CHEMISTRY
ALLEN
Study Package
For – JEE (Advanced)
JEE-Chemistry
EXERCISE-01 CHECK YOUR GRASP
SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER)
H OH
1. The product formed in the reaction + SOCl2 is-
Cl H H SO3H
H O Cl
(A) (B) (C) (D)
Cl H
aq.H 2 SO 4 PCl 5
CH3C CH
A B.
HgSO 4 Heat
(A) free radical (B) carbanion (C) cabocation (D) final product
7. To form alkane isonitrile, alkyl halide is reacted with:
(A) KCN (B) AgCN (C) HCN (D) NH 4CN
8. Which one of the following compounds most readily undergoes substitution by S N 2 mechanism ?
22
E
dry dry
(A) CH 3 —CH 2—Cl + Mg
ether
(B) CH3 CH CH2 + Mg
ether
Cl OH
CH3
dry
(C) CH3 C OH + Mg
ether
(D) All of them
CH3
11. Most stable carbocation formed from (CH 3) 3C–Br, (C 6H5) 3CBr,(C 6H 5) 2CHBr and C 6H5CH 2Br would be
(A) C 6H 5 C H 2 (B) (CH3)3 C (C) (C 6H 5) 3 C (D) (C 6H 5) 2 CH
alc. KOH
CH3 CH CH CH3
CH 3 CH(X)CH 2CH 3
CH2 CH CH2 CH3
E 23
OH
(I) CH 2 CH—OH (II) H3C (III) CH 3—CH 2 —OH (IV) CH3 CH CH3
CH2
OH
(A) II > I > III > IV (B) IV > III > II > I (C) II > IV > I > III (D) II > IV > III > I
Al O
aq.NaOH 2 3
23. Identify 'Z' in the following reaction series, CH3.CH2CH2Br (X)
Heat
(Y)
HOCl
(Z) :
(A) Mixture of CH3CH CH2 and CH3CH CH2 (B) CH3 CH CH2
Cl Cl OH OH OH Cl
(A) HI > HCl > HBr (B) HI > HBr > HCl (C) HCl > HBr > HI (D) HBr > HI > HCl
25. Ethyl alcohol reacts at a faster rate with HI than with HCl in forming the corresponding ethyl halides under
identical conditions mainly because -
(A) HI, being a stronger acid, protonates ethyl alcohol at oxygen much better and helps substitution
(B) the bond length in HI is much shorter than that in HCl
(C) I– is a much better leaving group
(D) I– is a much better nucleophile than Cl–
24
E
Cl Cl Cl Cl
(A) I < II < III < IV (B) IV < III < II < I (C) IV < I < II < III (D) IV < II < I < III
3. The order of decreasing nucleophilicity of the following is
(A) H 2O > OH – > CH 3COO – > CH 3O – (B) CH 3O– > OH – > CH 3COO – > H 2O
(C) CH3COO– > CH3O–> OH– > H2O (D) HO – > CH 3O –> CH 3COO –> H 2 O
4. The order of decreasing SN1 reactivities of the halides
CH 3 CH 2 CH 2 Cl CH 2 = CHCHClCH 3 CH 3 CH 2 CHClCH 3
I II III
(A) I > II > III (B) II > I > III (C) II > III > I (D) III > II > I
5. Consider the following anions.
O O O
O–
CF3–S–O– C6H5–S–O– CH3–C–O–
O O
(II) (III) (IV)
(I)
When attached to sp3- hybridized carbon, their leaving group ability in nucleophilic substitution reactions
decreases in the order
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
(A) I > II > III > IV (B) I > II > IV > III (C) IV > I > II > III (D) IV > III > II > I
– – –
6. The basicity of RO ,HO , RCOO , ROH, and H2O are of the order -
(A) HO– > RO– > H2O > ROH > RCOO–
(B) RO– > HO– > RCOO– > ROH > H2O
(C) H2O > ROH > RCOO– > HO– > RO–
(D) ROH > H2O > HO– > RCOO– > RO–
7. Which of the following are aprotic solvents :
(A) DMSO (B) DMF (C) H 2 O (D) CH 3 COOH
8. Which is/are true statements (s) :
(A) Protonation increases electrophilic nature of carbonyl group
(B) CF3 SO 3– is better leaving group than CH 3 SO 3–
(C) Benzyl carbonium ion is stabilised by resonance
OH
(D) CCl 3 CH is stable,due to H-Bonding
OH
E 25
Me
SOCl2
9. Ph C—OH
inC 5 H 5 N
Cl Cl
(A) (C)
NO2
NO2
Cl Cl
(C) (D)
NO2 NO2 NO2 NO2
11. A compound 'A' formula of C3H6Cl2 on reaction with alkali can give 'B' of formula C3H6O or 'C' of formula
C3H4. 'B' on oxidation gave a compound of the formula C3H6O2. 'C' with dilute H2SO4 containing Hg2+ ion
gave 'D' of formula C3H6O, which with bromine and alkali gave the sodium salt of C2H4O2. Then 'A' is
(A) CH 3 CH 2CHCl 2 (B) CH 3CCl 2CH 3 (C) CH 2ClCH 2CH 2Cl (D) CH 3 CHClCH 2Cl
12. Isobutyl magnesium bromide with dry ether and absolute alcohol gives
(A) CH3 CH CH2OH and CH 3CH 2MgBr (B) CH3 CH CH2 CH2 CH3 and Mg (OH) Br
CH3 CH3
(C) CH3 CH CH3 , CH2 CH2 and Mg(OH)Br (D) CH3 CH CH3 and CH 3CH 2OMgBr
CH3 CH3
14. On treatment with chlorine in presence of sunlight, toluene gives the product -
(A) o-chloro toluene (B) 2, 5-dichloro toluene
(C) p-chloro toluene (D) Benzyl chloride
CCl 4 acetone
(A) RCH 2 COOAg + I 2
RCH 2 I (B) RCH 2 Cl +NaI
RCH 2 I + NaCl
26
E
Na C 2 H 5 OH
(B) C 2 H 5 Br C 2 H 6 +HBr
CH3 CH3
E 27
CH3 OH CH3 Cl
(A) C + SOCl2 C (p) S N1
Ph Ph
(+) H (+) H
CH3 OH Cl
CH3
(B) C + SOCl2 Pyridine C (q) S N2
Ph
(+) H H5C6
(–) H
CH3 OH Cl
CH3
(D) C +HCl C (s) E2
H5C6 (+) H C6H5
(±) H
(B) Cl (q) 1
H3C
(C) (r) 91
H3C Cl
28
E
4. Statement-I : Primary benzylic halides are more reactive than primary alkyl halides towards S N 1 reaction.
Because
Statement-II : Reactivity depends upon the nature of the nucleophile and the solvent.
5. Statement-I : Vinylic halides are reactive towards nucleophilic substitution reaction.
Because
Statement-II : Reactivity is due to the polarity of carbon-halogen bond.
6. Statement-I : Ar yl halides undergo electrophilic substitution less readily than benzene.
Because
Statement-II : Ar yl halide gives only meta product w.r.t. electrophilic substitution.
7. Statement-I : Optically active 2-iodibutane on treatment with NaI in acetone undergoes racemisation.
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
Because
Statement-II : Repeated Walden inversions on the reactant and its product eventually gives a racemic
mixture.
8. Statement-I : Free radical chlorination of n-butane gives 72% of 2-chlorobutane and 28% of 1-chlorobutane
though it has six primary and four secondary hydrogens.
Because
Statement-II : A secondary hydrogen is abstracted more easily than the primary hydrogen.
9. Statement-I : Nucleophilic substitution reaction on an optically active alkyl halide gives a mixture of
enantiomers.
Because
Statement-II : The reaction occurs by S 1 mechanism.
N
10. Statement-I : Boiling point of alkyl halide increases with increasse in molecular weight.
Because
Statement-II : Boiling point of alkylhalides are in the order RI > RBr > RCI > RF.
E 29
Comprehension # 1
An organic compound A has molecular formula C10H17Br and it is non-resolvable. A does not decolourize
brown colour of bromine water solution. A on treatement with (CH 3) 2COK/(CH 3)3COH yields B as major
product. B on treatment with H2/Pt yields (C10H16) which on treatment with Cl2/hv yields three monochloro
derivative. Also B on boiling with acidic permanganate solution yields C(C 10 H 16 O 3 ). C on heating with
sodalime yields D (C9H 16O). D on reducing with LiAlH4 followed by heating the product with concentrated
H2 SO 4 yields E (C 9H 16) as major product. E on treatment with ozone followed by work-up with Zn–H 2 O
yields 6-Ketononanal.
1. Compound A is :
Br Br
Br
2. Compound B is :
3. Compound C is :
COOH O
O O COOH
CH2 H
(A) (B) (C) O (D) CH2
CH2 O O C=C
CH2 H
4. Compound D is :
Comprehension # 2
Nucleophilic substitution reactions generally expressed as
Nu – + R — L R— Nu + L –
30
E
–
(C) X + H3C —OH CH 3 —X + H 2 O
H
CH 3 Br CH 3 F CH 3 OH CH 3 OSO 2 CF3
3. (I) ( II) (III) (IV )
The correct order of decreasing reactivity of the above compounds towards CH 3 O – in an S N 2 reaction
is :
(A) I > IV > II > III (B) IV > I > II > III (C) IV > I > III > II (D) IV > II > I > III
4. Cl – CH3O – CH 3 S – I–
(I) (II) (II) ( IV )
Comprehension # 3
Nucleophilic aliphatic substitution reaction is mainly of two types : S N1 and S N2. The S N1 mechanism is
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
a two step process. Reaction velocity of SN1 reaction depends only on the concentration of the substrate.
Since product formation takes place by the formation of carbocation, optically active substrate gives (+)
and (–) forms of the product. In most of the cases the product usually consits of 5-20% inverted product
and 80-95% racemised species. The more stable the carbocation, the greater is the proportion of racemisation.
In solvolysis reaction, the more nucleophilic the solvent, the greater is the proportion of inversion.
CH3
(A) H5C6——–Br (B) H3C (C) H3C—Br (D) All of these
CH3 Br
2. Which of the following compounds will give S N1 and S N 2 reactions with considerable rate ?
CH3
I. C 6 H 5 —CH 2 —Br II. CH 2 =CH—CH 2 —Br III. CH 3 —CH(Br)CH 3 IV. H3C
CH3 Br
R1 R1
HOH
R——–X R——–OH
R2 R2
H2C CH3
CH3
(A) H5C6——–Br (B) Br
C2H5 C2H5
Br Br
H5C6——– —OCH3 H5C6——– —NO2
(C) (D)
+
CH3 NH3
Tr u e / Fals e
1. T 2. F 3. T 4. T 5. F
F i ll i n t h e B lank s
1. thioalcohol 2. nucleophilic substitution 3. sodium ethoxide, williamson's synthesis
4. reactive 5. vic-dihalides or alkylene halides 6. alcohols
7. glycol
Matc h th e C o lu m n
1. (A) r ; B q ; (C) s ; (D) p 2. (A) q ; (B) r ; (C) s ; (D) p
A s s er ti o n - R eas o n Q u es ti o ns
1. D 2. B 3. C 4. B 5. D 6. C 7. A
8. A 9. A 10. B
C o mp rehe ns i o n B as ed Q u e st i o ns
C o mp re he ns i o n # 1 : 1. (A) 2. (C) 3. (A) 4. (C)
C o mp re he ns i o n # 2 : 1. (C) 2. (D) 3. (B) 4. (B)
C o mp re he ns i o n # 3 : 1. (A) 2. (A) 3. (C)
32
E
Ph Ph
Ph
Cl Cl Cl
Cl
(I) (II) (III) (IV)
2. Select the member of each pair that shows faster rate of S N 2 reaction with KI in acetone.
(I) (II)
(b) CH 3–CH 2–CH 2 –Cl and CH 3–CH 2–CH 2 –Br
(I) (II)
CH3
(c) CH3–CH–CH2–CH2–Cl and CH3–C–CH2Cl
CH3 CH3
(I) (II)
Br CH3 Br
(d) CH3—CH2—CH2—CH—CH3 and CH3—CH—CH2—CH—CH3
(I) (II)
3. Of the following statements which are true for S N1 reaction.
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
E 33
CH2CH = CH2
7. Identify the product when A reacts with
(A)
EtO–
(a) CH3CH2CHCH3 (b) CH 3 CH 2 CH 2CH 2Br EtO–
Br
EtO– CH3
CH2CH2CHCH3
(CH3)3COK
(c) Br (d) H3CCCH2CH2Br
(CH3)3COH
CH3
CH2Cl
EtO–
(e)
EtOH
Cl Br
Br
(c) and (d) and
Cl
10. R – Mg – Br (A) on reaction with H2O forms a gas (B), which occupied 1.4 L/g at NTP. What is product
when R – Br reacts with benzene in presence of AlCl 3 ?
34
E
5. 1° > 2° > 3° Anion of acetic acid is more stabilised by resonance than phenoxide ion.
6. 1-chlorohexane
Because it follows Sn2 path.
CH2CH = CH2
7. (a) and para
Br
Ortho
Br
CHCH2CH3
(d) Br
–
(1, 2-H shift gives more stable benzylic carbocation)
CH=CHCH2CH3
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
CH3
CH3
CH3
9. Ease of backside attack (less steric hindrance) decides which undergoes S N2 faster (except in (b) in which
iodide is better leaving group). In all cases first one is fater than the other for S N2 reaction.
10. Gas B is CH 4 , hence A is CH 3MgBr. CH 3Br forms CH3 on reaction with benzene.
E 35
Br
SN2
H CH3 + N 3 –
(c) What will happen to the rate if the concentration of alkyl bromide in (b) is doubled?
(d) What will happen to the rate if the concentration of azide ion in (b) is doubled?
(e) How the sign of optical rotation of reactant and product are related in (b)
(f) When allowed to stand in dilute H 2SO 4, laevo-rotatory 2-butanol slowly loses optical activity.
2. Provide structure of major product in the following reaction indicating stereochemistry where appropriate:
D D
Cl O
O CH3OH O
(a) + CH3O–
O O OH
(c) + HO –
HO O
4. Which of the following alkyl halide could be successfully used to synthesize Grignard reagent and why other
fail?
Br
N Br
HO
(I) (II)
H2N Br
Br OH
(IV)
(III)
36
E
Identify B to F
8. Vinyl chloride does not give S N reaction but allyl chloride gives. Explain.
9. Arrange the following in the increasing order of their ability as a leaving group:
(a) CH3S–, CH3O–, CF3– and F–
(b) CF 3SO 3–, CH 3SO 3– and CH 3COO –
10. RBr when treated with AgCN in a highly polar solvent gives RNC whereas when it is treated with NaCN
it gives RCN. Explain.
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
E 37
1. (a) Though neopentylbromide is primary, bulky tertiary butyl group possess very large steric hindrance
–
to the attack of bulky nucleophile N 3 .
Br N3
SN2
(b) H CH3 + N 3– CH3 H
D D
D D
D
C C
2. (a) (b) CN + C
NC CH3 H3C CH3
H H NC
H
Cl O– O
3. (a) O – + Cl –
+ OCH3 O O
Cl
– Br OCH3
(b) Br + OCH3
O O–
–
O
–Br OCH3
O –
H2O O O–
Product O
HO
4. Only II can be used for successful synthesis of Grignard reagent, rest all contain acidic proton and will react
with R – (from Grignard reagent) forming alkane.
Br
5. O
A B C D
Br CN
6. (A) (B)
Br CN
38
E
O O
COOH
Br CN
(C) (D) (E)
COOH Br CN
O O
COOH
(F) (G)
COOH COOH
(decarboxylation takes place on heating when there is a keto group at - position)
(D) D D (E) Cl Cl
(F) Cl CH2OH
CH2 CH Cl CH2 CH Cl
••
Hence SN reaction in which Cl is replaced by nucleophile is not possible. In addition to this, sp2- hybridised
carbon is more acidic than sp3- carbon, hence removal of proton (H+) is easier than removal of halide (Cl–)
In allyl chloride, S N reaction is easier since allyl carbocation formed after removal of Cl – is stabilised by
resonance.
+
CH2 CHCH2Cl CH2 CHCH2+Cl–
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
Allyl carbocation
+ +
CH2 CH CH2 CH2 CH CH2
– – –
9. (a) CF3 < CH3O < CH3S ; (b) CH3COO– < CH3SO3– < CF3SO3–
10. As [CN] – is an ambident nuicleophile which ahve two nucleophile which have two nucleophilic sites and
can attack from either side. In a highly polar solvent, AgCN promotes the formation of carbocation R + ,
precipitation of AgBr.
•• •• ••
N C N
R—BR + Ag + [CN – ] C
fast –
•• •• R+ + CN– + Ag Br
R–N+ C
slow
In the absence of such promotion by Ag +, with Na+[CN] –, the resulting S N2 reaction is found to proceed
with preferential attack on the atom in the nucleophile which is more polarisable i.e. C.
–
NC – +R – Br [NC ....R....Br ] N C – R + Br –
Transition State
E 39
9. The number of possible enantiomeric pairs that can be produced during monochlorination of isopentane-
(A) 2 (B) 3 (C) 4 (D) 1 [IIT - 97]
10. During debromination of meso-2,3-dibromobutane, with Zn dust/CH3COOH the major compound formed
is - [IIT - 97]
(A) n-butane (B) 1-butene (C) cis-2-butene (D) trans-2-butene
40
E
H3C
(A) O2N NH2 (B) N NH2
H3C
H3C
N NO2 H3C
(C) H2C (D) N NO2
H3C
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
NH2
CH3 H CH3
H Cl CH3
CH3 H CH3
H CH3 OH
Br
?
HC C H is /are -
Br
(A) alcoholic KOH (B) Alcoholic KOH followed by NaNH 2
(C) aquesous KOH followed by NaNH 2 (D) Zn/CH 3 OH
23. In the following groups : [IIT -97]
(I) –OAc ; (II) –OMe ; (III) –OSO2Me ; (IV) OSO2CF 3
the order of leaving group ability is -
(A) I > II > III > IV (B) IV > III > I > II (C) III > II > I > IV (D) II > III > IV > I
Aq. KOH
24. CH3CH2CHCl2 ? [IIT 1991]
25. Draw the stereochemical structure of the products in the following reaction. [IIT 1994]
C2H5
Br H
OH / DMSO
S
N2
CH3
26. Give reasons : [IIT 2005]
H3C Br
CH3
(a) (i) acidic solution ; (ii) Br—
C 2 H 5 OH (aq.)
C 2 H 5 OH (aq.)
neutral
CH3 CH3
F F
CH3 F
C 2 H 5 OH NaOCH 3
(a) H3C
(b)
CH3 NO2
(c) base
O
Br
42
E
CH3 H CH3
MeO NO2
H Cl CH3
CH3 H CH3
MeO NO2
(K)
H OH CH3
CH3 H CH3
MeO NO2
(L)
OH H CH3
CH3 H CH3
MeO NO2
(M)
H CH3 OH
It mainly gives
(A) K and L (B) Only K (C)L and M (D) Only M
30. Match the following: [IIT 2006]
Column I
Column II
(A) CH3–CHBr–CD3 on treatment with alc. KOH gives (P) E1 reaction
CH2=CH-CD3 as a major product.
(B) Ph – CHBr - CH3 reacts faster than Ph-CHBr-CD3. (Q) E2 reaction
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
H3C Br
F
PhSNa
dim ethyl formamide
NO2
HBr
32. In the reaction OCH3 the products are [IIT 2010]
33. The total number of alkenes possible by dehydrobromination of 3-bromo-3-cyclopentylhexane using alcoholic
KOH is [IIT-2011]
34. KI in acetone, undergoes S N2 reaction with each of P, Q, R and S. The rates of the reaction vary as -
[IIT 2013]
O
Cl
H3C–Cl Cl Cl
P Q R S
(A) P > Q > R > S (B) S > P > R > Q
(C) P > R > Q > S (D) R > P > S > Q
35. Match the chemical conversions in List-I with the appropritate reagents in List-II and select the correct answer
using the code given below this lists - [IIT 2013]
Li st- I Li st-II
(P) Cl
(1) (i) Hg(OAc) 2 (ii) NaBH 4
(Q) ONa
OEt (2) NaOEt
(S)
(4) (i) BH 3 (ii) H 2O 2 /NaOH
OH
Codes :
P Q R S
(A) 2 3 1 4
(B) 3 2 1 4
(C) 2 3 4 1
(D) 3 2 4 1
44
E
C2H5
25. H OH
CH3
CH3
—C— OC2H5
26. (a) (i) Products are + HBr (aq.) ; Hence acidic.
CH3
Cl CH3 CH2
27. (B)
CH3
\\node6\E_NODE6 (E)\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-11\Eng\1. Alkyl halide & Aryl halide\Exe.p65
OCH3
CH3
28. (a) (b) (c)
H2C—C=CH—CH3 O
NO2
E 45
------------------------------------------------------------------------------------------------------------------------------------------------
Thank you for your love and support, we hope you are always being happy and get success in your life, we
are happy to see you again.