SubsUtution Reactions (S*,,t",, S* )

ET

1. Which of the following is not expected to be intermediate of the following reaction ?

I
Hzo
---+

,"rd ,rro ,.rd

i + NaI Acetone
^- ) L
product;' S product of the reaction is :
CHs ^z
cHz - cHs
 cHs 'r cr{?
r--l--H H I r+-H
9Hs
(u)
H-t-cH, rul n ' IIJ cHs (c) (o)
arr-fn
cHz - cHs CHz _ CHg cHz - cHs cH2 - cH3
3. Rate of S*z will be negligible in :

Br Br

(a) (b) ,.rO (d)

O
4. what is the major product obtained in the following reaction ?

d:-t'--*#-product

cHs
I

5. Cl -CH2 -C -CH2 - CHz - Cl + I- DMr- product; Major product of this reaction is:
I

cHs
CH^ cHs
t'
(a) I-CHz -f -ar, -CH: - Cl
I

(b) ct -cHz -c -cH2 -cH2 - r

I

CH, CH,
cHs cHs
I

(c) H2C=C-CH2-CH,
I

=61 (d) Ct -CHz -C -CH2 = CHz

I

CH,
Which of the following expressions is representative of the rate law for a S
*z r€oction ?
(a) Rate - k [electrophile] (b) Rate = k [electrophile] [nucleophile]
(c) Rate = k [nucleophile] 2 (d) Rate =k[electrophite]2
Acetone
7. NaI (1 mote) >,jfL,, Major product of this reaction is :
*rtk*
,,in{}I ronQ,! (c)#Gl rorbO<,n
 8. Which ,n;rlrjlowing alM halide undergo rearrangement in S *r
"t
u

t
(a)cHs-f
eI:,,.r eft n,,,1rr,.Lr
cH-cH3O) (d) All of these

g. ,r"T;"ling
Arrange three chlorides in decreasing order towards S
*r reoctivity.
(l)Ycr (2)ry CI
G)a CI
(a) 7>2>3 (b) z > 3 > 1

(c) 2>7>3 (d)s>2>l

1"O. Which compound undergoes nucleophilic substitution with NaCN at the fastest rate ?

,u, ,r.', rul

Br),/:,n (c) ,r--X.,^. (d) BrX\r .'
'X
11. Rank the following in order of decreasing rate of solvolysis with aqueous ethanol (fastest -+

f'' 1l<"'
slowest)

H2c=C-Br \-,/ \Br I'

CHs -CHCH2CH(GH3)z
(1) (2) (3)
(a)2>1>3 (b) 1>2>3
(c) 2>3>1 (4) 1>3>2
12. The reaction of 4-bromobenzyl chloride with sodium cyanide in ethanol leads to the
formation of :

(a) 4-bromobenzyl cyanide (b) 4-cyanobenzyl chloride

(c) 4-cyanobenzyl cyanide (d) +-bromo-2-cyanobenzyl chloride
L3. Which of the following reactant will not favour nucleophilic substitution reaction ?

(a) (b) Ph - Br

Br
cHs
I

(c) CHs -C - CH2 - Br (d) All the above

I

cHs
Br

1,4.
+oH-
H H
(r) (D
 Conversion of I to II :

(a) takes place by S*r (b) takes place by S *e

(c) takes place both by S *r and S *z (d) does not take place
L5. Which is the correct reaction coordinate diagram for the following solvolysis reaction ?

d:: ""d;:+ d;,

Reaction Coordinate
(b)
^.ft
o"l

Reaction Coordinate

(c,L Reaction Coordinate

Reaction Coordinate

14c labelled
\
16.
oar:: OCOR
RCO"H
product; Product of this reaction is

OCOR
:

(c) both (a) and (b) (d) None of these

I
-l- -cH,
17.
ol'*u" (A) cnrs*u > (B) , product (B) is :
 I I

,", ,r,ds-cH3
dcH2-s-cH3
s-cH3

...,dcH"-Br (d) None of these

18. represents the correct graph for S *z reaction

Which of the following rt ?

log (rate)

(a)

CHg - Br CH3 - CHz- Br CH3 - CH-

I, _
CHs CH3 -C - Br
cHs

log( rate)
(b)

Ct{3 - Br Et-Br i-Pr-Br t-Bu-

log (rate)

(c)

CH3 - Br Et-Br i-Pr-Br r-Bu- Br

(isopropyl)
 log (rate)
(d)

cH3-Br Et-Br i-Pr*Br t-Bu-Br

19. Which of the following graph represents correct graph for S*r r€zlction :

log (rate)

(a)
CHs - Br CH3 - CHs- Br CH3 - !H- Br
I

cHg
1"
cHs-g-8,
I

cHs

log (rate)
(b)

CH3 - Br Et-Br i-Pr-Br r-Bu-Br

log (rate)

(s)

CH3-Br Et-Br i-Pr-Br r-Bu-Br

 log (rate)
(d)

cHs
pound in
S
*r f€ilCtion ?
(a) CHs -CHz -CHz -CHz -Br orCH3 -CHz -!H-CH,
Br
CH" cHs
t'
-CHz or
I

(b) CH3 -C -CH2 CHs -CH- CH -CH:

ll
Br Br

Br Br

,.,ooro
CH.J CH.J
I I

(d) cH3 -c -cH3 or CH3 -C -CHs

I I

Br I
22. What is the major product of the following reaction ?

H2C = CH -CHz -OH-;ffi-rProduct

Br
: CH -CH2 - Br
I

(a) CHg - CH - CHz -'Br (b) H2C

Br OH
I I

(c) CHs -CH -CHz -oH (d) cH3 -cH-cHz -oH

23. S*r and S*z products are same with (excluding stereoisomer) :

CI

(a)
G CI
*,eJ'
(c)

+ CI
(d) Ph - CH
lr,
-CH-CH3
It
24. Consider the nucleophilic attacks given below. Select in each pair that shows the greater S*z
reaction rate.
o
Br + -CN -cN
(A)
(r)
or -UA*3+(II)

(B) H3C-Br--SH or HsC-Br+CHTSH

(irr. (IV)

(c)GBr cr or A-o', + rI- in DMSo

\-rlr
(V) (u)

r,)GBr+cl- or GBr + I- in methanol

CVII) olrr)
ABCD .\BCD
(a) (I); (M; ffI); (ull) O) (ll) ; (lll) : Ol : (\{il)
(c) (I); (III); (V); VIII) (d) (l) ; (lII) : Ol : 011)
25. Which of the rwo stereoisomers of 4t-bur_v*lc-v-clohexr-l iodide ,'ll-l-) rvill undergo S^oz
substitution with 128I- faster, and why ?
H
1127

w' (B) H
(a) A will react faster because it is the more stable of the two isomers
1727

(b) A will react faster because it will yield a more stable product, and the rransition state for
both reactions is of the same energy
(c) A will react faster because the approach of 128I- can depart unhindered.
(d) B will react faster because it is less stable than A, and the transition srare for both
reactions is of the same energy
26. (Z)2-Butene reacts with Br2lH2O. The resulting bromohydrin when treaied
with
methoxide in methanol . underg:oes an intramo,-lecular S reaction.
*,
consideration the stereocheqri.cal consequences of the reacd]on
Taking into
mechanism in,Iolved,
choose the final product(s) of these rransformations.

o
(I)
rT;A;"' tu) nac,,iftg;, (uI)

(a) (I) only

,T;A:?,,
(b) (II) only
(c) (III) only (d) Equal amounrs of (I) and (II)
27. Rank the following species in order of decreasing nucleophiliciry in a polar protic solvent
(most -+ least nucleophilic) :

o
ll
cH3cH2cHzo- cH3cH2cH:S - cH3cH2c- o-
(1) 2 (3)
(a)S>l>2 (b)2>3>1 (cj l>3>2 (d)2>1>3
Identifu products of the gir-en reactions :

Reaction-1
e(:, CH -'---'-
.CC.]i.
cu,co-:-.
)product

.-..OTs
Reaction-2 ____-+
CH3CO2.\a
product
cH3co2H
NMe2

.,,G:XCHS \-cHs
o + enantiomer
NMe2

(b)
..Yttr*
enanriom.,,
NMe2
{1-o)fcHs
(c) single product is obtained in both the reactions

,.,fio\-cHs single product obtained in both the reactions

jail:r::rri:irii :i:iriiirr:i,i

.#,s

I
o
l]
(d
k
29. bo
o

CH3-X Me-CH2-X Me2CH-X Me3CH-X

Which of the following is true about given graphs A and B?
(a) A -+ S*r B -+ Sooz (b) ArS*2, B-+S*r
(c) A & B-+ E1 (d)A&B+E2
30. In each of the following groups, which is the strongest (best) nucleophile ?

(r) (1) H3C -O- (Z) AO- (3) H3 C -S- in CHrOH

(II) (1) oH- (2) H2o (3) NH, in DMF
I .o-
(rrr) (1) I (2) \o (3) CH3O- in DMSO
(a) I,3 ; II,3 ; III,2 (b) I,2;I1,1 ; III,3
(c) I,l;11,2; III,1 (d) I,3; II,1 ; III,3
o
81. @>_$ -,.rr)a-cH2 NaNH2
dimethory ethane
(A) ; Product (A) is :
(Major)
o
o o
,r, @l-r.rr)g
o
o
-cH=cHz o)
@ne o
(d) None of these

32. Which of the following reaction is an elimination reaction ?

H
Br KI
(a) * IBr + KBr
[frH "'oo, O-, Br
H
--------)

(.) NaocH,,
af:, Od.r,
(d) both (a) and (b)
 cr .ffii-
Bs' Product
+ cHz _
Which of the following products can be obtained from above reaction ?

(") L;l-cHz (c) ,o) Auorthese

- ocH3o) .rr$ U{."r'
34. What is the principal product of the following reaction ?

cHs
H4Br
H-J-H
I
+ NNs#Product
HT-CI
cHs
cHs cHs cHs

(a) H
H #n,
*, (b)
H
H (c)
r.rr--l-H
n#H (d)
H-J-
H--{-H
N,

H
I

-J-CI H H*cr cr-1-H

cHs cHg cHs
35. What would be the effect of increasing solvent polariry on the rate of each of the following
reactions ? (Nu = D€utrfll nucleophile)
(A) Nu + R * L-----+t$r-^ * r-
(a) increases (b) decreases (c) constant (d) cannotbeprediaed
(B)R-L@----+Ro +:I
(a) increases (b) decreases (c) constant (d) cannot predict
36. Which of the following is most reactive toward S*z t€action ?

(a) CHz = CH -CH2 -Cl (b) Ph -cH2 -cl

(c) Me - o^Cl (d) Ph - C- cH, -
il-
Cl

o
37, 4-chloro-1-butanol + NaOH -
"f--tal--l!C{UA-+tfl
Product (B) of the above reaction is :

(a) O ru)
rJ (c) 5lt" (d)
\ztH2-cH3
38. In the given pairs of alkyl-halide, in which pair the first compound is more reactive than
second compound toward S r€ilCtion ?
(a) (CI{s )2CHBr or CHs"z -CHz -CH2 - Br
(b) CHs -CH2 -CHz-Br or CHs -CHz -CH2 -I
(c) Ph - Br or CHs -CHz -CH2 - Br
(d) CH2 : CH -CH2 -Cl or H2C : CH -Cl
39. In the given pair of reaction in which pair the second reaction is more reactive than first
toward Srz reection ?
(a) CHs -CHz -Cl+CHs -CH2 -O- ---+ Et-O-Et (or)
CHz -CHz -Cl + CH3 -CHz -OH--+ Et -O - Et
(b) cH3 - cHz - cI + Eto- Et - o - Et (or)
cHs -cHz -cl + EtS- -+
---) CHs -CHz -S - Et
(c) _Et-Cl+CH"O ---)Et-O-CHs (or)
(1m) tzl_l
Et-Cl+ CHrO--)
(2m) Et -O -CHg
(1m)
o
(d) Et - Br + ph.p-----+ Et - pphs (or)

Et-Br-Ph:N-+E+-frofr,
40. Among the follon'rng pair of reactions in which pair the second reaction is more reactive than
first in S.-: r€sCrion ?
(a) Me3CCl - H:O- \Ie.COH (or) Me3CBr - H2O---+ Me3COH
(b) Me3CCl * CH3OH--------+ \{e3C OCH 3 (or) Me.C-Cl * H:O
-

MerC-OH
(c) Me3CCl+ H2O -----> (or) Me3CCl- H20
(1M) (2M)
(d) All of these
4r. Which is a true statement concerning the transition state of an S
*z r€flction ?
(a) Ciosely resembles a carbocation intermediate
(b) The electrophile is responsible for the reaction
(c) Lower is energy than the starting materials
(d) Invoives both the nucleophile and electrophile
42. Increasing the concentration of a nucleophile in a typical s*z reaction by a factor of 10 will
cause the reaction rate to :
(a) increase by a factor of 10 (b) increase by a factor of 102
(c) decrease by a factor of 10 (d) remain about the same
43. Decreasing the concentration of an electrophile in a typical s *z reaction by a factor of 3 will
cause the reaction ratio to :
(a) increase by a factor of 3 (b) increase by a factor of 32
(c) decrease by a factor of 3 (d) remain about the same
44. Increasing the concenffation of an electrophile in a typical s^,2 reaction by a factgr of 3 and
the concenffarion of the nucleophile by a factor of 3-will chd'iige the reaciion rate to :
(a) increase b1' a factor of 6 (b) increase by a factor of 9
(c) decrease br- a factor of 3 (d) remain about the same I

45. Consider the follon ing reaction and select the best choice that represents the reaction.

Nao -scHrcH,
Product

9Hs CH" CH"

(a) H
cH2cH3 ,,,dil1i,.n,
cHq 9Hs
t' 9Hs
(.) s-cH2cHs
OtscH2cH3
I
(d)
04
rvr"lH
lx KSH )
46. n,lO Product: Identify the product.
H
SH H SH
ira"lH NIefH
I

HS \IC H|vr"
(a) ur-|.-, (b) e,fo (c) Et D (d)Et
I D
H SH H
47. The reaction,
HOH
--.X- + SOCI2
--+
+ so2 + HCI
proceeds by the........... nnechanism.
(a) S*i (b) S*z (c) sB, (d) S*r
48. Consider the following anions.
oO
q"
o
illl
CFs-S-cl-
"ll
CoHs -S-o- lt
cHs-c-o-
I!
oo
(I) (II ) (xr) (u)
When attached ro sp3-hybridized carbon, their leaving group abiliry in nucleophilic
substitution reaction decreases in the order :
(a) I > II> III > IV (b) t> II > IV> III (c) IV> I > II > III (d) IV> III > II > I
 CH" o@
"
H --- "rl" =-) Principal
sNa
Ph
organic Product of the reaction will be :
Jo

Ph Ph
Ph
-]-
(c) H-l-ct
cH3 n-fcrr,
(d)H I Ph
I I
Ph Ph
50. Reaction of R-2-butanol with p-toluenesulphonyl chloride in pyridine followed by reaction
with LiBr gives:
(a) R-2-buryl bromide (b) S-2-butyl tosylate
(c) R-2-buryl tosylate (d) S-2-butyl bromide
51. The compound which undergoes S*r reaction most rapidly is :

c.i$,, curln,
(c) CH2Br rar$s,
52. Addition of KI accelerates the h1'droly'sis of primary a\'1 halides because :
(a) KI is soluble in organic solvents
(b) the iodide ion is a n-eak base and a poor leaving group
(c) the iodide ion is a strong base
(d) the iodide ion is a pon'erful nucleophile as well as a good leaving group
53. Which of the following phrases are not correcdy associated with S
*r r€action ?

(1) Rearrangement is possible

(2) Rate is affected by polanw of solvent
(3) The strength of the nucleophile is important in determining rate
(4) The reactivity series is tertian' > secondary > primary
(5) Proceeds with complete inversion of configuration
(a) 3, 5 (b) 5 only
,:, 2,3, s (d) 3 only
 (A) NBS (B) KSH (c)
-*3'-- > > , Product (B) is :

d
A
(d)

55. Energy profile diagram for an exothermic reaction, A -l-* g - :--15 3 , D, is given below.

t
PE.

Progress of the reaction -*

The rate determining step of the reaction is :

(a) A->B (b) B+C (c) C-+D (d) can not predict

cHg

s6. NBS>Jf]
@$
Major product is (A) is :

57.
,",Oa *,d"
Cl
-LiBr'zDMSo
S* z conditions
(c)

, Major product (X)

4 Br

The productX is :
 ,rr%r,
58.
",[\'2
Relative rate of reaction of the following amine with methyl iodide is:

A
1*j
(
(A)
N
/\n \,/*.-(c)
(a)A>B>C (b)A>C >B (c)B>C>A (d)B>A>C
H
PhcH2o\ \ 'ors

se. Hn
)1t'x!1.r,
I
Nal
Dimethyl sulfoxide

ocH3

Major product which you expect in the above reaction is :

H H
, \;ors o.r,nil!.., '
)c-"( 'g-<ocH3
2' -'\a.:o.n,
@) -J
tr' L
H I
(b) .)f
HH I

ocH3 ocH3
I
H
o.r.,rf,!..-n ocH"ptiLtr.. ors
).-'\ 'i"'2'ocu' \a - .-l
(c) ,1 (d) J' '.'<Y
L ocH3
HH t
ocH3
HS
\aOH in
(A)
60. aqueous ErOii
(major)
c6H1os
HCI
Major product of the above reaction is:
S

.,,o (d)
o
 o,
Yr
61. cHg-f-f'- - cHg --------+ Major product of the reaction is:
CH3 OTs
Ph
.nr),c_ lrq
(a) ,t'n
\CH,
(b) cH"-c-cH-cHz
"l
cHs/
cHs

cHs\ cHs\
l+r.'Ph ^ ^/Ph
u
cHr/L -- -rgt,
(d)
cHr/ -
ICJ C: C
\cHs

62. The decreasing order of reactivity of the compounds given belorv torvards soivolysis under
identical conditions is :
CI C1

cHg-9-CHs
I I

C
C1

O f -.r,
I

cHs -

A
(r)
HgC

(D
o
(rrr)
(a)II>III>I (b)I>II>III (c) III>II>I (d)II>I>III

OH

68
0G",,
1.One Eq. NaOH
(A); Product (A) is :
2 MeBr

(a) oH (b) OMe (c) (d) None of these

64. (R)-2-octyl tosylate is solvolyzed in water under ideal S*r conditions. The product(s) will
be:
(a) R-2-octanol and S-2-octanol in a 1 : 1 ratio
(b) R-2-octanol and S-2-octanol in a 1.5 : 1 ratio
(c) R-2-octanol only
(d) S-2-octanol only
65. From each of the following pairs select the compound that will react faster with sodium
iodide in acetone :
Pair-A: (1) 2- Chloropropane (2) 2- Bromopropane
Pair-B: (3) 1- Bromobutane (4) 2- Bromobutane

(a) 1,3 (b) 1,4 (c) Z3 (d) Z4

66. Among the given halides, which one will give same product in both S
*r and S
*z r€&ctions.
!', ,/\,/cHs
(r) cHs - cH -cH2 -cH-cHs ,,,, (_L.,
Br

(u)eI (M CHs -CH

I
- Br
Et
(a) (III) only (b) (r) & (rr) (c) (III) & (nD (d) (I), (u) & (IV)
67. Product(s) formed during this reaction islare :

*
CHz-CHz-OTs
1'oll
AcOH
,Product? [c. = isotopic carbonl
* *

,u qcHz-cHz-oAc G) qCHZ_CHZ_OAC
*

(c) (d) Both (a) & (b)

qtH2-cH2-ors
excess HI (conc')
68. Anisole reflux
Product

,",@r + cH3r + cH3oH

", @r
r.l
@-oH + cH3r tal
@on + cH3cH2r

69. Which 9{ lt. following compounds would react faster with NaCN in an S*z r€oction ?
OMe
(?)X,.' ,0,$or, (c) M{N (d)$OTs
 HC
-CNa+Cl-CH2 -CHz -CHz - I ----+ (A); Majorproduct (A) is:
(a) H-C :C -CH2 -CHz -CH2 - I (b) CHz =CH-CH2-I
(c) H-C :C- CHz-CHz -CH2 -Cl (d) CH2 =CH-CH2 -Cl
71. what is the major product obtained in the following reacrion ?
Et'o
+ cH3
- Br , Product.
Gt*"
,"rO orftn'
CHq
---r s
"r',2 >A; The productA is :
+ oH-

')3:"
H

(a) (b) ,:>o(:"

(c) Both (a) and (b) are correcr (d) None is correct

73. Me2C = CH - CHz - CHz - Ct ='11 ,

CaCO3
(X); Major product of the reaction is :

OH
I

(a) Me-C-CHz-CH2-CH2 (b) Me2C = CH - CHz - CHz - OH

I

Me
OH
(c) Me2C : CH - CH- CH2 - OH (d)>l*.,
OH

HBr , (A) (5'-on n,',,r,

Y
74. ,
A \

cH2oH
cH2oH ocH3
Product (A) and (B) respectively are :

r"'qo" and G)q"" and

CH2Br Br CH2Br OH
ii,
liili:li,f,,',lii,:i;.,:*iilii

,.,q"'and
CH2Br OH cH2oH ocH3

75. Relative rate of reaction with HzO.

/o
I

[-oNS---o-[-O^.",]
(a) (i) > (ii) > (iii) (b) (ii) > (i) > (iii)
(c) (iii) > (ii)> (i) (d) (iii) > (i) > (ii)

oo KNHz n-c+Ho-Br ,
76. ll ll 2 eq'
, 1P, '
NH3(l)

+1
t \.,A.. then H3oo

End product (P) of the above reaction is

oo
:
oo
(a) (b)
_J
AA
-]
I

oo oo
AA AA
77.
(c)

I (d)

-i
Which of the following statements is correct regarding the rate of hydrolysis of the
compounds (A) and (B) byS*r reaction ?

I FBr O,F. FBr

v A
\-/
B
 (a) A reacts faster than B (b) B reacts faster than A
(c) Both A and B reacts at the same rate (d) Neither A nor B reacts
78. What are reactant X and product Y in the following sequence of reactions ?

o
il
- -+ "'#r".r
Reacta
o
Bridine f M/- H Product Y

Reactant X Product Y

ta)
H, H3c:/.,\ \/-\/rN3
H"." LJ
-H

"'[M>/"7

(c)..:\-/:_ ,,|\o/"7
(d) '':Se/; ',1\O/),
79. Transition state of given S1,r, is :

QI #(!)I:
.z\zCHz-B' n n- .--zCHz-o-R

6e 3 (+)
9R OR
lrr
(a) :..N ;. (b) /-\ : ..,...s "
\_/\*,
:

Br
1 6 (+)
 6 (_)

9R
(c) (d) ,F\, ,.s'
\_/H
:
Br
6 (-)

80. CoHrsBr + OH- ---+ C6H13OH + Br-is an example of:

(a) Nucleophilic addition (b) Nucleophilic substitution
(c) Electrophilic addition (d) Electrophilic substitution
(e) Free radical substitution
81. Transition state 2 is structurally most likely as :

(a) intermediate 1 (b) transition state 3

(c) intermediate 2 (d) product

,,4

x = Number of aromatic compound obtained when above compound undergo complete

acidic hydrolysis.
(a) 1 (b) z (c) 3 (d) +
Sp 1 and Sp 2 reactions are
(q) Both stereospecific
(b) Both stereoselecrive
(c) Stereoselective and stereospecific respectively
(d) Stereospecific and srereoselective respectively
 {srrrs .rffii.,,
84. Most reactive compound toward Srr is :

,,,d ,,d (c,/{'-',.,,d

1. (a) 2, (b) 3. (c) 4. (a) lr. (b) 6. (b) 7, (b) 8. (d)

9. (b) 10. (a) 11. (c) a2. (a) 13. (d) 14" (d) 18. (b) 16. (c)

47. (a) 18. (a) lg. (c) 2(J. (d) 21. (b) 22. (a) Zg,i,. (c) 24. (c)

25. (d) 26. (d) 27. (d) 28. (a) 29. (a) 30, (d) 31. (b) s2. (d)
33. (d) 3,4. (c) 35. A(a) 35. B(b) 36. (d) i37. (b) 38. (d) 39. (b)

4(J. (d) 41, (d) 42, (a) 43. (c) M. (b) 45. (c) 46. (d) 47, (a)

48. (b) 49. (b) 50. (d) 51. (b) 52. (d) 53, (a) 54. (b) ttb. (a)

56. (a) 57. (b) 58, (c) 59. (c) 60. (b) 61. (c) 62. (d) 63. (a)

64. (b) 65. (c) 66. (c) 67. (d) 68. (c) 69. (d) 7o. (c) 71. (c)

72. (b) 7$, (d) 74. (b) 75." (c) 76. (d) 77. (b) 78. (b) 79. (d)
80. (b) 81. (c) 82. (b) 83, (c) 84. (d)