:–

Q.1 CH2 — C— N — O — C — Ph 

Q.2 Decreasing order of nucleophilicity of the H

(IV) Cl + Cl , H4°

(A) P > Q > R > S (B) Q > P > R > S Me

14 NBS COONa CHO CH3

OH (D) H3C –CH –CH = CH – CH2 – CH3