Halogen Derivative Module PDF

ETOOSINDIA
INDIA’S NO. 1 ONLINE COACHING
IIT-JEE ChEmistry by N.J. sir

ORGANIC ChemIstRy
IR
.S
.J
HALOGEN DERIVATIVES
N
1
-------------------------------------------------------------------------------------------------------
ETOOS Education Pvt. Ltd.
Plot No. 68, Near Union Bank of India, Rajeev Gandhi Nagar, Kota, Rajasthan – 324005
Mob. No. : 9214233360
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
IR
Polar O O
H H/ R H/ NH 3
Polar aprotic
O O O
CH3 CH3
S C—N CH—
3 C—N
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 O—H H
O
O O
O
H H H H —
O O (c) CH—
3 C—O CH—
3 C — OH
O—H
.J
H H H (d) R — O— R — OH
Solvation of cation Solvation of anions
S 
(e) H H H—S
Polar aprotic solvent .. 
Can solvate only cations & not anions (f) R — SH R — .S. :
CH3 +
N
(g) H3O H2O

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:-
2
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
O
4 Components
4. R—O—H > R—C—O—H
(1) R  Substrate
O
(2) L  Leaving group
—
5. R — O— > R—C—O (3) Solvent (4) Nucleophile.
Rule 3:- Types of nucleophilic substitution.

If e— donating atoms are of different size in polar 1. SN1 2. SN2 3. SNAR
protic solvent 4. SN NGP
5. SN i
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
IR
 .. 
If e— donating atoms are of different size in polar 2. R  Nu  R — Nu
aprotic solvent R1
Nucleophilicity  basicity R1 . .
1. Slow 
 + L
C—L rds. C
Leaving group (L):- Particles which are substituted
R2 R2 R3
by stronger nucleophiles or depart from a molecule to
.S
generate carbocation are leaving groups. R3
1 R1
 Leaving group ability  .. Θ
Base strength 2. + Nu 
C
 Weak bases are good leaving groups.
 . . R2 R3
R L  R  L R1
R1
 R2 Nu Nu R2
1. I > Br— > Cl— >> F—
.J
O
2. H H > OH
— R3 R3
O —
3. R H > R— O Characteristics
O (1) rate = k [R — L]1; rate is independent on
— concentration of nuclophile.
4. R—C—O > R — O—
N
O (2) rate is directly proportional to stability of

O carbocation
–
5. O — S — CH3 < O — S — CF3 (3) Rearrangement possible
(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. –
–
< O—S—
O—S— —N (7) Normally 3° – carbocation & resonance
CH3 stabilized carbocation support this reaction
O O
mechanism if attacking Nuclophile is neutral
Nucleophilic substitution (SN – Reactions) polar protic solvent.
. . . .
Nu
R — L   R — Nu + L
3
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
(8) Solvolysis (SN1) Q.2 SN1 reactions are also known as solvolysis as
O .. Θ
H H solvent molecules behave as Nu . Write
Ph — CH2 – Cl Ph – CH2 — OH + HCl
the product in each case.
H2O
(1) Ph — CH2 — Br  
Q.1 Compare the rate of SN1 reaction:- CH3OH

(2) Ph — CH2 — Br  
EtOH
(a) Ph — CH2 — Cl Ph — CH — Cl (3) Ph — CH2 — Br 
O
Ph ||
(i) (ii) H—C—OH
Ph (4) Ph — CH2 — Br 
PhOH
Ph — C — Cl (5) Ph — CH2 — Br 
IR
Ph Ans: (1) Ph — CH2 — OH
(iii) (2) Ph — CH2 — OCH3
I I I (3) Ph — CH2 — OEt
O
||
(b) (4) Ph — CH2 — O — C — H
(5) Ph — CH2 — OPh
.S
(i)
I
(ii)
I
(iii)
I Q.3 Which SN1 reaction is expected to occur
rapidly.
O
(c) 1. (a) (CH3)3 CCl + H H (CH3)3 C OH+ HCl
O O
(i) (ii) (iii) (b) (CH3)3 CBr + H H  (CH3)3 C OH + HBr
(d) CH3 — O — CH2 — Cl
.J
(i)
CH3 — O — CH2 — CH2 — Cl 2. (a) Cl + EtO—  O — Et + Cl—
(ii)
CH—Cl CH—Cl
2
2
1.0 M 1.0 M
(e) (b) Cl + tO—  O — Et + Cl—
N
2.0 M 1.0 M
(f) CH3 — O — CH = CH — CH2 — Cl &
CH3 — O — CH2 — CH = CH — CH2 — Cl
3. (a) Cl + EtO—  O — Et + Cl—
(g) (i) 100% 
Ph — CH — Cl 
H2O
1.0 M 1.0 M
CH3
80%H2O
(ii) Ph — CH — Cl   (b) Cl + EtO—  O — Et + Cl—
20%EtOH
CH3 1.0 M 1.0 M 1.0 M 2.0 M
Ans: (a) (iii) > (ii) > (i) (b) (ii) > (iii) > (i) Ans. (1) b > a (2) a < b (3) a = b
(c) (i) > (ii) > (iii) (d) (i) > (ii)
(e) (i) > (ii) (f) (i) > (ii) (g) (i) > (ii)
4
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
Q.4 Compare rate of SN1 reaction H OTS H OTS
O
1. (a) Cl + H H  4.
O
 (b) Br + H H  (a) (b)
O
Cl + H H  5. Br
2. (a)
Br
O (a) (b)
 (b) Cl + CH3 H 
O 6.
3. (a) Cl + H H 
Me
O
IR
Cl + H Br CH—Br
 (b) H  2
(a) (b)
Ans. (1) a > b (2) b > a (3) a > c > b > d
(4) a < b (5) a < b (6) b > a
Ans. (1) (b) Br (better leaving group)
.S O Q.6 These substrates cannot give SN1. Explain
(2) (b) H H better solvation
1. 2. CH2 = CH — Cl 3.
(3) (a) Cl
(double bond character)
Cl Cl
Q.5 Compare rate of SN1 CH3
Me
Me 4. CH— C — F 5. CH3 — CH2 — F
3
1.
Me Me CH3
.J
CH3
Me 6. CH— C — CH— Br 7.
OTS
32
Me OTS Cl
(a) (b) CH3
t–Bu ( O , F & CH3 – O cannot be substituted

t–Bu
N
strong bars & weak leaving groups)
2. SN2 reaction nucleophilic substitution

SN2 — Reaction
Nucleophilic Substitution 2nd order
. .
Cl Cl Nu + R—L  Nu – – R – – L
(a) (b)
I Cl Br Cl . .
Nu — R + L
O O O Characteristics:-
3. x x
O
1. Nu + C—L Nu - - - C - - - L 
y z
(a) (b) (c) (d) y z
5
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
x
(C)(i) Br + (C6H5)3N 
Nu — C +L
y     
 z (ii) Br+ (C6H5)3P 
1
2. rate of reaction  . (D) (i) Br + CH3O— 
Bulkiness in x, y & z
. . 1.0 M  1.0 M
3. rate  strength of Nu
. . (ii) Br + CH3O— 
4. rate  Leaving group ability of L
5. Inversion of configuration takes place. ‘ 1.0 M  2.0 M
Ans. (A) i > ii (B) I < ii (C) ii > i (D) ii > i
Characteristics Q.3 1– Bromobicyclo [2.2.1] heptane is extremely

Q.1 Compare rate of SN2 reaction:– unreactive in either SN1 or SN2 reaction.
IR
1. CH3 — CH2 — CH2 — Br & CH—CH—Br Explain:
3
SN1 X
CH3
(Bridge Head position)
(i) (ii)
2. CH3 — CH2 — CH2 — CH2 — Cl

(i) Br
CH3 — CH2 — CH2 — CH2 — I SN2 X
3.
.S (ii)
CH3 — CH — CH2 — Cl Q.4

(Walden unreason not possible)
Write the products of SN2 reaction:–

(i) H KSH 
1. H 
CH3 — CH2 — CH2 — CH2 — Cl
| Cl Br
CH3 Br
(ii) ACO— 
2. D H 
.J
4. Br H D
Cl
(i) (ii) CH3
CH3
5. Cl KSH 
Cl 3. Cl 
H
N
(i) (ii) Et
Ans. (1) 1 > 2 (2) 2 > 1 (3) 1 > 2 CH3
(4) 1 < 2 (5) 1 > 2 4. KSH 

Cl — CH—
2 C — CH—
2 CH 2— Cl
Q.2 Compare rate of SN2 reaction:– CH3
—
(A)(i) Cl + CH3 — CH2 — O  NaCN (1 eq)
   or Cl
(ii) Cl+ CH3 — CH2 — OH  CH2 I
NaCN  6. KSH(1eq)
5.   
(B)(i) Cl + CH3 — CH2 — O— 
     I
(ii) Cl + CH3 — CH2 — S—  Br
7. KSH 
Br — CH2 — CH = CH — Br 
(1eq)
6
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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) CH—N
3 — CH— Cl2
.S CH3
(8) CH3 — F
CH3
(9) CH—
3 C — Cl
CH3
(10) Br
.J
(11) CH3— C — Et
Cl
CH—Cl
N
(12)
Cl
(13)
CH3
(14) CH3 —C — CH2 — Cl
CH3
(15) — CH—
2 Cl
7
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
Q.6 Explain
–
OH + CH3 — O — CH3  No.
Reaction Q.14 Explain:–
H  O
CH — O — CH  2CH OH H H
3 3 3 (a) CH3 — S — CH2 — CD2 — I
CH3 CH3 — S — CH2 — CD2 — OH
Q.7 TSCl  A 
NaCN  B
H OH 
–
D (b) ACO / ACOH
14  
CH—
2 CH 2
O
I
Q.8 KSH + CH3 — O S CH3 
IR
O +
14
CH—
2 CH—OAC
2
Q.9 Compare rate of hydrolysis
Ph 14
H H H S H CH—
2 CH—OAC
2
CH3
Q.10
.S
SPh Cl
(a)
Cl
(b)
H
Explain mustard gas hydrolysis at a very high

Cl
(c)
Q.15 H
HO H
HBr 
Br 
CCl4
rate:– CH3
Cl — CH2 — CH2 — S — CH2 — CH2 —Cl
CH3
Q.11 Explain:–
–
OTS H Ph ACO / ACOH
Q.16  
.J
–
ACO / ACOH TSO H
 
CH3
OTS
OTS
+ Q.17
(1) H — O — CH2 — CH2 — CH2 — Br
N
O
 +

 + Br + H
CH3
Q.12 H HBr 
Br  (2) H — O — CH2 — CH2 — Br 
CCl 
H OH 4
(3) NH2—CH2 — CH2 — CH2 — CH2 — Br
CH3
OH/H2O

 
Q.13 Compare rate of hydrolysis:–
SH
SH
SN1’
H2O
CH3—CH=CH—CH2—Cl 
I CH3—CH=CH—CH2—OH+ CH3— CH —CH=CH2
I |
(a) (b) OH
8
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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 /R—OH 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:
.J
N
9
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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 1.0M3  CH3O  1.0M   CH3 CH2CH2OCH3  Br 
OR
CH3CH2CH2Br 1.0M  CH3O  2.0M  CH3CH2CH2OCH3  Br 
.J
(2)
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
 CH3 3 CBr  H2O   CH3 3 COH  HBr
N
(2)
(B) (1)  CH3 3 CCl  H2O   CH3 3 COH  HCl

OR
(2)  CH3 3 CCl  CH3OH   CH3 3 COCH3  HCl
EtOH
(C) (1)  CH3 3 CCl  1.0M  CH3CH2O 1.0M    CH3 3 COCH2CH3  Cl
OR
EtOH
(2)  CH3 3 CCl   2.0M  CH3CH2O  1.0M    CH3 3 COCH2CH3  Cl
EtOH
(D) (1)  CH3 3 CCl  1.0M  CH3CH2O 1.0M    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
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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
the rates of the reaction showed the following
IR
H
order: (CH3)3CBr > CH3Br > CH3CH2Br >
Cl
(CH3)2CHBr
Provide an explanation for this order of
(C) H H l reactivity
?
CH3OH
D
.S 9. What would be the effect of increasing solvent
polarity on the rate of each of the following
nucleophilic substitutions reactions?
Cl
CH3 (a) Nu: + R  L  R  Nu+ + :L–
H2 O
(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
.J
unreactive in either SN2 or SN1 reaction one reactant with two reactive sites) compete
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 CH 3
(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, 4–Dichlorohexane (1 mole) + NaI (1 NaOH in
C6 H10S
aqueous EtOH
mole) acetone
 C 6H10 ICl  NaCl H Cl
(C) 1, 2–Dibromoethane (1 mole) +
NaSCH2CH2SNa   C 4H8 S2  2NaBr
11
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
IR
IIT-JEE ChEmistry by N.J. sir ORGANIC chemistry
Comparison of SN1, SN2, E1 & E2
Reactant Neutral Nucleophiles or Bases Weak Nucleophiles Strong Bases /Nucleophiles
R
O
HH
O
HR
S
HH
S O RO / EtO / CH3 O / O /Et N
.S
H    || 3 1
—
.. I , SH , CN , CH3– C –O
NH3
.. ..   
.N. , N , .N. : , Br , SCN , R– S ,
 
(X  F) CH3 —X SN2 SN2 SN2
Ph — CH2 — X
Ph— CH2—CH2—X .J SN1(Solvolysis)
SN2
SN2
SN2
SN2
E2 (formation of conjugated double. Bond)

N
SN2 {Exception in sterically hirdered base
R—CH2—X 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
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
IR
.S
.J
N
13
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
DPP-02 Time: 30 Minutes
1 2 1 2 EtONa /EtOH
Comparison of SN , SN , E & E
(7) CH2=CH— CH —CH3 
| NaI / Acetone 
(1) Ph — CH2 — Br   Br

H2O
KSH  (8) NaH 

 O — H 
(2) KCN 

 CH3 —CH2 —CH2 —Br
EtONa/ EtOH (A)   (B)
IR

Cl CH3
|
(9) CH3 — C — CH — CH3 EtOH 

| | 
CH3 —O /CH3OH CH3 Br
(3) CH3 — CH2 — Br  
(4)
.S H2O

CH3OH
(10) (a) CH3 — O— + Br 
   (b) O— + CH3 — Br 


Cl EtONa/ EtOH
 
CH3
O /
OH

(11) To prepare CH3—O—CH , which of
.J
  CH3
Et3N the following will give better yield:–
(1) CH3 — ONa + CH3 — CH — CH3 
|
NaI / Acetone  CH3
(5) R-2-chloropentane 
(2) CH3 — CH — ONa + CH3 —I 
NaN3
N
  |
CH3
 
CH3 —C—O
|| (12) Styrene (C6H5 — CH = CH2) is to be prepared
O by dehydrohalogenation using alc.KOH.
 Which of the following will give better yield.
EtO / EtOH Ph
(1) alc.KOH 

CH3—CH
Br
NaCN 
 Ph
H H  |
(2) alc.KOH 
EtONa/ EtOH CH2 — CH2 — Br 
(6)  

CH3 NaI / Acetone 
OTS 
14
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
(13) Write mechanism which accounts for the O
following products. ||
(a) HO — CH2 — CH2 — Br (h) 3-Chloropentane + CH3 — C — O—
O
OH /H2O ||
  CH3 —C—OH
O  
50C
(b) NH2 —CH2—CH2—CH2 —CH2 — Br
 25C 
(i) OH + (R) -2-bromobutane 
OH /H2O
 
N
H 25C
(j) (S)-3-bromo-3-methylhexane  
CH OH 3
(14) Major Product of reactions I

(k) (S)-2-bromooctane 
CH3OH/50C
IR
(E1, E2, SN1 & SN2)
(a) CH3—CH2 — CH2 — CH2 — CH2 —Br
(15) Major product (E1,E2,SN1 or SN2)
CH3CH2OH Cl
+ CH3 — CH2 — O— 
50C H
I
(a)  
CH3OH
(b)
.S CH3—CH2— CH2 — CH2 — CH2 —Br
+ O— 

OH/50C

H
D
Cl
H I
(b)  
H CH3OH
—
(b) Br + CH3O 
CH3OH/50C D
Cl
.J
H I
(c)  
(c) Br + O—  CH3OH

OH/50C D
H
Cl
Cl H2O/CH3OH
(d) CH3  
N

I / Acetone
(e) 
50C H
D
Cl (16) Give major product (E1, E2, SN1 or SN2)

CH3OH/ (a) CH3 — CH2 — CH2 — Br
(f) CH 3  
25C CH3 —OH
+ CH3 — O—  
50C
CH3OH (b) CH3 — CH2 — CH2 — Br

(g) 3-Chloropentane + CH3O—  
50C
+ O—  OH 

50C
15
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
CH3 Et
 50C 
(c) C — Br + SH 
CH3OH Et Br CH3OH
Et
(e)  
H 25C
Et
Et
Br 
Et  CH3OH (16) Consider the reaction of I with
(d) + OH  
50C CH3—CH2— Cl.
Et
(a) Would you expect the reaction to be SN1 or
SN2
(b) The rate constant of the reaction at 60°C is 5
× 10–5 L mol–1 sec–1. What is the reaction rate

IR
if [ I ] = 0.1 mol/L and [CH3 — CH2 — Cl ] =
0.1 mol/L.
.S
.J
N
16
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
DPP- 03 Time: 30 Minutes
—
E1CB - 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
—
Saytzeff Hoffmann OH 
IR
Q.7 

L.G. % Hoffmann +
N
L.G. Tendency
 —
– N (Me)3 90% Q.8 OH 

 + 
– S (Et)2 74% N
–F 70%
— Br
.S 19%
Q.9
+
N
OH 


—
EtO/EtOH 
 + OH/  
95% 5% Q.10 + 
N(Me)3
+ N
T.S. has more carbanion character.
.J
+ Hoffmann exhaustive methylation
N(Me)3
Q.1 CH3 — CH2 — CH2 — NH2 
1. CH3I

Q.1  2. Ag O(moist) 2
3. 
N
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 Me—CH2— 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
17
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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) 
 
OH 
IR
Q.9 CH3— C —CH2—CH2—F 

—
EtO  Q.7 MCPBA 

Q.10 CH3 — C — CH2 — CH2 — F  
||
O N
—
Q.11 EtO 
CH3 — C — CH2 — CH2 — F  O
 ||
|| 
Q.8 Ph — C — O — CH2 — CH3 
E1
.SO
CH3 Q.9
S
|| 
CH3—CH2— C —S—CH2—CH3 
| O
Q.1 
Ph — CH2 — CH2 — N — Me  ||
| Q.10 
CH3 — CH2 — C — O — CH2 —CH3 
O— O
O—C—CH3 
.J
Q.11 
H2O2 
Q.2   (A) 
O—C—CH3
Me—N—Me O
Ph
N
Q.3 

Me
N
—
Me
O
18
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
HALOGEN DERIVATIVES
Classification
Aliphatic Unsaturated Aromatic

CH2 =CH–Cl (Vinyl)
CH2 =CH–CH2–Cl (Allyl)
IR
Saturated
(Benzyne) Side chain
CH3–CH2–CH2–Cl (1°)
Monohalogen CH3–CH–CH3 (2°) CH2–Cl
Cl
Cl NO2 SN1/SN2
.S CH3
CH 3–C–CH3 (3°) (SNAR)
Cl
Cl Cl
CH3–CH (gem) (geminal)
dihalogen Cl
CH3–CH–CH (Vic) (Vicinal)
Cl Cl
.J
CH 2–CH2–CH 2 (Isolated)
Cl Cl
Polyhalogen CHCl 3 (Chloroform)

N
CCl4 (Carbon tetrachloride pyrene)
General Method of Preparation Br2

(1) Form alkanes _ _ _ _ _ _
h
XX Br2
R—H  R—X + H—X Q.2 CH 3—CH—CH 2—CH 3
h hv
X2 = Cl2 or Br2 CH3 Cl2
---- % of 3°
Cl2 = Non – Selective ; Br2 = Selective hv mono-chloroproduct
X2  F2 and X2  I2 Cl2/ h
F2 = uncontrollable ; I2 = reversible CH3 Monochloro
Q.3
Cl2 Br2/ h
Q.1 % =_ _ _ + % = _ _ _ Monobromo
h
(2) From alkenes
R
1 
: R2 : R3  1: 3.8 : 4.5
R—CH = CH2
HX
R— CH —CH3
CCl4 |
X
19
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
: Markownikoff addition; Classical carbocation NBS 
CH3 — CH = CH2  CH2 — CH = CH2
HBr |
R — CH = CH2 R—CH2—CH2—Br
R – O – OR Br
Anti – markownikoff addition peroxide effect
or Kharash effect
Q.1 HCl Mechanism:–

C H 3— C H = C H 2 A O O
CCl4
HCl(R–O–OR) HBr(R–O–OR)
HBr/CBr4 C C
h  
B (1) N–Br  N + Br
D
C
C C
Q.2 Write mechanism:– O
CCl3 O
IR
CCl4 O
(a) 
Peroxide
C
Cl
CBr3 (2) CH2 = CH – CH2 – H + N
(b) ICBr 3
 C
Peroxide
O
I O
CCl3
(c)
.S BrCCl3

Peroxide
Br


CH2 = HC – CH2 + H–N
C
(3) Reed’s Reaction O

 
SO2Cl2 (3) CH2 = CH – CH2 + Br 
R — H   R—Cl + SO2  HCl 
h  CH2 = CH – CH2 – Br
SO2Cl2  Sulphuryl Chloride
.J
Q.1 NBS 
CH3  CH2Br
Mechanism. (free radical substitution)
O O
1. h   + SO2 + NBS  Br
Cl—S—Cl  Cl Cl—S Q.2  +
Br
N
O O
 NBS  Q.4 NBS 
Cl Q.3  
  
2. R—H + Cl  H—Cl + R +  Cl  R— Cl.
(Reaction rate is slow; selective and better Cl2
method then direct halogenation) CH3 – CH  CH2  CH2 – CH  CH2
500C
Imp. |
O Cl
C at high temperature free radical substitution

(4) NBS N–Br (N-Bromo Succinimide) and not Non-classical carbocation addition
C
(5) From alcohols
O (a) Darzen’s process
20
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
1
CH3 R—O—R
CH3 (1) Cl Cl
 R—Cl + R’—Cl + POCl3
SOCl2 P—Cl
H OH  H Cl Cl
Cl
D D Cl
+ SO2 + HCl (Retention of configuration) |
CH3 CH3 (2) R — C — R1  R — C — R1 + POCl3
SOCl2 || |
H OH .. Cl H O Cl
N
D D +
Cl Cl
P
+ SO2 + HCl (inversion of configuration) Cl Cl
Cl
OH SOCl2 Cl
A |
IR
Q.1
CH3 (3) R —C —H  R — C — H + POCl3
SOCl2 || |
.. B O Cl
N
+
Cl Cl
CH3 P
SOCl 2 Cl Cl
H .S D C Cl
Q.2 H OH Cl Cl Cl
SOCl2 (4) + P—Cl  + POCl3
Ph .. D
O
N Cl Cl Cl
(6) From ethers
R—O—R’ HI
 
(b) R—OH + Lucas Reagent (HCl/ZnCl2) (anhydrous)
HCl/ ZnCl2 R—OH + R’– I (SN2)
R—OH   R—Cl (Turbidity)
HI(Conc.)
R—O—R’  
.J
Test todistinguish1 / 2 / 3  alcohol.
R—OH + R’– I (SN1)
3  alcohol  within sec onds
 R—O—R’ HI

2  alcohol  within minutes  (excess)
 R— I + R’– I
1  alcohol 
 w i thin hrs 
N
R—OH HI 
 R—I
HI 
KBr Q.1 O CH3 
R—OH  No. Reaction
PCl3 OH + CH3 – I
(c) R—OH   R—Cl + H3PO3
(SN2)
PCl5 O HI(Conc.)
R—OH   R—Cl Q.2  
O
I + OH
i 2
+ P Cl (SN (or SN )
Cl Cl O HI(anhydrous)
2
Q.3  
(high temperature SN dominates)
PCl5 CH3 – I + OH
21
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
(7) Halide exchange Reaction Q.5 ONa + Br 
(a) Finkelstein Reaction
NaI 
Cl  I + NaCl.
acetone (2) Haloform Reaction
NaBr Br + NaCl.
acetone O
I2 /NaOH
CH2—C—H 
(b) Swartz Reaction 
NaF/DMF  R—F + NaCl.
R—Cl  O
or AgF CHI3 +
+ H—C—O— Na
(8) H.V.Z. Reaction (Hell Volhard Zelinesky) (yellow)
O O O
IR
2 NaOH/ I
RedP  CH —C—OH Q.1 C—CH3  

CH3—C—OH 
Cl 2
2
Cl O
NaOH/ I2
O Q.2 CH3—C  

O O
O
Imp H—C—OH
.S Ph—C—OH C—OH
NaOH/ I2
Q.3 C—CH3  

× × ×
(a) Hunds diecker Reaction Nucleophilic Substitution
O KCN dry. Ag2O
1. AgOH K L
R—C—OH  R — Br
2.Br2 /CCl4 /  R–C C–Ag KNO2
J A
Properties of Halogen Derivatives R’MgX
.J
B
(1) Williamson ether synthesis AgNO2 R’Na
R—ONa + R1 — Cl  I R—Cl C
,
R—O—R1 + NaCl (SN2) RCuLi
2
D
RSNa
H alc.AgNO3
E
Q.1 ONa + CH3 — Cl 
N
AgCN RONa
 
G F
Q.2 ONa + CH3 — Cl 
 
(4) Hoffmann exhaustive alkylation
Q.3 ONa + CH3 — Cl  NH3
CH3—Cl 
 
CH3
Q.4 ONa + CH2–Br  CH —N +—CH
3 3 Cl—




CH3
22
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
(5) With AgNO3(aq) & AgNO3(alc.)
Gives ppt. with
Substrate aq. AgNO3 alc. AgNO3

1. C—C—C—Cl
2. C—C—C
Cl
C
C—C—C
3.
Cl
IR
4. Cl
.S Cl
5.
Cl
6.
7. C = C — Cl
.J
8. C = C – CH2 – Cl
9. Cl
N
10. CH2–Cl
23
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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 can’t be SN1 (B) II can’t 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 :
N
(A) Ethyl ether (B) Ethanol

(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
24
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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)
N
(A) (B)
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
25
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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
IR
100%
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]
25C
 Cl
OH OH
Br CO2H OH H
(A) Both method 1 and method 2 are appropriate (A) H (B) H
H OH
.J
for carrying out this conversion
(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 Q.28 Which of the following can not give SN1 reaction
appropriate easily ?
Br Br
N
Br Br
Q.24 The major product in the given reaction
CH2Br (A) (B) (C) (D)
+ NH3 
Br
Q.29 In the given reaction :
CH2NH2 CH2NH2
O
(i ) NaN 3
(A) (B)    [X]
( ii) HOH
Br NH2
CH2Br [X] will be
(C) (D) All of these OH
N3
NH2
OH N3
(A) (B)
Q.25 In the given reaction :
Br OH
CH 3  C  CNa
    OH
Et 2 O /  (C) Mixture of (A) and (B) (D)
the products are :
26
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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
IR
S
CH3 CH3 OCH3 NO2
CH3 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–]
.S Cl
(D) rate = k[CH3Br]° [OH–]°
Q.38 Correct order of rate of hydrolysis for following
Q.32 Non-occurrence of the following reaction compounds is
Br– + CH3OH BrCH3 + OH–, is due to 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
.J
Q.33 The reactivity of 2-bromo-2-methylbutane (I), 1-
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
Q.39 Which reaction conditions (reagents) is suitable for
Me
N
H the following reaction :

KSH
Q.34 Et D 
H
?
SH H 
H – C – OH Br – C – H
(A) Me H (B) Me H
Et D Et D D D
H SH (A) Br2 / CCl4 (B) SOBr2
SH SH (C) HBr / conc. H2SO4 (D) PBr3
(C) HS Me (D) H Me Q.40 Arrange these compounds in order of increasing

Et D Et D SN2 reaction rate :
H H O
Q.35 Which reaction proceeds faster with NaI is DMSO.
CH2Cl Cl Br Cl Br
Cl
(I) (II) (III) (IV)
(A) CH3 (B) (A) III < I < II < IV (B) III < II < I < IV
(C) IV < III < I < II (D) III < IV < I < II
27
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
Q.41 The reaction of SOCl2 on alkanols to form alkyl (B) Me2C = CH – CH2 – CH2 – OH
chlorides gives good yields because (C) Me2C = CH – CH – CH2 – OH
(A) Alkyl chlorides are immiscible with SOCl2 OH
OH
(B) The other products of the reaction are gaseous
and escape out (D) CMe2
(C) Alcohol and SOCl2 are soluble in water Q.46 The major product formed in the following reaction
(D) The reaction does not occurs via intermediate is :
formation of an alkyl chloro sulphite OH
H2SO 4
CH3  
heat
CH3 CH3
Q.42
SOCl
 (A) H3C
OH Pyridine
  2
H
CH3 CH3
IR
D (A) CH3
Major product (A) is : CH3 (B)
H3C H3C
CH3 CH3
CH3 CH3
(A) H Cl (B) Cl H
D D
H (C) (D)
(C) H2C = CH2 (D) H2C = C H3C H2C
CH3 CH3
Q.43 H
.SCH3
SOCl2
OH   (A)
D
Q.47 In the given pairs, which pair represent correct
order of rate dehydrohalogenation reaction
(A) Cl <
D Cl
Major product (A) is :
CH3 CH3 (B) Cl <
(A) H Cl (B) Cl H Cl
.J
D D (C) <
H I Br
(C) H2C = CH2 (D) H2C = C (D) CH3 – CH2 – Cl < CD3 – CD2 – Cl
D
Q.44 In the given reaction : CH3
.. .
N
H D  C 2H5 O 
CH3 – CH2 – S HOH Q.48  ? Major product is :
.. – CH2 – CH2 – Br   [X] H Br C 2H5OH
[X] will be : CH3
*
(A) CH3 – CH2 – S – CH H3C H
2 – CH2 – OH (A) C=C
*
(B) CH3 – CH2 – S – CH2 – CH H CH3
2 – OH
H3C CH3
(C) 1 : 1 mixture of (A) and (B) (B) C=C
(D) 2 : 1 mixture of (A) and (B) H H
H3C CH3
(C) C=C
H2 O
Q.45 Me2C = CH – CH2 – CH2 – Cl   (X) H D
Major product of above reaction is H3C H
OH (D) C=C
(A) Me – C – CH2 – CH2 – CH2 D CH3
Me
28
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
C6H5 Me
Q.49 CH3 H  alcoholic, KOH
   A (A) H Na CH Br
OH 
  
3

Br H E2
C6H5 D
CH3 C6H5 CH3 C6H5 Me
C C SOCl2 CH ONa
(B) H OH    
3

(A) (B)
C C
D
H C6H5 C6H5 H
Me
H CH3
PCl CH ONa
C (C) H OH 
3
  
3

(C) (D) None is correct
C D
C6H5 C6H5 Me
Q.50 The rate of elimination (using EtONa) of :. H  / MeOH
IR
(D) H OH   
Br Br
Et
(I) (II) (III) Q.5 SN2 reaction will be negligible in
Br Br Br Br Br
t-Bu t-Bu
(A) I > II > III (B) I > III > II (A) (B) (C) (D)
(C) II > I > III
.S (D) III > I > II
Q.6 Rate of SN2 depends on
EXERCISE – II (A) Conc. of Nucleophile (B) Conc. of substrate

(C) Nature of leaving group (D) Nature of solvent
Q.1 SN1 & SN2 is not favourable in
Q.7 Correct statement(s) for the product(s) of following
(A) H2C = CH – Cl (B) Ph – CH2 – Cl
reaction.
(C) Ph – Cl (D) H2C = CH – CH2 – Cl
Q.2 SN1 & SN2 product are same in (excluding Cl2 / 500C
CH2 = CH – CH2 – Ph  
stereoisomer)
.J
Cl (A) Four different products are formed
(B) Two optically active products are formed
(A) (B)
(C) The optically active compound formed here
Cl
can also be made by the reaction of HCl
(C) (D) Ph – CH – CH – CH3 (D) The reaction path is free radical substitution.
N
CH3 Cl
Cl Q.8 In the given pair in which pair the first compound is
Q.3 Which of the following statements is/are true ? more reactive than second to SN2 reaction.
(A) CH3 – CH2 – CH2 – I will react more readily (A) Cl CH2Cl
than (CH3)2CHI for SN2 reactions.
(B) CH3 – CH2 – CH2 – Cl will react more readily Cl
than CH3 – CH2 – CH2 – Br for SN2 reactions. (B) Cl
(C) CH3 – CH2 – CH2 – CH2 – Br will react more
readily than (CH3)3C – CH2 – Br for SN2 reactions.
(D) CH3 – O – C6H4 – CH2Br will react more (C)
Cl Cl
readily than NO2 – C6H5 – CH2Br for SN2
reactions. Cl
Cl
(D)
Q.4 In which of the following case configuration about
chiral C* is retained :
29
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
Q.9 A gem dichloride is formed in the reaction : CH3
(A) CH3CHO and PCl5 (B) CH3COCH3 and PCl5 H
(B) CH3 – C – OH 


(C)CH2 = CH2 and Cl2 (D) CH2 = CHCl and HCl

CH3
Q.10 Match List – I with List – II for given SN2 reaction & CH3 – C = CH2 (2) Carbocation
select the correct answer from the codes given
CH3
below
Z – CH2Br + CH3O Z – CH2 – OCH3 + Br alc.KOH
(C) CH3 – CH2 – Br   
List – I List – II (relative reactivity) 
(A) H– (P) 0.1 CH2 = CH2 (3) Carbanion
(B) CH3 – (Q) 3
(C) C2H5 – (R) 1
CH3 Br
(D) CH–
(S) 100
alc.KOH / 
CH3 (D) CH3 – C – CH3  
IR
CH3
Q.11 In which product formation takes place according
CH3 – C = CH2 (4) Free radical
to Hoffmann’s rule

t–Bu O K
CH3
(A) CH3CH2 – CH – CH3

Br

(B) CH3CH2 – CH – CH3 CH3CH2OK EXERCISE – III

.S Q.1 Identify A, B, C, D, E and F in the following series
Br of reaction.
 CH3
Br2 aq.KOH Na
(C) CH3CH2 – CH – N —– CH3 OH  h
A B C
CH3 alc.KOH
CH3
NBS +C
OH D E F
(D) CH3CH2CH – CH3 

S(CH3)2 Q.2 What are the products of the following reactions?
CH3
Q.12 Which of following are correct for given reaction
(a) CH3 – C – Cl + OCH3 
.J

 CH3
N OH CH3
(b) CH3 – C – O– + CH3 – X 
(A) Major product of reaction is CH3
N
N
Q.3 Complete the following by providing the structure

CH3
of (A),(B), (C) and (D).
(B) Major product is PBr Alc.KOH
(i) CH3CH2CH2OH 
3
 (A)   (B)
N HBr NH
 (C) 
3
 (D)
(C) The reaction is thermal elimination reaction
(E1CB) Alc.KOH H / H2 O 
(D) The reaction is E2 reaction (ii) CH3CH2CH2I   (A)   (B)
SOCl2 H
  (C)  (D)
LiAlH4
Q.13 Match the List I (reaction) with List II (reaction
intermediate) and select the correct answer using
NBS Alc.KOH
the codes given below the Lists. (iii) CH3CH2CH = CH2   (A)  
Light
List I List II Li List II
alc.KOH /  HBr
(A) CF3 – CHCl2   (B)   (C)
CF2 = CCl2 (1) Transition state
CH3CHO / H2O HBr
(iv) CH3CH2MgBr    (A) 
Alc.KOH
(B)   (C)
30
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
Q.4 CH3 – CH2I reacts more rapidly with strong base in Q.12 Treatment of 2-bromobutane with hot alcoholic
comparison to CD3CH2 I KOH gives a mixture of three isomeric butenes
(A), (B) and (C). Ozonolysis of the minor product
(A), gives formaldehyde and another aldehyde in
equimolar amounts. What are the structural
Q.5 Propose a mechanism for the following reactions. formulae of (A),(B) and (C)?
OH
CH3 CH3 Q.13 A hydrocarbon C8H10 (A) on ozonolysis gives
H2O compound C4H6O2 (B) only. The compound (B)
C – Br CH3
can also be obtained from the alkyl bromide
CH3 C3H5Br (C) upon treatment with magnesium in dry
Q.6 Each of the following alcohols has been subjected
ether followed by CO2 and acidification. Identify
to acid catalyzed dehydration and yields a mixture (A), (B) and (C) and also give equations for the
of two isomeric alkenes. Identify the two alkenes in
reactions.
each case, and predict which one is the major
product on the basis of the Zaitsev rule.
IR
H3C OH EXERCISE – IV(A)
(a) (CH3)2CCH(CH3)2 (b)
Q.1 Aryl halides are less reactive towards nucleophilic
OH substitution reaction as compared to alkyl halides
OH due to [IIT 1990]
(A) The formation of less stable carbonium ion
(B) Resonance stabilization
(c)
(C) The inductive effect
(D) sp2 hybridised carbon attached to the halogen
Q.7
.S H
Give the major product (with proper explanation)
when following halogen compounds are treated
Q.2 Arrange the following compounds in order of
increasing dipole moment
Toluene
[IIT 1996]
m-dichlorobenzene
with sodium ethoxide.
CH2Br I II
(a) CH3 – CH – CHCH3 (b)
CH3 o-dichlorobenzene p-dichlorobenzene
Br CH3
III IV
(A) I < IV < II < III (B) IV < I < II < III
.J
(c) CH3
(C) IV < I < III < II (D) IV < II < I < III
Cl
Q.3 (CH3)3CMgCl reaction with D2O produces :
[IIT 1997]
Q.8 2-chloro-3-methylbutane on treatment with
alcoholic potash gives 2-methylbutene-2 as major (A) (CH3)3CD (B) (CH3)3OD
product. (C) (CD3)3CD (D) (CH3)3OD
N
Q.9 KCN reacts with R – I to give alkyl cyanide, while Q.4 The order of reactivity of the following alkyl halides
AgCN results in isocyanide as major product. for a SN2 reaction is : [IIT 2000]
Q.10 Predict the product(s) and write the mechanism of (A) RF > RC > R – Br > R – I
each of the following reactions. (B) R – F > R – Br > R – Cl > R – I
HI (1mole) excess HI (C) R – Cl > R – Br > RF > R I
(i) 
(ii) 
O O (D) R – I > RBr > R – Cl > R – F
Q.5 Identify the set of reagents / reaction conditions ‘X’
Q.11 Convert and ‘Y’ in the following set of transformation :
(i) CH2 – CH3  CH = CH2 CH3 – CH2 – CH2Br X
 Product
Y
 CH3 – CH –CH3 [IIT 2002]
(ii) CH3CH2CH = CH2 CH3CH2CH2CH2NH2
Br
(iii) CH3CH2CH = CH2 CH2 = CH – CH = CH2 (A) X = dilute aqueous NaOH, 20°C; Y = HBr /
(iv) OH – CH2 – CH2CH = CH2  acetic acid, 20°C
O
31
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
(B) X = concentrated alcoholic NaOH, 80°C; Y = Q.9 The major product of the following reaction is
HBr / acetic acid 20°C [IIT 2008]
Me Br
(C) X = dilute aqueous NaOH, 20°C; Y =  
Br2/CHCl3, 0°C PhS Na
F 
dimethylformamide
(D) X = concentrated alcoholic NaOH, 80°C; Y =
Br2 / CHCl3, 0°C
Q.6 CH3MgBr + Ethyl ester  which can be formed as NO2
product [IIT 2003] Me SPh Me SPh
(excess) F F
CH2CH3
CH3
(A) (B)
(A) HO CH2CH3 (B)
HO CH2CH2CH3
CH2CH3 CH2CH3 NO2 NO2
Me Br SPh
IR
Me
CH2CH3 CH3
SPh SPh
(C) HO (D) HO (C) (D)
CH2CH3 CH3
CH3 CH3
NO2 NO2
Q.7 Match the following [IIT 2006]
HBr
Column I
.S Column II Q.10 In the reaction OCH3 
 the products are
(A) CH3 – CHBr – CD3 on (P) E1 reaction
(A) Br OCH3 and H2 (B) Br and CH3Br
treatment with alc.
KOH gives (C) Br and CH3OH (D) OH and CH3Br
CH2 = CH – CD3 as a [IIT-JEE 2010]
Q.11 The total number of alkenes possible by
major product dehydrobromination of 3-bromo-3-cyclopentylhexane
(B) Ph – CHBr – CH3 reacts (Q) E2 reaction using alcoholic KOH is [IIT-JEE 2011]
Q.12 The major product of the following reaction is
faster than O
.J
C [IIT-JEE 2011
Ph – CHBr – CD3 NH
(i) KOH
C (ii) Br CH2Cl
(C) Ph – CD2–CH2Br (R) E1 cb reaction
O
on treatment with O O
C2H5OD/C2H5O– C C
(A) Br (B) N CH2Cl
N
N–CH2
gives Ph – CD = CH2 C C
as the major product. O O
O
(D) PhCH2CH2Br and (S) First order reaction O
C
C
PhCD2CH2Br react with N
(C) N (D) C
same rate O–CH2 Br O CH2 Cl
Q.8 The reagent(s) for the following conversion,
[IIT 2007] [II
Br
?
Br  H H
(A) alcoholic KOH
(B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2
(D) Zn/CH3OH
32
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
EXERCISE – IV(B) C6H5
Alcoholic KOH
Q.1 Identify the major product in the following
Q.4 (a) C6H5CH2CHCl  Heat
 A + B Write
reactions : [IIT 1993] structures of (A) and (B).
Cl HI( excess )
(b) (CH3)2CHOCH3    A + B Write
Heat
alcoholic
(i) C6H5 – CH2 – CH – CH3    ?
KOH  structures of A and B. [IIT 1998]
HBr
 ? Q.5 Complete the following reaction with appropriate
structures of products / reagents. [IIT 1998]
(ii) C6H5COOH + CH3Mg I ? + ?
CH =CH2
Br2 (i)NaNH (3equi .)
 (A)   2 
 (B)
Q.2 An alkyl halide X of formula C6H13Cl on treatment (II) CH3 I
with potassium tertiary butoxide gives two isomeric
alkenes Y and Z (C6H12). Both alkenes on Q.6 What would be major product ?[IIT-JEE 2000]
hydrogenation give 2, 4-dimethylbutane. Predict CH3
IR
the structures of X, Y and Z. [IIT 1996] CH3 – C – CH2Br 2 
5C H OH
 ?

CH3
Q.3 Predict the structure of the intermediates/products
in the following reaction sequence- [IIT 1996]
Br
H Ph Na I
 C
MeO .S H Acetone
Ph
.J
N
33
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
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
(iv) A, CH3CH2CHOHCH3; B, CH3CH2CHBrCH3; C, CH3CH = CH – CH3
Q.4
.S
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
34
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360
Br
alc . KOH
Q.11 (5) CH 3—CH 2 — C — CH 2—CH 2—CH 3   CH 3—CH = C — CH 2—CH 3 (Cis/Trans) + CH 3—CH 2 — C — CH 2—CH 3
CH 3—CH 2 — C = CH — CH 2—CH 3 (Cis/Trans)
Q.12 (A)
O O
C C
–
N — H + OH :N: + H2O
C C
O O
IR
Br— —CH2—Cl O
C
N—CH2— —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
N
CH3
Br
CH – CH2Br C  CNa CCCH3
NaNH (liq.)
2 CH I
3
Q.5 (A)    
    (B) 3
CH3
Q.6 CH3 – C = CHCH3
35
-------------------------------------------------------------------------------------------------------
Mob. No. : 9214233360

Halogen Derivative Module PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Halogen Derivative Module PDF

Uploaded by

Copyright:

Available Formats

ETOOSINDIA

INDIA’S NO. 1 ONLINE COACHING

IIT-JEE ChEmistry by N.J. sir

Polar protic Solvent:– .. 

(g) H3O H2O

Rule 3:- Types of nucleophilic substitution.

O (2) rate is directly proportional to stability of

Q.1 Compare the rate of SN1 reaction:- CH3OH

t–Bu ( O , F & CH3 – O cannot be substituted

strong bars & weak leaving groups)

2. SN2 reaction nucleophilic substitution

Characteristics Q.3 1– Bromobicyclo [2.2.1] heptane is extremely

2. CH3 — CH2 — CH2 — CH2 — Cl

CH3 — CH — CH2 — Cl Q.4

Write the products of SN2 reaction:–

(4) CH2 = CH — CH2 — Cl

Explain mustard gas hydrolysis at a very high

Q.20 R — X + Reagent  Product

(B) (1)  CH3 3 CCl  H2O   CH3 3 COH  HCl

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

Ph— CH2—CH2—X .J SN1(Solvolysis)

E2 (formation of conjugated double. Bond)

KSH  (8) NaH 

   (b) O— + CH3 — Br 

(14) Major Product of reactions I

Cl (16) Give major product (E1, E2, SN1 or SN2)

CH3OH (b) CH3 — CH2 — CH2 — Br

Q.6 CH3 — N — CH2 — CH2 — CH3

Aliphatic Unsaturated Aromatic

Polyhalogen CHCl 3 (Chloroform)

CCl4 (Carbon tetrachloride pyrene)

General Method of Preparation Br2

Q.1 HCl Mechanism:–

(3) Reed’s Reaction O

C at high temperature free radical substitution

Substrate aq. AgNO3 alc. AgNO3

(A) Ethyl ether (B) Ethanol

For the given reaction

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

H the following reaction :

(C) HS Me (D) H Me Q.40 Arrange these compounds in order of increasing

EXERCISE – II (A) Conc. of Nucleophile (B) Conc. of substrate

(C)CH2 = CH2 and Cl2 (D) CH2 = CHCl and HCl

Q.3 Complete the following by providing the structure

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

– C  N : structure with lone pair on N thus R attacks on N atom and R – N  C is formed.

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

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

You might also like