Halogen Derivative

IIT-JEE ChEmistry by N.J.
sir ORGANIC ChemIstRy
IR
.S
.J
HALOGEN DERIVATIVES
N
1
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ETOOS Academy Pvt. Ltd.
F-106, Road No. 2, Indraprastha Industrial Area, End of Evergreen Motors (Mahindra Showroom), BSNL Office Lane,
Jhalawar Road, Kota, Rajasthan (324005)
SUBSTITUTION & ELIMINATION
Solvents are most important for reactions since they provide medium for chemical reactions.
Molecular collisions are possible only in gaseous phase or in solvent phase.
Solvent
Cl
NonPolar C Cl ; ; CS2
Solvent Cl Cl
Polar protic
Polar O O
H/ R H/ NH 3
IR
H
Polar aprotic
O O O
CH3 CH3
S CN CH
3 CN
CH3 CH3 H CH3 CH3
.S DMSO DMF DMA
Polar protic Solvent: ..

Can solvate both cations & anions (a) CH3 .NH
. CH3NH2
H ..
H H O (b) CH3 .O. : CH3OH
O H
H H OH H
O
O O
O
H H H H
O O (c) CH
3 CO CH
3 C OH
OH
H H H (d) R O R OH
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Solvation of cation Solvation of anions
S
(e) H H HS
Polar aprotic solvent ..
Can solvate only cations & not anions (f) R SH R .S. :
CH3 +
(g) H3O H2O
N
S CH3 Ans. (a) 1>2 (b) 1>2 (c) 1>2

CH3 O
O=S (d) 1>2 (e) 1<2 (f) 1<2
O CH3 (g) 1<2
S Rule 2:
CH3 CH3
For atoms of comparable size, better e donor

Nucleophiles:- They are e pair donors . Particles is better nucleophile (lower electronegativity
which donate e pair to generate covalent or better e donor)
..
coordinate bonds are nucleophiles. 1. CH3 NH2 > CH3 O H
..
2. R NH2 > R OH
Strength of Nucleophile
Rule-1 () charge .. ..
Conjugate bases are strong nucleophiles compared 3. NH2 < NH2
to acids:- O
4. ROH > RCOH
2
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O (2) L Leaving group
(3) Solvent (4) Nucleophile.
5. R O > RCO
Types of nucleophilic substitution.
Rule 3:-
If e donating atoms are of different size in polar 1. SN1 2. SN2 3. SNAR
NGP
protic solvent 4. SN 5. SNi 6. SN1
Nucleophilicity size of atom 7. Benzyne.
(a) R OH < R SH
(b) (C6H5)3N < (C6H5)3P SN1 Nucleophilic substitution first order:-
. .
(c) F Cl Br I 1. R L R L
..
If e donating atoms are of different size in polar 2. R Nu R Nu
aprotic solvent R1
R1
IR
Nucleophilicity basicity Slow . .
1. C + L
CL rds.
Leaving group (L):- Particles which are substituted R2 R2 R3
by stronger nucleophiles or depart from a molecule to R3
generate carbocation are leaving groups. R1
1 ..
Leaving group ability
Base strength 2. C + Nu
R L
.S
Weak bases are good leaving groups.
R

L
. .
R2
R1
R3
R1
R2 Nu Nu R2
1. I > Br > Cl >> F
O R3 R3

2. H H > OH
O
Characteristics
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3. R H > R O
O (1) rate = k [R L]1; rate is independent on
concentration of nuclophile.

4. RCO > R O (2) rate is directly proportional to stability of
O O carbocation
(3) Rearrangement possible
5. O S CH3 < O S CF3
N
(4) Planar carbocation can be attacked from both

O O sides
Methylsulphonate Trifluoro methylsulphonate (5) Supported by polar protic solvent.
(Mesylate) (Triflate) (6) 2 step reaction
O O
O
6.

< OS (7) Normally 3 carbocation & resonance
OS N
stabilized carbocation support this reaction
O O CH3 mechanism if attacking Nuclophile is neutral
polar protic solvent.
Nucleophilic substitution (SN Reactions)
. .
Nu . . (8) Solvolysis (SN1)
R L R Nu + L O
H H
Ph CH2 Cl Ph CH2 OH + HCl
4 Components
(1) R Substrate
3
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Q.1 Compare the rate of SN1 reaction:- EtOH
(3) Ph CH2 Br
(a) Ph CH2 Cl Ph CH Cl O
||
HCOH
Ph (4) Ph CH2 Br
(i) (ii)
Ph PhOH
(5) Ph CH2 Br
Ph C Cl Ans: (1) Ph CH2 OH
(2) Ph CH2 OCH3
Ph (3) Ph CH2 OEt
(iii) O
I I I ||
(4) Ph CH2 O C H
(b) (5) Ph CH2 OPh
IR
(i) (ii) (iii) Q.3 Which SN1 reaction is expected to occur
I I I rapidly.
O
1. (a) (CH3)3 CCl + H H (CH3)3 C OH+ HCl
(c) O
(b) (CH3)3 CBr + H H (CH3)3 C OH + HBr
.SO
(i) (ii) (iii)
(d) CH3 O CH2 Cl 2. (a) Cl + EtO O Et + Cl
(i)
CH3 O CH2 CH2 Cl
(ii) 1.0 M 1.0 M
CHCl
2
CHCl
2
(b) Cl + tO O Et + Cl
(e)
2.0 M 1.0 M
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(f) CH3 O CH = CH CH2 Cl & 3. (a) Cl + EtO O Et + Cl
CH3 O CH2 CH = CH CH2 Cl
100% 1.0 M 1.0 M
(g) (i) Ph CH Cl
H2O
CH3 (b) Cl + EtO O Et + Cl
N
80%H2O
(ii) Ph CH Cl
20%EtOH 1.0 M 1.0 M 1.0 M 2.0 M
CH3 Ans. (1) b > a (2) a < b (3) a = b
Ans: (a) (iii) > (ii) > (i) (b) (ii) > (iii) > (i)
(c) (i) > (ii) > (iii) (d) (i) > (ii) Q.4 Compare rate of SN1 reaction
(e) (i) > (ii) (f) (i) > (ii) (g) (i) > (ii) O
1. (a) Cl + H H
1
Q.2 SN reactions are also known as solvolysis as O
.. (b) Br + H H
solvent molecules behave as Nu . Write
the product in each case. O
2. (a) Cl + H H
H2O
(1) Ph CH2 Br
O
CH3OH Cl + CH3 H
(2) Ph CH2 Br (b)
4
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O
3. (a) Cl + H H 6.
O
Cl + H H Me
(b)
Br CHBr
2
(a) (b)
Br (better leaving group) Ans. (1) a > b (2) b > a (3) a > c > b > d
Ans. (1) (b)
(4) a < b (5) a < b (6) b > a
O
(2) (b) H H better solvation Q.6 These substrates cannot give SN1. Explain
(3) (a) Cl
(double bond character) 1. 2. CH2 = CH Cl 3.
IR
Q.5 Compare rate of SN1 Cl
Me Cl
Me CH3
1. 4. CH C F 5. CH3 CH2 F
Me Me 3
CH3
Me
OTS CH3
Me OTS
.StBu
(a)
tBu
(b)
6. CH C CH Br 7.
32
CH3
Cl
( O , F & CH3 O cannot be substituted

strong bars & weak leaving groups)
2.
SN2 reaction nucleophilic substitution
SN2 Reaction
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Cl Cl Nucleophilic Substitution 2nd order
(a) (b) . .
Nu + RL Nu R L
I Cl Br Cl
. .
O O O Nu R + L
3.
N
O Characteristics:-
x x
1. Nu + CL Nu - - - C - - - L
(a) (b) (c) (d)
y z
y z
H OTS H OTS x
4. Nu C +L
y
z
(a) (b) 1
2. rate of reaction .
Bulkiness in x, y & z
5. Br . .
3. rate strength of Nu
Br . .
(a) (b) 4. rate Leaving group ability of L
5. Inversion of configuration takes place.
5
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(ii) Br + CH3O
Characteristics
Q.1 Compare rate of SN2 reaction: 1.0 M 2.0 M
1. CH3 CH2 CH2 Br & CHCHBr Ans. (A) i > ii (B) I < ii (C) ii > i (D) ii > i
3
CH3 Q.3 1 Bromobicyclo [2.2.1] heptane is extremely

(i) (ii) unreactive in either SN1 or SN2 reaction.
Explain:
2. CH3 CH2 CH2 CH2 Cl SN1 X
(i)
(Bridge Head position)
CH3 CH2 CH2 CH2 I
(ii)
3. CH3 CH CH2 Cl Br
(i) SN2 X
IR
CH3 CH2 CH2 CH2 Cl (Walden unreason not possible)
|
CH3
(ii) Q.4 Write the products of SN2 reaction:
1. H KSH
H
4. Br
Cl Cl Br
(i) (ii)
5.
.S Cl
Cl 2. D
Br
ACO
H
H D
(i) (ii)
Ans. (1) 1 > 2 (2) 2 > 1 (3) 1 > 2 CH3
(4) 1 < 2 (5) 1 > 2 CH3
3. KSH
2 H Cl
Q.2 Compare rate of SN reaction:
.J

(A)(i) Cl + CH3 CH2 O Et
CH3
or KSH
Cl+ CH3 CH2 OH 4. Cl CH C CH CH 2 Cl
(ii) 2 2
CH3
NaCN (1 eq)
(B)(i) Cl + CH3 CH2 O
N
Cl

Cl + CH3 CH2 S CH2 I
(ii)
NaCN 6. KSH(1eq)
(C)(i) Br + (C6H5)3N 5.

(ii) Br+ (C6H5)3P I
Br
(D) (i) Br + CH3O 7. KSH
Br CH2 CH = CH Br
(1eq)
1.0 M 1.0 M
6
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Q.5
Reactant SN1 SN2
(1) Cl
(2) CH2 = CH Cl
(3) CH2 Cl
(4) CH2 = CH CH2 Cl
(5)
IR
Cl
(6) CH3 O CH2 Cl
(7) CHN
3 CH Cl2
CH3
(8) .S CH3 F
CH3
(9) CH
3 C Cl
CH3
(10) Br
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(11) CH3 C Et
Cl
CHCl
2
(12)
N
Cl
(13)
CH3
(14) CH3 C CH2 Cl
CH3
(15) CH
2 Cl
7
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Q.6 Explain Q.14 Explain:
O
OH + CH3 O CH3 No. Reaction H H
H (a) CH3 S CH2 CD2 I
CH O CH
3 2CH OH
3 3
CH3 S CH2 CD2 OH
CH3
Q.7 TSCl
A B NaCN
H OH
(b) ACO / ACOH
14
D CH
2 CH 2
O I
Q.8 KSH + CH3 O S CH3 +

14
O CH
2 CHOAC
2
IR
Q.9 Compare rate of hydrolysis
14
Ph CH
2 CHOAC
2
H H H S H
CH3
SPh Cl Cl H Cl H HBr
Q.15 Br
(a) (b) (c) CCl
.S HO H 4
Q.10 Explain mustard gas hydrolysis at a very high CH3

rate:
Cl CH2 CH2 S CH2 CH2 Cl CH3

Q.11 Explain: H Ph ACO / ACOH
OTS Q.16
TSO H
ACO / ACOH
CH3
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OTS Q.17
OTS
+ (1) H O CH2 CH2 CH2 Br
O
+

+ Br + H
CH3
N
(2) H O CH2 CH2 Br

Q.12 H HBr
Br
CCl (3) NH2CH2 CH2 CH2 CH2 Br
H OH 4
CH3 OH/H2O

Q.13 Compare rate of hydrolysis:
SH SN1
SH
H2O
CH3CH=CHCH2Cl
CH3CH=CHCH2OH+ CH3 CH CH=CH2
I |
I OH
(a) (b)
8
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Cl
HO
Q.18
2
Q.19 EtOH

Cl
Q.20 R X + Reagent Product

. .
Reagent Nu Product
1. aq. KOH OH
2. aq. NaOH OH
IR
3. Na2CO3 (aq.) OH
4. Moist Ag2O OH

5. RO /ROH R O
..
6. NH3 NH3
..
7. R NH2 R NH2
8.
.S NaSH SH
O
9. dry Ag2O Ag Ag

10. KCN CN
11. AgCN Ag CN:
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N
9
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IIT-JEE ChEmistry by N.J. Sir ORGANIC chemistry
DPP NO-01 Time: 30 minutes
1. Which alkyl halide would you expect to react more rapidly by an SN2 mechanism? Explain your answer
(A) CH3CH2CH2Br or (CH3)2 CHBr
(B) CH3CH2CH2CH2Cl or CH3CH2CH2CH2I
(C) CH3 2 CHCH2Cl or CH3CH2CH2CH2CI
(D) CH3 2 CHCH2CH2Cl or CH3CH2CH CH3 CH2CI
(E) C6H5Br or CH3CH2CH2CH2CH2CI
2. Which SN2 reaction of each pair would you expect to take place more rapidly in a protic solvent?
IR
(A) (1) CH3 CH2CH2Cl CH3CH2O CH3CH2CH2OCH2CH3 Cl
OR
(2) CH3CH2CH2Cl CH3 CH2OH CH3 CH2CH2OCH2CH3 HCl
(B) (1) CH3 CH2CH2Cl CH3CH2O CH3CH2CH2OCH2CH3 Cl
OR
(2) CH3CH2CH2Cl CH3 CH2S CH3CH2CH2SCH2CH3 Cl

(C)
.S (1) CH3CH2CH2Br C6H5 3 N CH3 CH2CH2N C6H5 3 Br
OR

(2) CH3CH2CH2Br C6H5 3 P CH3CH2CH2P C6H5 3 Br
(D) (1) CH3CH2CH2Br 1.0M3 CH3O 1.0M CH3 CH2CH2OCH3 Br
OR
(2) CH3CH2CH2Br 1.0M CH3O 2.0M CH3CH2CH2OCH3 Br
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3. Which SN1 reaction of each pair would you expect to take place more rapidly? Explain your answer.
(A) (1) CH3 3 CCl H2O CH3 3 COH HCl
OR
(2) CH3 3 CBr H2O CH3 3 COH HBr
N
(B) (1) CH3 3 CCl H2O CH3 3 COH HCl

OR
(2) CH3 3 CCl CH3OH CH3 3 COCH3 HCl
(C) (1) CH3 3 CCl 1.0M CH3CH2O 1.0M
EtOH
CH3 3 COCH2CH3 Cl
OR
EtOH
(2) CH3 3 CCl 2.0M CH3CH2O 1.0M CH3 3 COCH2CH3 Cl
(D) (1) CH3 3 CCl 1.0M CH3CH2O 1.0M EtOH
CH3 3 COCH2CH3 Cl
EtOH
(2) CH3 3 CCl 1.0M CH3CH2O 2.0M CH3 3 COCH2CH3 Cl
(E) (1) CH3 3 CCl H2O CH3 3 COH HCl
(2) C6H5Cl H2O C6H5OH HCl
10
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4. Write conformational structures for the
substitution products of the following deuteri (D) 4,Chloro-1-butanol + NaH
compound: H2
heat
C4H8CIONa C4H8O NaCl
Et 2O Et 2O
Cl
H (E) Pr opyne NaNH2
l
(A) ? 3
NH CH3I
D
CH3OH
liq.NH3
C3H3Na C4H6 Nal
H
Cl
H 8. When the alkyl bromides (listed here) were
l
(B) ? subjected to hydrolises in a mixture of ethanol
CH3OH
and water (80% C2H5OH/20% H2O) at 55oC,
H
H the rates of the reaction showed the following
IR
order: (CH3)3CBr > CH3Br > CH3CH2Br >
Cl
(CH3)2CHBr
Provide an explanation for this order of
(C) H H l reactivity
?
CH3OH
D
9. What would be the effect of increasing solvent
polarity on the rate of each of the following
.S Cl
CH3
H2 O
nucleophilic substitutions reactions?
(a) Nu: + R L R Nu+ + :L
(D) ?
(b) R L+ R+ + :L
H CH3 OH
10. Competition experiments are those in which

5. 1-Bromobicyclo [2.2.1] heptane is extremely two reactants at the same concentration (or
one reactant with two reactive sites) compete
.J
unreactive in either SN2 or SN1 reaction
explanations for this behaviour. for a regent. Predict the major product
resulting from each of the following
competition experiments:
6. When ethyl bromide reacts with potassium CH3
cyanide in methanol, the major product is
(a) Cl CH2 C CH2 CH3 Cl l
some CH3CH2NC is formed as well, however.
N
Write Lewis structures for the cyanic both CH3

products, land provide a mechanistic
explanation of the course of the reaction CH3
(b) Cl C CH 2 CH 2 Cl H 2O
7. Give structures for the products of each of the CH 3

following reactions:
H F
+ NaI (1 mol) C5 H8FI NaBr 11. Predict the structure of the product of this
acetone
Br H reaction:
(A)
HS H
(B) 1, 4Dichlorohexane (1 mole) + NaI (1 NaOH in
C6 H10S
aqueous EtOH
mole) acetone
C 6H10 ICl NaCl H Cl
(C) 1, 2Dibromoethane (1 mole) +
NaSCH2CH2SNa C 4H8 S2 2NaBr
11
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IIT-JEE ChEmistry by N.J. sir ORGANIC chemistry
IR
Comparison of SN1, SN2, E1 & E2
Reactant Neutral Nucleophiles or Bases Weak Nucleophiles Strong Bases /Nucleophiles
R
O
HH
O
HR
S
HH
S
H
O
||

RO / EtO / CH3 O / O /Et N 3 1
.. I , SH , CN , CH3 C O
.S
NH3
.. ..
.N. , N , .N. : , Br , SCN , R S ,

(X F) CH3 X SN2 SN2 SN2
Ph CH2 X
Ph CH2CH2X .J SN1(Solvolysis)
SN2
SN2
SN2
SN2
E2 (formation of conjugated double. Bond)

SN2 {Exception in sterically hirdered base
N
RCH2X SN2 SN2 O / OH or Et N, 3
2
E is major product}
R CH R SN1(low Temp.)
|
Br E1 ( high Temp. SN2 E2
R
|
R C Br SN1 (low Temp.) SN1 (low Temp.) E2
|
R E1(high Temp.) E1 (high Temp.)
12
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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)
DPP-02 Time: 30 Minutes
1 2 1 2
Comparison of SN , SN , E & E CH3
|
(1) Ph CH2 Br (9) CH3 C CH CH3 EtOH

H2O | |
CH3 Br
KSH

(2) KCN
(10) (a) CH3 O + Br

EtONa/ EtOH

(b) O + CH3 Br
IR
Cl
CH3 O /CH3OH CH3
(3) CH3 CH2 Br
(11) To prepare CH3OCH , which of
H2O
CH3
(4) CH3OH the following will give better yield:
(1) CH3 ONa + CH3 CH CH3

.S Cl EtONa/ EtOH

O /
OH

(2) CH3 CH ONa + CH3 I
|
CH3

|
CH3
Et3N
(12) Styrene (C6H5 CH = CH2) is to be prepared
(5) R-2-chloropentane NaI / Acetone
by dehydrohalogenation using alc.KOH.
NaN3 Which of the following will give better yield.
.J
Ph
(1) alc.KOH

CH3CH
CH3 CO
|| Br
O Ph
|
(2) alc.KOH
CH2 CH2 Br
EtO / EtOH
N
NaCN
(13) Write mechanism which accounts for the
H H following products.
EtONa/ EtOH
(6) (a) HO CH2 CH2 Br

CH3 NaI / Acetone
OTS OH /H2O

EtONa /EtOH O
(7) CH2=CH CH CH3 (b) NH2 CH2CH2CH2 CH2 Br
| NaI / Acetone

Br OH /H2O

NaH N
(8) O H H
CH3 CH2 CH2 Br

(A) (B) (14) Major Product of reactions
(E1, E2, SN1 & SN2)
13
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(a) CH3CH2 CH2 CH2 CH2 Br Cl
H I
(b)
CH3CH2OH H CH3OH
+ CH3 CH2 O
50C
D
Cl
(b) CH3CH2 CH2 CH2 CH2 Br
H I
(c)
+ O CH3OH
OH/50C D
H
Cl
(c) Br + CH3O
CH3OH/50C CH3
H2O/CH3OH
(d)
(d) Br + O
H
OH/50C
IR
D
Cl

I / Acetone (16) Give major product (E1, E2, SN1 or SN2)
(e)
50C (a) CH3 CH2 CH2 Br
CH3 OH
+ CH3 O
.S Cl 50C
CH3OH/
CH 3 (b) CH3 CH2 CH2 Br
(f)
25C
+ O OH

50C
(g) CH3OH
3-Chloropentane + CH3O CH3

50C 50C
(c) C Br + SH
O CH3OH
|| Et
(h) 3-Chloropentane + CH3 C O H
.J
O Et
||
CH3 COH
Et Br CH3OH
50C (d) + OH
50C
25C Et
(i) OH + (R) -2-bromobutane
N
25C Et
(j) (S)-3-bromo-3-methylhexane
CH OH 3
Et Br
I (e)
CH3OH

(k) (S)-2-bromooctane 25C
CH3OH/50C
Et
(15) Major product (E1,E2,SN1 or SN2)

(16) Consider the reaction of I with
Cl CH3CH2 Cl.
H
I (a) Would you expect the reaction to be SN1 or
(a)
CH3OH
SN2
D
(b) The rate constant of the reaction at 60C is 5
H 105 L mol1 sec1. What is the reaction rate

if [ I ] = 0.1 mol/L and [CH3 CH2 Cl ] =
0.1 mol/L.
14
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DPP- 03 Time: 30 Minutes
1CB
E - Mechanism Q.5 Ph CH2 CH CH3 OH

Hoffmann V/S Saytzeff alkene (elimination) |
1. F
EtONa

EtOH Q.6 OH/

I +
N
+ +
CH3 CH3
IR

Saytzeff Hoffmann OH
Q.7

L.G. % Hoffmann +
N
L.G. Tendency

N (Me)3 90% Q.8 OH

+
S (Et)2 74% N
F
Br
.S 70%
19%
Q.9 OH

+
N
EtO/EtOH
+ OH/
95% 5% Q.10 +
N(Me)3
N
.J
+
T.S. has more carbanion character.
+ Hoffmann exhaustive methylation

N(Me)3
Q.1 CH3 CH2 CH2 NH2
1. CH3I

Q.1 2. Ag O(moist) 2
N
3.
1. CH3 I
Q.2
EtO/ 2. Ag2O(moist)
Q.2 3.
NH2
F 1. CH3 I
Q.3 N
2. Ag2O
Me 3.
| EtO/
Q.3 MeCH2 C CH2 Me 1. CH3 I
| Q.4
2. Ag2O
N(Me)3 3.
N
H
N+ 1. CH3 I
Q.5
EtO/ 2. Ag2O(moist)
Q.4 3.
N
H
15
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1. CH3 I Ph
Q.6
2. Ag2O Q.4
3. Me
N N
H
Me
O
O Me Me
N
1. CH3 I 1. CH3 I
Q.7 (A) (B) 1.H2O2
2. Ag2O 2. Ag2O Q.5

N 3. 3. 2.
Q.6 CH3 N CH2 CH2 CH3

Q.8 CHCl2 CF3 alc.KOH
|
Ph
O
|| MCPBA (A)

Q.9 OH
CH3 C CH2CH2F
IR

EtO Q.7 MCPBA

Q.10 CH3 C CH2 CH2 F
||
O N

Q.11 EtO
CH3 C CH2 CH2 F O
||
||
O Q.8 Ph C O CH2 CH3
E1
.S CH3 Q.9
S
||
CH3CH2 C SCH2CH3
| O
Q.1
Ph CH2 CH2 N Me ||
| Q.10
CH3 CH2 C O CH2 CH3
O O
OCCH3
Q.11
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H2O2
Q.2 (A)
OCCH3
MeNMe O
Ph

N
Q.3
Me
N

Me
O
16
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HALOGEN DERIVATIVES
Classification
Aliphatic Unsaturated Aromatic

CH2 =CHCl (Vinyl)
CH2 =CHCH2Cl (Allyl)
Saturated
Side chain
IR
(Benzyne)
CH3CH2CH2Cl (1)
Monohalogen CH3CHCH3 (2) CH2Cl
Cl
Cl NO2 SN1/SN2
CH3
CH 3CCH3 (3) (SNAR)
Cl
.S dihalogen
CH3CH
Cl
Cl
(gem) (geminal)
Cl
CH3CHCH (Vic) (Vicinal)

Cl Cl
CH 2CH2CH 2 (Isolated)
Cl Cl
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Polyhalogen CHCl 3 (Chloroform)
CCl4 (Carbon tetrachloride pyrene)

N
General Method of Preparation Br2

Q.2 CH 3CHCH 2CH 3
(1) Form alkanes hv
CH3 Cl2
XX ---- % of 3
RH RX + HX hv mono-chloroproduct
h
X2 = Cl2 or Br2 Cl2/ h Monochloro
Cl2 = Non Selective ; Br2 = Selective Q.3 CH3
X2 F2 and X2 I2 Br2/ h
Monobromo
F2 = uncontrollable ; I2 = reversible
Cl2 (2) From alkenes
Q.1 % =_ _ _ + % = _ _ _
h HX
RCH = CH2 R CH CH3
R1 : R2 : R3
1: 3.8 : 4.5 CCl4 |
X
: Markownikoff addition; Classical carbocation
Br2
_ _ _ _ _ _ HBr
h R CH = CH2 RCH2CH2Br
R O OR
17
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Anti markownikoff addition peroxide effect Mechanism:
or Kharash effect O O
C C
Q.1 HCl h
C H 3 C H = C H 2 A (1) NBr N + Br
CCl4
C
HBr/CBr4 C
HCl(ROOR) HBr(ROOR)
B O
D O
C O
Q.2 Write mechanism: C
CCl4 CCl3
(a) (2) CH2 = CH CH2 H + N
Peroxide C
Cl
CBr3 O
O
IR
(b) ICBr 3

Peroxide C

I CH2 = HC CH2 + HN
CCl3 C
BrCCl3
(c)
Peroxide O

.S Br (3) CH2 = CH CH2 + Br
CH2 = CH CH2 Br
(3) Reeds Reaction
SO2Cl2
R H RCl + SO2 HCl NBS
h Q.1 CH3 CH2Br
SO2Cl2 Sulphuryl Chloride
NBS Br
Mechanism. (free radical substitution) Q.2 +
O O Br
.J
1. h + SO2 +
ClSCl Cl ClS Q.3 NBS Q.4
NBS

O O

Cl Cl2
CH3 CH CH2 CH2 CH CH2
Cl 500C
N
2. RH + Cl HCl + R + R Cl. Imp. |

(Reaction rate is slow; selective and better Cl
method then direct halogenation)
at high temperature free radical substitution
O and not Non-classical carbocation addition
C (5) From alcohols
(4) NBS NBr (N-Bromo Succinimide) (a) Darzens process
C CH3 CH3
SOCl2
O H OH H Cl
NBS
CH3 CH = CH2 CH2 CH = CH2 D D
|
Br + SO2 + HCl (Retention of configuration)
18
-------------------------------------------------------------------------------------------------------
CH3 CH3 Cl
SOCl2 |
H OH .. Cl H (2) R C R1 R C R1 + POCl3
N || |
D D O Cl
+
+ SO2 + HCl (inversion of configuration) Cl Cl
P
OH SOCl2 Cl Cl
Q.1 A Cl
CH3 Cl
SOCl2 |
.. B (3) R C H R C H + POCl3
N || |
O Cl
CH3 +
IR
SOCl 2 Cl Cl
H D C
Q.2 P
H OH Cl Cl
Ph SOCl2 Cl
.. D
N
Cl Cl Cl
(4) + PCl + POCl3
O
Cl Cl Cl
(b) ROH + Lucas Reagent (HCl/ZnCl2)
.S
HCl/ ZnCl2
ROH RCl (Turbidity)
Test todistinguish1 / 2 / 3 alcohol.
(6) From ethers
ROR HI

(anhydrous)
3 alcohol within sec onds ROH + R I (SN2)

2 alcohol within minutes HI(Conc.)
ROR

1 alcohol
w i thin hrs ROH + R I (SN1)
.J
HI ROR HI

ROH RI (excess)
ROH KBr
No. Reaction R I + R I
PCl3
(c) ROH RCl + H3PO3 HI
(SN2) Q.1 O CH3
N
PCl5
ROH RCl
O OH + CH3 I
i 2
+ P Cl (SN (or SN )
Cl O HI(Conc.)
Cl Q.2
(high temperature SN2 dominates)
I + OH
PCl5
ROR
1
O HI(anhydrous)
(1) Cl Cl
RCl + RCl + POCl3 Q.3
PCl
Cl
Cl CH3 I + OH
19
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(7) Halide exchange Reaction
(a) Finkelstein Reaction (2) Haloform Reaction
NaI
Cl I + NaCl.
acetone O
NaBr Br + NaCl.
I2 /NaOH
CH2CH
acetone
O
(b) Swartz Reaction
CHI3 +
NaF/DMF RF + NaCl.
RCl + HCO Na
or AgF (yellow)
O
(8) H.V.Z. Reaction (Hell Volhard Zelinesky) 2 NaOH/ I
O Q.1 CCH3

O
RedP CH COH O
CH3COH
IR
2
Cl 2
NaOH/ I2
Cl Q.2 CH3C

O
O O O NaOH/ I2
Q.3 CCH3

Imp HCOH PhCOH COH
Nucleophilic Substitution
(a)
O
.S
Hunds diecker Reaction K
KCN
RC CAg
dry. Ag2O
KNO2
L
1. AgOH J A
RCOH R Br
2.Br2 /CCl4 / RMgX
B
AgNO2 RNa
Properties of Halogen Derivatives I RCl C
,
(1) Williamson ether synthesis RCuLi
2
D
.J
RONa + R1 Cl RSNa
ROR1 + NaCl (SN2) H alc.AgNO3
E
AgCN RONa
G F
Q.1 ONa + CH3 Cl

N
Q.2 ONa + CH3 Cl (4) Hoffmann exhaustive alkylation

NH3
CH3Cl
Q.3 ONa + CH3 Cl CH3
CH N +CH
3 3 Cl
Q.4 ONa + CH2Br CH3

Q.5 ONa + Br
20
-------------------------------------------------------------------------------------------------------
(5) With AgNO3(aq) & AgNO3(alc.)
Gives ppt. with
Substrate aq. AgNO3 alc. AgNO3

1. CCCCl
2. CCC
Cl
C
CCC
3.
Cl
IR
4. Cl
Cl
5.
.S
Cl
6.
7. C = C Cl
.J
8. C = C CH2 Cl
9. Cl
N
10. CH2Cl
21
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EXERCISE I Q.7 Which of the following compounds is most rapidly
hydrolysed by SN1 mechanism.
(A) C6H5Cl (B) Cl CH2 CH = CH2
Q.1 Which one of the following compounds will be (C) (C6H5)3CCl (D) C6H5CH2Cl
most reactive for SN1 reactions :
I Cl Br Cl Me Me
Me
OH OH
O (B) O O (D) Q.8 HO H H Cl I H OH
(A) (C) II
Et Et Et
O B A
Steps I and II are
Q.2 Consider the following groups : (A) I cant be SN1 (B) II cant be SN1
(I) OAc (II) OMe (C) I SN1 & II SN2 (D) I SN2 & II SN1
(III) O SO2 Me (IV) O SO2 CF3
The order of leaving group nature is : Q.9 What are A & B in the following reaction ?
(A) I > II > III > IV (B) IV > III > I > II Cl
IR
(C) III > II > I > IV (D) II > III > IV > I Mg / THF ( i) CH CHO
A 3 B
(ii) aq. NH4 Cl
Q.3 Arrange the following compounds in order of Br
decreasing rate of hydrolysis for SN1 reaction : MgCl CHOHCH3
(I) CH2 Br (II) H3C CH2 Br
(A) &
Br Br
(II)CH3 CH2
.S CH2 Br Cl Cl
CH3
(IV) (B) &
CH CH2 Br MgBr CHOHCH3
CH3 MgCl MgCl
(A) II > III > IV > I (B) IV > III > II > I
(C) III > IV > II > I (D) I > II > III > I (C) &
Br CHOHCH3
Q.4 Consider the given reaction : (D) None of these
HBr
CH3 CH = CH CH2 OH [P]
SN 1' Q.10 Which will give white ppt. with AgNO3?
.J
In the given reaction the product [P] is : (A) Cl (B) Cl
(A) CH3 CH = CH CH2 Br
Br (C) (D) Both A & C
CH2Cl
(B) CH3 CH CH = CH2
(C) CH2 = CH CH = CH2 Q.11 When ethyl bromide is treated with moist Ag2O,
Br main product is :
(A) Ethyl ether (B) Ethanol
N
(D) CH3 CH CH2 CH2 OH (C) Ethoxy ethane (D) All of the above
Q.5 The given compound CH3 O CH2 Br gives Q.12 When ethyl bromide is treated with dry Ag2O,main
which one of the following reactions : product is :
(A) Only SN1 (B) Only SN2 (A) Ethyl ether (B) Ethanol
(C) SN1 as well as SN2 (D) E1 (C) Ethoxy ethane (D) All of the above
Q.6 Among the bromides I-III given below, the order of Q.13 Consider the SN1 solvolysis of the following
reactivity in SN1 reaction is : halides in aqueous formic acid :
O Br Br CH3
CH3
(I) (II) (III) (I) CH CH CH3 (II)
CH3
Br Br Br Br
(A) III > I > II (B) III > II > I
(C) II > III > I (D) II > I > III (III) C6H5 CH C6H5 (IV)
Br
22
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Which one of the following is correct sequence of D D
the halides given above in the decreasing order of OH
HI
their reactivity? Q.18 ?

SN1
(A) III > IV > II > I (B) II > IV > I > III
H H
(C) I > II > III > IV (D) III > I > II > IV
Major product is :
D D D
Q.14 In the given pair in which pair the first compound is I
more reactive than second for SN1 reaction I
(A) (B)
(A) Cl CH2Cl
D
(B) Cl I
D
Cl (C) (D) None of these
D
(C)
IR
Cl Cl Q.19 Which one of the following compounds will give
Cl Cl enantiomeric pair on treatment with HOH ?
(D) C2H5 CH3
(A) C6H5 C I (B) CH3 C Br
C2H5 C 2H 5
Q.15 Which of the following is most reactive toward H C2H5
SN1.
(C) C6H5 C Br (D) C2H5 C Br
(A)
.S CH2 Cl
(B)
CH2 Cl
Q.20
D
For the given reaction

CH3
R1 R1
HOH
H CH3 R C X R C OH
CH2 Cl CH2 Cl
R2 R2
Which substrate will give maximum racemisation ?
(C) (D) CH3 CH3
.J
(A) C6H5 C Br (B) CH2 = CH C Br
OCH3 NO2
C2H5 C2H5
Q.16 Which compound undergoes hydrolysis by the SN1 Br
mechanism at the fastest rate ? Br
C6H5 C NO2
CH3 CH3 Br C6H5 C OCH3
(C) (D)
(A) (B)
N
Br
NH3
CH3
CH3 Br CH3

(C) (D) Q.21 In the given reaction :

Br Cl
Cl
Q.17 Arrange the following compounds in decreasing CH OH
order of their reactivity for hydrolysis reaction
3
[X]
(I) C6H5 CH2 Br (II) C6H5 CH C2H5 O Cl
(excess)
Br
Br Cl OCH3
CH3 Cl Cl
(III) (IV) CH
Br (A) (B)
(A) I > II > III > IV (B) IV > II > I > III O OCH3 O OCH3
(C) III > IV > II > I (D) IV > III > II > I
23
-------------------------------------------------------------------------------------------------------
Cl OCH3 C C CH3
OCH3 Cl (A) and
(C) (D) Br
20% 80%
O Cl O Cl
C C CH3
Cl (B) +
NaOH
Q.22 A. is
excess 20% 80%
Cl
O Cl C C CH3
(A) (B) (C)
OH OH
OH OH 100%
(C) (D)
(D)
OH Cl
100%
IR
Q.23 Compare the two methods shown for the
preparation of carboxylic acids : Q.26 Which of the following nucleophile will show
Mg
Method 1 : RBr
RMgBr minimum reactivity towards SN2 reaction :
diethyl ether
(I) CO
(A) Me3CO (B) MeO

2
RCO2H

(ii) H3O H
(C) (D) Me2CHO
NaCN
Method 2 : RBr
.S RCN
O
H O, HCl
2 RCO2H
heat Q.27 In the given reaction
Which of the following statements correctly OH
describes this conversion ? H NaOH
H [X]
25C
Cl
OH OH
Br CO2H OH H
(A) Both method 1 and method 2 are appropriate (A) H (B) H
for carrying out this conversion H OH
.J
(B) Neither method 1 nor method 2 is appropriate O
for carrying out this conversion. (C) Mixture of (A) and (B) (D) H
(C) Method 1 will work well, but method 2 is not
appropriate H
(D) Method 2 will work well, but method 1 is not
appropriate Q.28 Which of the following can not give SN1 reaction
easily ?
N
Q.24 The major product in the given reaction Br Br

Br Br
CH2Br
(A) (B) (C) (D)
+ NH3
Br
CH2NH2 CH2NH2
Q.29 In the given reaction :
(A) (B) O
(i ) NaN 3
Br NH2 [X]
( ii) HOH
CH2Br
[X] will be
(C) (D) All of these
NH2 N3 OH
Q.25 In the given reaction : OH N3
(A) (B)
Br
CH 3 C CNa
OH
Et 2 O /
(C) Mixture of (A) and (B) (D) OH
the products are :
24
-------------------------------------------------------------------------------------------------------
Q.30 In the given reaction : Cl CH2Cl
CH3 CH CH2 CH2 CH CH3
OTs OTs (C) (D)
(i) SH (one equivalent) Q.36 Which of the following is most reactive toward SN2.
(ii) KOH CH2 Cl CH2 Cl
[x]
(A) (B)
[X] will be :
OTs S H CH3
(A) CH3 CH CH2 CH2 CH CH3 CH2 Cl CH2 Cl
(B) CH3 CH CH2 CH2 CH CH3
(C) (D)
S S
CH3 CH3 OCH3 NO2
IR
CH3 S
CH3
(C) (D) S
Q.37 In which of the following, replacement of Cl is
most difficult?
Q.31

For CH3Br + OH CH3OH + Br
(A) (B) Cl
Cl
the rate of reaction is given by the expression :
(A) rate = k [CH3Br] (B) rate = k [OH] (C) Cl (D)
(C) rate = k [CH3Br] [OH] Cl
(D) rate = k[CH3Br] [OH]
Q.32
.S
Non-occurrence of the following reaction
Br + CH3OH BrCH3 + OH, is due to
Q.38 Correct order of rate of hydrolysis for following
compounds is
Br Br
(A) Attacking nucleophile is stronger one
(B) Leaving group is a strong base
(C) Alcohols are not good substrate (I) (II)
(D) Hydroxide ions are weak bases
Q.33 The reactivity of 2-bromo-2-methylbutane (I), 1-

.J
bromopentane (II) and 2-bromopentane(III) Br
Br
towards SN2 displacement is such that : (III) (IV)
(A) I > II > III (B) I > III > II
(C) II > III > I (D) II > I > III (A) III > II > IV > I (B) I > II > III > IV
(C) III > I > II > IV (D) III > II > I > IV
I
Me H Q.39 Which reaction conditions (reagents) is suitable for
N
KSH
Q.34 Et D the following reaction :
H
SH H ?

(A) Me H (B) Me H
H C OH Br C H
Et D Et D
H SH D D
SH SH (A) Br2 / CCl4 (B) SOBr2
(C) HBr / conc. H2SO4 (D) PBr3
(C) HS Me (D) H Me
Et D Et D Q.40 Arrange these compounds in order of increasing
H H SN2 reaction rate :
O
Q.35 Which reaction proceeds faster with NaI is DMSO.
CH2Cl
Cl Cl Br Cl Br
(A) CH3 (B) (I) (II) (III) (IV)
(A) III < I < II < IV (B) III < II < I < IV
(C) IV < III < I < II (D) III < IV < I < II
25
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Q.41 The reaction of SOCl2 on alkanols to form alkyl Q.46 The major product formed in the following reaction
chlorides gives good yields because is :
(A) Alkyl chlorides are immiscible with SOCl2 OH
(B) The other products of the reaction are gaseous
H2SO 4
CH3
and escape out
heat
(C) Alcohol and SOCl2 are soluble in water CH3
(D) The reaction does not occurs via intermediate H3C
formation of an alkyl chloro sulphite
CH3 CH3
CH3 (A) CH3 (B) CH3
Q.42
SOCl2
(A) H3C H3C
H OH Pyridine
CH3 CH3
D
Major product (A) is :
CH3 CH3
(C) (D)
IR
(A) H Cl (B) Cl H H3C H2C
CH3 CH3
D D
H Q.47 In the given pairs, which pair represent correct
(C) H2C = CH2 (D) H2C = C order of rate dehydrohalogenation reaction
D
(A) Cl <
CH3 Cl
SOCl2
Q.43 H
.S
D
(A)
OH
Major product (A) is :

(B)
(C)
Cl <
Cl
CH3 CH3 <

I Br
(A) H Cl (B) Cl H (D) CH3 CH2 Cl < CD3 CD2 Cl
D D
CH3
H
(C) H2C = CH2 (D) H2C = C H D C 2H5 O
.J
Q.48 ? Major product is :
D H Br C 2H5OH
Q.44 In the given reaction : CH3

.. . H3C H H3C CH3
CH3 CH2 S HOH (A) (B)
.. CH2 CH2 Br [X] C=C C=C
[X] will be : H CH3 H H
(A) CH3 CH2 S CH * H3C CH3 H3C H
2 CH2 OH
N
(C) C=C (D) C=C

(B) CH3 CH2 S CH2 CH *
2 OH H D D CH3
(C) 1 : 1 mixture of (A) and (B)
(D) 2 : 1 mixture of (A) and (B) C6H5
Q.49 CH3 H alcoholic, KOH
A
H2 O
Q.45 Me2C = CH CH2 CH2 Cl (X) Br H E2
Major product of above reaction is C6H5
OH CH3 C6H5 CH3 C6H5
(A) Me C CH2 CH2 CH2 C C
Me
(A) (B)
C C
(B) Me2C = CH CH2 CH2 OH H C6H5 H
C6H5
(C) Me2C = CH CH CH2 OH
H CH3
OH C
OH (C) (D) None is correct
C
(D) CMe2 C6H5 C6H5
26
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Q.50 The rate of elimination (using EtONa) of :. Me
Br Br H / MeOH
(D) H OH
(I) (II) (III) Et

Br
Q.5 SN2 reaction will be negligible in
t-Bu t-Bu
Br Br Br Br
(A) I > II > III (B) I > III > II
(C) II > I > III (D) III > I > II
(A) (B) (C) (D)
EXERCISE II Q.6 Rate of SN2 depends on

(A) Conc. of Nucleophile (B) Conc. of substrate
Q.1 SN1 & SN2 is not favourable in (C) Nature of leaving group (D) Nature of solvent
(A) H2C = CH Cl (B) Ph CH2 Cl
(C) Ph Cl (D) H2C = CH CH2 Cl Q.7 Correct statement(s) for the product(s) of following
IR
reaction.
Q.2 SN1 & SN2 product are same in (excluding Cl2 / 500C
stereoisomer) CH2 = CH CH2 Ph
Cl (A) Four different products are formed
(B) Two optically active products are formed
(A) (B) (C) The optically active compound formed here
can also be made by the reaction of HCl
.S Cl (D) The reaction path is free radical substitution.
(C) (D) Ph CH CH CH3 Q.8 In the given pair in which pair the first compound is
more reactive than second to SN2 reaction.
CH3 Cl
Cl (A) Cl CH2Cl
Q.3 Which of the following statements is/are true ? Cl

(A) CH3 CH2 CH2 I will react more readily (B) Cl
than (CH3)2CHI for SN2 reactions.
(B) CH3 CH2 CH2 Cl will react more readily (C)
.J
than CH3 CH2 CH2 Br for SN2 reactions. Cl Cl
(C) CH3 CH2 CH2 CH2 Br will react more
Cl Cl
readily than (CH3)3C CH2 Br for SN2 reactions.
(D)
(D) CH3 O C6H4 CH2Br will react more
readily than NO2 C6H5 CH2Br for SN2
reactions. Q.9 A gem dichloride is formed in the reaction :
(A) CH3CHO and PCl5 (B) CH3COCH3 and PCl5
N
Q.4 In which of the following case configuration about (C)CH2 = CH2 and Cl2 (D) CH2 = CHCl and HCl
chiral C* is retained :
Me
Q.10 Match List I with List II for given SN2 reaction &
Na CH Br
(A) H OH

3
select the correct answer from the codes given
below
D
Z CH2Br + CH3O Z CH2 OCH3 + Br
Me List I List II (relative reactivity)
(A) H (P) 0.1
SOCl2 CH ONa
(B) H OH
3
(B) CH3 (Q) 3
(C) C2H5 (R) 1
D CH3
(D) CH
(S) 100
Me
CH3
PCl CH ONa
(C) H OH
3

3

27
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Q.11 In which product formation takes place according EXERCISE III
to Hoffmanns rule Q.1 Identify A, B, C, D, E and F in the following series

(A) CH3CH2 CH CH3 tBu O K of reaction.

Br2 aq.KOH Na
Br A B C
h
alc.KOH
(B) CH3CH2 CH CH3 CH3CH2OK NBS +C
D E F
Br
CH3 Q.2 What are the products of the following reactions?
(C) CH3CH2 CH N CH3 OH CH3
CH3 CH3 (a) CH3 C Cl + OCH3
OH
(D) CH3CH2CH CH3
CH3
CH3
S(CH3)2
(b) CH3 C O + CH3 X
IR
Q.12 Which of following are correct for given reaction
CH3

N OH Q.3 Complete the following by providing the structure
of (A),(B), (C) and (D).
PBr Alc.KOH
(i) CH3CH2CH2OH
3
(A) (B)
(A) Major product of reaction is HBr
(C)
3 NH
(D)
N

Alc.KOH H / H2 O
.S
(B) Major product is
CH3
N
(ii) CH3CH2CH2I
SOCl2
H
(C) (D)
(A)
LiAlH4
NBS
(B)
Alc.KOH
(iii) CH3CH2CH = CH2 (A)
Light
(C) The reaction is thermal elimination reaction HBr
(E1CB) (B) (C)
(D) The reaction is E2 reaction CH3CHO / H2O HBr
(iv) CH3CH2MgBr (A)
Alc.KOH
(B) (C)
Q.13 Match the List I (reaction) with List II (reaction
.J
intermediate) and select the correct answer using
the codes given below the Lists. Q.4 CH3 CH2I reacts more rapidly with strong base in
List I List II comparison
Li to CD3CHList
2 I II
alc.KOH /
(A) CF3 CHCl2 Q.5 Propose a mechanism for the following reactions.
CF2 = CCl2 (1) Transition state OH
CH3 CH3 CH3
H2O
N
H
(B) CH3 C OH
C Br CH3
CH3 CH3
CH3 C = CH2 (2) Carbocation
Q.6 Each of the following alcohols has been subjected
CH3 to acid catalyzed dehydration and yields a mixture
of two isomeric alkenes. Identify the two alkenes in
alc.KOH
(C) CH3 CH2 Br

each case, and predict which one is the major
product on the basis of the Zaitsev rule.
CH2 = CH2 (3) Carbanion H3C OH
(a) (CH3)2CCH(CH3)2 (b)
Br OH
alc.KOH / OH
(D) CH3 C CH3
CH3
CH3 C = CH2 (4) Free radical (c)
CH3
H
28
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Q.7 Give the major product (with proper explanation) Q.2 Arrange the following compounds in order of
when following halogen compounds are treated increasing dipole moment [IIT 1996]
with sodium ethoxide. Toluene m-dichlorobenzene
CH2Br
(a) CH3 CH CHCH3 (b) I II
CH3
Br CH3 o-dichlorobenzene p-dichlorobenzene
III IV
(c) CH3 (A) I < IV < II < III (B) IV < I < II < III
Cl (C) IV < I < III < II (D) IV < II < I < III
Q.8 2-chloro-3-methylbutane on treatment with

alcoholic potash gives 2-methylbutene-2 as major Q.3 (CH3)3CMgCl reaction with D2O produces :
product. [IIT 1997]
(A) (CH3)3CD (B) (CH3)3OD
Q.9 KCN reacts with R I to give alkyl cyanide, while
(C) (CD3)3CD (D) (CH3)3OD
IR
AgCN results in isocyanide as major product.
Q.10 Predict the product(s) and write the mechanism of
Q.4 The order of reactivity of the following alkyl halides
each of the following reactions.
for a SN2 reaction is : [IIT 2000]
HI (1mole) excess HI
(i)
(ii)
(A) RF > RC > R Br > R I
O O (B) R F > R Br > R Cl > R I
Q.11 Convert (C) R Cl > R Br > RF > R I
(i)
.S CH2 CH3 CH = CH2
Q.5
(D) R I > RBr > R Cl > R F
Identify the set of reagents / reaction conditions X

(ii) CH3CH2CH = CH2 CH3CH2CH2CH2NH2 and Y in the following set of transformation :
X
CH3 CH2 CH2Br Product
(iii) CH3CH2CH = CH2 CH2 = CH CH = CH2 Y
CH3 CH CH3 [IIT 2002]
(iv) OH CH2 CH2CH = CH2
O Br
.J
(A) X = dilute aqueous NaOH, 20C; Y = HBr /
Q.12 Treatment of 2-bromobutane with hot alcoholic acetic acid, 20C
KOH gives a mixture of three isomeric butenes
(A), (B) and (C). Ozonolysis of the minor product (B) X = concentrated alcoholic NaOH, 80C; Y =
(A), gives formaldehyde and another aldehyde in HBr / acetic acid 20C
equimolar amounts. What are the structural (C) X = dilute aqueous NaOH, 20C; Y =
formulae of (A),(B) and (C)? Br2/CHCl3, 0C
N
(D) X = concentrated alcoholic NaOH, 80C; Y =

Q.13 A hydrocarbon C8H10 (A) on ozonolysis gives Br2 / CHCl3, 0C
compound C4H6O2 (B) only. The compound (B)
can also be obtained from the alkyl bromide
C3H5Br (C) upon treatment with magnesium in dry Q.6 CH3MgBr + Ethyl ester which can be formed as
ether followed by CO2 and acidification. Identify product [IIT 2003]
(A), (B) and (C) and also give equations for the
(excess)
reactions.
CH2CH3
CH3
EXERCISE IV(A) (A) HO CH2CH3 (B)
HO CH2CH2CH3
CH2CH3 CH2CH3
Q.1 Aryl halides are less reactive towards nucleophilic
substitution reaction as compared to alkyl halides
due to [IIT 1990] CH2CH3 CH3
(A) The formation of less stable carbonium ion (C) HO (D) HO
CH2CH3 CH3
(B) Resonance stabilization
(C) The inductive effect CH3 CH3
2
(D) sp hybridised carbon attached to the halogen
29
-------------------------------------------------------------------------------------------------------
Q.7 Match the following [IIT 2006] Q.12 The major product of the following reaction is
O
Column I Column II
(A) CH3 CHBr CD3 on (P) E1 reaction C [IIT-JEE 2011
(i) KOH
NH
treatment with alc. C (ii) Br CH2Cl
KOH gives
O
CH2 = CH CD3 as a O O
major product
(B) Ph CHBr CH3 reacts (Q) E2 reaction C C
(A) NCH2 Br (B) N CH2Cl
faster than
Ph CHBr CD3 C C
(C) Ph CD2CH2Br (R) E1 cb reaction O O
O
on treatment with O
C2H5OD/C2H5O C
C
gives Ph CD = CH2 N
(C) N (D) C
as the major product.
(D) PhCH2CH2Br and (S) First order reaction OCH2 Br O CH2 Cl
IR
PhCD2CH2Br react with
same rate
Q.8 The reagent(s) for the following conversion, EXERCISE IV(B)
[IIT 2007] Q.1 Identify the major product in [II the following
Br reactions : [IIT 1993]
?
Br H H Cl
(A) alcoholic KOH alcoholic
(B) alcoholic KOH followed by NaNH2 (i) C6H5 CH2 CH CH3 ?
KOH
Q.9
.S
(C) aqueous KOH followed by NaNH2
(D) Zn/CH3OH
The major product of the following reaction is

HBr
?
(ii) C6H5COOH + CH3Mg I ? + ?
[IIT 2008] Q.2 An alkyl halide X of formula C6H13Cl on treatment

Me Br with potassium tertiary butoxide gives two isomeric

PhS Na
alkenes Y and Z (C6H12). Both alkenes on
F
dimethylformamide hydrogenation give 2, 4-dimethylbutane. Predict
the structures of X, Y and Z. [IIT 1996]
.J
Q.3 Predict the structure of the intermediates/products
NO2
Me Me in the following reaction sequence- [IIT 1996]
SPh SPh
Br
F F H Ph Na I
C
(A) (B) MeO H Acetone
Ph
C6H5
N
NO2 NO2 Q.4 (a) C6H5CH2CHCl

Alcoholic KOH
A + B Write
Me Br Me SPh Heat
structures of (A) and (B).

SPh SPh HI( excess )
(C) (D) (b) (CH3)2CHOCH3 A + B Write
Heat
structures of A and B. [IIT 1998]
Q.5 Complete the following reaction with appropriate
NO2 NO2
structures of products / reagents. [IIT 1998]
HBr
Q.10 In the reaction OCH3
the products are CH =CH2
Br2 (i)NaNH (3equi .)
(A) 2
(B)
(A) Br OCH3 and H2 (B) Br and CH3Br (II) CH3 I
Q.6 What would be major product ?[IIT-JEE 2000]

(C) Br and CH3OH (D) OH and CH3Br CH3
[IIT-JEE 2010] CH3 C CH2Br 2
5
?
C H OH
Q.11 The total number of alkenes possible by
dehydrobromination of 3-bromo-3-cyclopentylhexane CH3
using alcoholic KOH is [IIT-JEE 2011]
30
-------------------------------------------------------------------------------------------------------
ANSWER KEY
EXERCISE - I
Ques. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. A B A B C A C C B D B C A C C B B B C C
Ques. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. A B C A B A D C C C C B C D B D D A D C
Ques. 44 42 43 44 45 46 47 48 49 50
Ans. B B A C D C A C A A
EXERCISE II
Ques. 1 2 3 4 5 6 7 8
Ans. A,C B,C A,C A,C A,B,C A,B,C,D A,B,C,D B,D
Ques. 9
Ans. A,B,D
IR
Q.10 (A) S ; (B) Q ; (C) R ; (D) P Q.11 A, C, D Q.12 A, C Q.13 (A) 3 ; (B) 2 ; (C) 1 ; (D) 1
EXERCISE III
Q.1 Q.2
Q.3 (i) A, CH3CH2CH2Br ; B, CH3CH = CH2 ; C, CH3CHBrCH3; D, CH3CHNH2CH3
(ii) A, CH3CH = CH2; B, CH3CHOHCH3; C, CH3CHClCH3; D, CH3CH2CH2
(iii) A, CH3CHBrCH = CH2; B, CH2 = CH CH = CH2; C, CH3CHBrCH = CH2 & CH3CH = CH CH2Br
Q.4
.S
(iv) A, CH3CH2CHOHCH3; B, CH3CH2CHBrCH3; C, CH3CH = CH CH3
The elimination of HI (or DI) in presence of strong base shows E2 elimination. The rate determining step involves
breaking up of C H (or C D) bond. The C D bond being stronger than C H and thus elimination is faster in
case of CH3 CH2I.
Q.5 Q.6 Stability of alkene by -hydrogen Q.7
KOH(alc )
Q.8 H3C CH CH CH3 CH3 C = CH CH3 + CH3 CH CH = CH2
.J
CH3 Cl CH3 CH3
major minor
Elimination occurs according to saytzeff rule. The major product is one which involves elimination of H from less
hydrogenated carbon.
Q.9 KCN is an ionic compound [K+(:C )] in which both C and N carry a lone pair electron. Carbon carrying lone
pair of electrons is more reactive and thus alkyl attacks carbon to give alkyl cyanide AgCN being covalent has Ag
N

C N : structure with lone pair on N thus R attacks on N atom and R N C is formed.
Q.10 Q.11 Q.12
Mg (i) CO2 ozonolysis
Br MgBr (ii) H O C OH C C
ether 3
Q.13
Cyclopropyl O
bromide (C) Cyclopropane (B) Dicyclopropyl (A)
carboxylic acid acetylene
EXERCISE IV(A)
Ques. 1 2 3 4 5 6
Ans. B,D B A D B D
Q.7 A Q ;B Q; C R, S; D P, S
Q.8 B
Q.9 A
Q.10 D
31
-------------------------------------------------------------------------------------------------------
Br
alc . KOH
Q.11 (5) CH 3CH 2 C CH 2CH 2CH 3 CH 3CH = C CH 2CH 3 (Cis/Trans) + CH 3CH 2 C CH 2CH 3
CH 3CH 2 C = CH CH 2CH 3 (Cis/Trans)
Q.12 (A)
O O
C C

N H + OH :N: + H2O
C C
O O
IR
Br CH2Cl O
C
NCH2 Br
C
O
Q.1
.S Br
EXERCISE IV(B)
(i) C6H5 CH = CH CH3 ; C6H5 CH CH2 CH3

(ii) C6H5COOMgI + CH4
CH3 CH3 CH3 CH3
Q.2 (X) : CH3 C CH CH3 ; (Y) : CH2 = C CH CH3 ; (Z) : CH3 C CH CH3
Cl CH3 CH3
.J
I
H Ph
Q.3 MeO H (NGP due to MeO, so retention of configuration.
Ph
CH3
Q.4 (a) Cis and trans forms of stibene C6H5CH = CHC6H5 ; (b) CHI + CH3I
CH3
N
Br
CH CH2Br C CNa CCCH3
NaNH (liq.)
2 CH I
3
Q.5 (A)
(B) 3
CH3
Q.6 CH3 C = CHCH3
32
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Halogen Derivative

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IIT-JEE ChEmistry by N.J.

sir ORGANIC ChemIstRy

Polar protic Solvent: ..

S CH3 Ans. (a) 1>2 (b) 1>2 (c) 1>2

(4) Planar carbocation can be attacked from both

( O , F & CH3 O cannot be substituted

CH3 Q.3 1 Bromobicyclo [2.2.1] heptane is extremely

(4) CH2 = CH CH2 Cl

Q.8 KSH + CH3 O S CH3 +

Q.10 Explain mustard gas hydrolysis at a very high CH3

(2) H O CH2 CH2 Br

Q.20 R X + Reagent Product

(B) (1) CH3 3 CCl H2O CH3 3 COH HCl

H the rates of the reaction showed the following

10. Competition experiments are those in which

Write Lewis structures for the cyanic both CH3

7. Give structures for the products of each of the CH 3

(X F) CH3 X SN2 SN2 SN2

E2 (formation of conjugated double. Bond)

CH3 CH2 CH2 Br

(15) Major product (E1,E2,SN1 or SN2)

+ Hoffmann exhaustive methylation

Q.6 CH3 N CH2 CH2 CH3

Aliphatic Unsaturated Aromatic

CH3CHCH (Vic) (Vicinal)

Polyhalogen CHCl 3 (Chloroform)

CCl4 (Carbon tetrachloride pyrene)

General Method of Preparation Br2

2. RH + Cl HCl + R + R Cl. Imp. |

Q.2 ONa + CH3 Cl (4) Hoffmann exhaustive alkylation

Substrate aq. AgNO3 alc. AgNO3

For the given reaction

(C) (D) Q.21 In the given reaction :

Q.24 The major product in the given reaction Br Br

Q.33 The reactivity of 2-bromo-2-methylbutane (I), 1-

Major product (A) is :

CH3 CH3 <

Q.44 In the given reaction : CH3

(C) C=C (D) C=C

(I) (II) (III) Et

EXERCISE II Q.6 Rate of SN2 depends on

Q.3 Which of the following statements is/are true ? Cl

Q.8 2-chloro-3-methylbutane on treatment with

Identify the set of reagents / reaction conditions X

(D) X = concentrated alcoholic NaOH, 80C; Y =

The major product of the following reaction is

[IIT 2008] Q.2 An alkyl halide X of formula C6H13Cl on treatment

NO2 NO2 Q.4 (a) C6H5CH2CHCl

structures of (A) and (B).

Q.6 What would be major product ?[IIT-JEE 2000]

Q.5 Q.6 Stability of alkene by -hydrogen Q.7

CH 3CH 2 C = CH CH 2CH 3 (Cis/Trans)

(i) C6H5 CH = CH CH3 ; C6H5 CH CH2 CH3

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