ALKYL HALIDES & ARYL HALIDES

Structure and Nomenclature

Alkyl halides are commonly designated by the formulas R-X, where R is any simple alkyl or
substituted alkyl group. For example,
CH3
 Br
CH3–C–CH3 H2C = CH - CH2 Br

Allyl bromide Cyclohexyl bromide
Cl 3-bromo-1-propene
tert-Butyl chloride
2-chloro-2-methylpropane

CH3

CH3-CH-CH3 CH3-CH-CH2-Cl CH3-C-CH2Br
  
Br CH3 CH3
Isopropyl bromide Isobutyl chloride Neopentylbromide
2-bromopropane 1-Chloro-2-methyl 1-bromo-2,2-dimethylpropane
propane
H2C=CH-CC-CH=C-CH3 CH2Cl O2N CH2Br

Br p-nitrobenzylbromide
Benzyl chloride
6-Bromo-1,5-heptadien-3-yne
H2C=CHCl CH2-CH2 CH2-CH2
Vinylchloride    
Br Br OH Br
1, 2-dibromoethane Ethylene
bromohydrin
H Cl 2-bromoethanol

Cyclohexyl chloride

Substituted alkyl halides undergo, of course, the reactions characteristic of their other
functional groups nitration of benzyl chloride, oxidation of ethylene bromohydrin, addition to
allyl bromide but as halides they react very much like ethyl or isopropyl or-tert-butyl halides.
Compounds in which halogen atom is attached directly to an aromatic ring (aryl halides,
e.g., bromobenzene) differ so much from the alkyl halides in their preparation and properties
that they will be discussed separately.
Illustration 1: The heterolytic bond dissociation energy of C – Cl bond in vinyl chloride 207
kcal/mol as compared to 191 kcal/mol in the case of C – Cl bond in ethyl
chloride. Given explanation for this observation is
Solution: CH2  CH  Cl
Vinyl chloride

XX – 
CH2 = CH – Cl XX  CH2 – CH = Cl
XX XX

As we can see that C = Cl bond is formed in vinyl chloride so its bond

dissociation energy 207 kcal / mol as compared 191 kcal/mol for C – Cl bond.

Rankers-JEE by Saurabh Maurya

Physical Properties

Because of greater molecular weight, haloalkanes have considerably higher boiling points
than alkanes of the same number of carbons. For a given alkyl group, the boiling point
increases with increasing atomic weight of the halogen, so that fluoride has the lowest
boiling, and iodide the highest boiling point. In spite of polarity alkyl halides are insoluble in
water, probably because of their inability to form hydrogen bonds. They are soluble in typical
organic solvents.

Preparation
1. From Alcohols (Replacement of OH by X)
PX3
ROH R-X
or HX
Examples :
Conc . HBr
CH3CH2CH2OH CH3CH2CH2Br
or
NaBr,H2SO4


PBr3
-CH-CH3    -CH-CH3
| |
OH Br
P I2
CH3 CH2 OH   CH3CH2I
ROH + PCl5  RCl + POCl3 + HCl
ROH + SOCl2  RCl + SO2 + HCl
2. Halogenation of Hydrocarbons
X
R-H 2
 R-X + HX
h
Examples :
CH3 CH3
| |
CH3 –C–CH3  CH3–C–CH2Cl
Cl 2 , heat or light

| |
CH3 CH3
CH3 CH3 CH3
| Cl2 | |
CH3–CH–CH3 light, 25o CH3–CH–CH2 Cl + CH3–C–CH3
|
Cl
major minor

CH3 CH3 CH3

| | |
Br2
CH3–CH–CH3 light, 146 o CH3–CH–CH2Br and CH3–C–CH3
|
Br
trace over 99%

Rankers-JEE by Saurabh Maurya

3. Side Chain Halogenation of Alkylbenzenes
CH3 CH2X

X2, h a benzyl halide

CH3 CH X2

2X2, h a benzal halide

CH3 CX3

3X2, h a benzotrihalide
CH2 CH3 CH-CH3
Br2, h
Br
heat
1-Bromo-1-phenylethane
(only product)
CH3 CH2Br
Br2 , reflux ,
light
Benzylbromide

4. Addition of Hydrogen Halides to Alkenes (Discussed under alkenes)

| | | |
–C=C– HX –C-C–
| |
H X

5. Addition of Halogens to Alkenes and Alkynes

X
| | | |
 C  C    C C
X2

| |
X
(Vicinal dihalide)

X X
| |
2X2 –C-C–
–CC–
| |
X X

6. Halide Exchange

R-X + I- acetone
  RI + X-

An alkyl iodide is prepared often from the corresponding bromide or chloride by

treatment with a solution of sodium iodide in acetone ; the less soluble bromide or
sodium chloride precipitates from the solution and can be removed by filtration.

Rankers-JEE by Saurabh Maurya

 A halide ion is an extremely weak base. Its reluctance to share its electrons is shown
by its great tendency to release a hydrogen ion, that is, by the high acidity of the
hydrogen halides.

When attached to carbon, halogen can be readily displaced as halide ion by other,
stronger bases. These bases have an unshared pair of electrons and are seeking a
relatively positive site, i.e., are seeking a nucleus with which to share their electrons.

Alkyl halides are nearly always prepared from alcohols, which are available
commercially or are readily synthesized. Although certain alcohol tend to undergo
rearrangement during replacement of -OH by -X, this tendency can be minimized by
use of phosphorus halides.

Certain halides are best prepared by direct halogenation. The most important of
these preparations involve substitution of -X for the unusually reactive allylic or
benzylic hydrogens.
| | | | | |
–C–C=C– –C–C=C–
| |
H X
Allylic hydrogen An allyl halide

| |
–C– –C–
| |
H X
A benzyl halide

Basic, electron rich reagents are called nucleophilic reagents. The typical reaction
of alkyl halides is nucleophilic substitution.

Nu- + -
R-Nu + X-
or + R :X  or
Nu: [R:Nu]+
Nucleophile + substrate Product + Leaving Group

The order of reactivity is RI>RBr>RCl>RF.

Reactions of Alkyl Halides

1. Nucleophilic Substitution

RX + -OH  ROH + X- Alcohol

” + H2O  ROH Alcohol
” + -OR'  R OR' Ether
(Williamson synthesis)
” + -CCR'  R-CCR' Alkyne
” + I-  RI Alkyl iodide

Rankers-JEE by Saurabh Maurya

 ” + -CN  RCN Nitrile
o
||
” + R'COO-  R' c -OR Ester
” + :NH3  RNH2 Primary amine
” + :NH2R'  RNHR' Secondary amine
” + :NH R'R"  RNR'R'' Tertiary amine
” + SH  RSH
-
Thiol (mercaptan)
” + :SR  RSR'
'
Thioether (sulfide)
RX + ArH + AlCl3  Ar R Alkyl benzene
(Friedel Craft reaction)

CO2C2H5 CO2CH2CH3 (Malonic ester synthesis)

-
RX+ CH R-CH
CO2C2H5 CO2CH2 CH3

COCH3
-
(Acetoacetic ester synthesis)
RX+ CH CH3COCH CO2C2H5
CO2C2H5 |
R
[We can see that alkyl halides can be transformed into a variety of other functional
groups. We will study the reactions separately, but they have been summarized
here.]

2. Dehydrohalogenation

Elimination
| | | |
 C  C    C = C 
base

| |
H X

3. Preparation of Grignard reagent

dry
RX + Mg R Mg X
ether

4. Reduction

RX + M + H+  RH + M+ + X-
Examples :

(CH3)3C Cl Mg
 (CH3)3C MgCl D

2O
 (CH3)3CD

Rankers-JEE by Saurabh Maurya

Characteristic Reaction Chart For Alkyl Halides

1
RCH2 CH2 OH RCH2 CH2 OR RCH2 CH2MgX
aq.
KOH PX3 R'OK Mg
'
R'X RCH2 CH2 R
Na
KNH2 Redn.
RCH2 CH2 - NH2 R-CH2-CH2-X RCH2CH3
X2,h
KSH KNO2
KOH
HX alc. AgCN
RCH2 CH2SH KCN
RCH2 CH2 NO2
RCH=CH2 RCH2 CH2 NC
R-CH2 CH2-CN

Nucleophilic Displacement By SN1 and SN2 Mechanisms

SN1 SN2

Steps Two : (1) R:X Slow


 R+ + X- One : R:X + Nu-  RNu
Carbonium ion + X-
or R:X + Nu  RNu+
-
(2) R+ + Nu- fast
 RNu or X
R+ + :Nu  RNu+
Rate =K [RX] (1st order) =K[RX] [:Nu-] (2nd order)

— —
Nu C X
TS of slow step C+......X-

Stereochemistry Inversion and racemization Inversion (backside

attack)
Molecularity Unimolecular Bimolecular
Reactivity
structure of R 3o> 2o> 1o> CH3 CH3> 1o> 2o> 3o
Determining Stability of R+ Steric hindrance in R
factor group
Nature of X RI> RBr> RCl> RF
Solvent effect on rate Rate increases in polar solvent RI> RBr> RCl> RF
with Nu- there is a large
rate increase in polar
aprotic solvents.
Effect of nucleophile Rate depends on
nucleophilicity
I- > Br- > Cl- ; RS- > RO-
Catalysis Lewis acid, eg. Ag+, AlCl3, ZnCl2 None
Competition reaction Elimination, rearrangement Elimination

Rankers-JEE by Saurabh Maurya

The SN2 Reaction

Mechanism and Kinetics

The reaction between methyl bromide and hydroxide ion to yield methanol follows second
order kinetics; that is, the rate depends upon the concentrations of both reactants :

CH3Br +-OH  CH3OH + Br-

rate = K [CH3Br] [OH–]

The simplest way to account for the kinetics is to assume that reaction requires a collision
between a hydroxide ion and a methyl bromide molecule. In its attack, the hydroxide ion
stays far away as possible from the bromine; i.e. it attacks the molecule from the rear and
begin to overlap with the tail of the sp3 hybrid orbital holding Br. The reaction is believed to
take place as shown:

— + Br—
HO: — C Br — HO C
HO C Br
(Inversion)

In the T.S. the carbon is partially bonded to both -OH and -Br; the C-OH bond is not
completely formed, the C-Br bond is not yet completely broken. Hydroxide has a diminished
-ve charge, since it has begun to share its electrons with carbon. Bromine has developed a
partial negative charge, since it has partly removed a pair of electrons from carbon. At the
same time, of course, ion dipole bonds between hydroxide ion and solvent are being broken
and ion-dipole bonds between bromide ion and solvent are being formed.

As the -OH becomes attached to C, 3 bonds are forced apart (120o) until they reach the
spoke arrangement of the T.S ; then as bromide is expelled, they move on to the tetrahedral
arrangement opposite to the original one. The process has often been likened to the turning
inside out of an umbrella in a gale.

The SN2 Reaction

Stereochemistry

Both 2-bromo-octane and 2-octanol are chiral.

C6H13 C6H13

H Br H OH

H3C H3C
(-)-2-Bromooctane (-)-2-Octanol

The (-) bromide and the (-) alcohol have similar configurations, i.e. -OH occupies the same
relative position in the (-) alcohol as -Br does in the bromide.

Rankers-JEE by Saurabh Maurya

When (-)-2-bromooctane is allowed to react with sodium hydroxide under SN2 conditions,
there is obtained (+)-2-octanol.

C6H13
C6H13
NaOH
H Br HO H
SN2
H3C
H3C
(-)-2-Bromooctane (+)-2-Octanol

In Fisher projection the above reaction can be represented as follows :

C6H13 C6H13
NaOH
H Br HO H
SN2
CH3 CH3

We see that -OH group has not taken the position previously occupied by -Br; the alcohol
obtained has a configuration opposite to the bromide. A reaction that yields a product
whose configuration is opposite to that of the reactant is said to proceed with
inversion of configuration.

The SN2 Reaction

Reactivity

In SN2 reactions the order of reactivity of RX is CH3X>1o>2o>3o.

Differences in rate between two SN2 reactions seem to be chiefly due to steric factors (bulk
of the substituents) and not due to electronic factors i.e. ability to withdraw or release
electrons.

Relative Reactivity Towards I-

H H CH3 CH3
| | | |
H-C-Br > CH3-C-Br > CH3-C-Br > CH3-C-Br
| | | |
H H H CH3
Methyl (150) Ethyl (1) Isopropyl (0.01) Tert-butyl (0.001)

H CH3 H
| | |
-C-Br > -C-Br > -C-Br
| | |
H H CH3

Rankers-JEE by Saurabh Maurya

The SN1 Reaction

Mechanism and Kinetics

The reaction between tert-butyl bromide and hydroxide ion to yield tert-butyl alcohol follows
first order kinetics; i.e., the rate depends upon the concentration of only one reactant,
tert-butyl bromide.
CH3 CH3
| |
CH3-C-CH3 + - OH CH3-C-CH3 + Br—
| r. d. s 
Br

CH3 CH3
| |
CH3-C-CH3 + - OH fast CH3-C-CH3
 |
OH

Rate = K[RBr]
SN1 reaction  follows first order kinetics.
Stereochemistry

When (-)-2-bromo octane is converted into the alcohol under conditions where first-order
kinetics are followed, partial racemization is observed.

The optically active bromide ionizes to form bromide ion and the flat carbocation. The
nucleophilic reagent then attaches itself to carbonium ion from either face of the flat ion.

It the attack were purely random, we would expect equal amounts of two isomers; i.e. we
would expect only the racemic modification. But the product is not completely racemized, for
the inverted product exceeds its enantiomer.

We can say in contrast to SN2 reaction, which proceeds with complete inversion; an SN1
reaction proceeds with racemization though may not be complete.
OH

— C
R' R" OH (a)
R sp2
R attack R R' R" Both enantiomers may be
from top
C+ R" (Inversion) formed in equal amounts
C R' (b) or one may exceed the
Br
attack from
R R' R" others.
bottom
—
C
OH
OH
r.d.s  formation of carbonium ion. Retention.

Rankers-JEE by Saurabh Maurya

Reactivity of an alkyl halide depends chiefly upon how stable a carbonium ion it can form.

In SN1 reactions the order of reactivity of alkyl halides is Allyl, benzyl >3o>2o>1o>CH3 X.

Aryl Halides

Aryl halides are the compounds that contain halogen atom directly attached to the benzene
ring. They have general formula ArX.

Cl Cl Cl Cl
| | | |

NO2
| |
NO2 NH2
Chlorobenzene m-chloronitro benzene p-chloronitro benzene p-chloro aniline

Any halogen compound that contains a benzene ring is not classified as aryl halide. e.g.
Benzyl chloride is not an aryl halide, but is a substituted alkyl halide.

Exercise 1: C7H7Cl has four isomers A1, A2, A3 and A4

A4   Benzene, Identify A1, A2, A3 and A4
I ) KMnO 4
II ) Soda lim e, 

Preparation methods of Aryl halides

Halogenation

Ar – H + X2    Ar – X + HX
Lewis acid
((X = Cl, Br)

For introducing only the halogen at para position, the Lewis acid thallium acetate is used.

NH – CO – CH3 NH – CO – CH3
| |
Br
Tl(OAC)3
Acetanilide |
Br

From diazonium salts


N2 Cl
|
Ar – H H  Ar – NO2 
HNO3
2SO4
 Ar – NH2 
reduction
Sn/HCl

NaNO 2
HCl

0-5°
Benzene diazonium chloride

Rankers-JEE by Saurabh Maurya

 
N2Cl F
| |
HBF4
(Schiemann reaction)


N2Cl Cl
| |
CuCl
(Sandmeyer reaction)

 Cl
N2Cl |
|
Cu Powder (Gatterman reaction)
+HCl


N2Cl– I
| |
KI
heat

Illustration 1: Prepare p-chlorotoluene from p-nitrotoluene

Solution: NO2 NH2 N2+Cl– Cl

 
Sn / HCl
  
NaNO2 HCl

CuCl

0 5 C

CH3 CH3 CH3 CH3

Exercise 2: Prepare p-chlorobenzoic acid from p-chloronitrobenzene

Properties of Aryl halides

Reactivity

Unlike alkyl halides, aryl halides are less reactive towards Nucleophilic substitution
reactions, this can be attributed to their electron release via resonance.
 
Cl Cl Cl Cl  Cl
| | || H || H ||

H
I II III IV V

Structures III, IV and V stabilise chlorobenzene molecule and give a double bond character
to the carbon-chlorine bond. Now because of this the carbon-chlorine bond has more
strength and hence aryl halides are more stable towards Nucleophilic substitution reactions.
In Alkyl halides the carbon atom attached to halogen is sp3 hybridized and in aryl halides it is
sp2, hybridized, as sp2 hybridized carbon is more electronegative it does not permit the
chlorine atom to get displaced with the bonded pair of electrons.

Rankers-JEE by Saurabh Maurya

Nucleophilic Substitution reactions

Aryl halides undergo Nucleophilic substitution reactions when a strong Electron withdrawing
group is present on the benzene ring. Electron withdrawing groups activate the benzene ring
towards nucleophilic substitution in aryl halides whereas Electron donating groups
deactivate the ring.

Mechanism: Bimolecular displacement mechanism

Cl Nu Cl Nu Cl Nu Cl Z Cl
|
H H

|
Fast H
Z
|
–
+ Cl

Any factor that stabilizes the carbanion will increase the rate of Nucleophilic substitution
reaction by dispersing the charge present on resonating structures. An electron withdrawing
group present at meta position does not activate the ring as much as it does from ortho and
para position. This can be known by looking at following resonance structures.
Z Cl Z Cl Z Cl

NO2 NO2 NO2 (Meta)

Z Cl Z Cl Z Cl

(Para)

NO2 NO2 NO2

Elimination – addition mechanism

In the absence of an electron withdrawing group, nucleophilic substitution takes place in
presence of very strong bases, but the mechanism is entirely different from what we have
seen in bimolecular nucleophilic substitution reactions. These reaction proceed by a
mechanism called benzyne mechanism.
X X
+ NH2  + NH3

X
 +X
Benzyne
NH2 NH2
+ NH2  + NH3  + NH2

Rankers-JEE by Saurabh Maurya

Benzyne is a symmetrical intermediate and can be attacked by nucleophile at both the
positions.

14 Cl 14 NH2 14
NH2
 +
NH2

Isotopic labelling confirmed that there is an equal chance of abstraction from both carbons.
An aryl halide which does not contain alpha hydrogen with respect to halogen does not
undergo this reaction. In the reactions involving Benzyne intermediates, two factors affect
the position of incoming group, the first one is direction of aryne formation. When there are
groups ortho or para to the leaving group, then, the following intermediates should be
formed.

Z Z Z Z
| | | |
X
NH NH2

2

Intermediate
|
X

when a meta group is present, aryne can form in two ways, In such cases

Z Z Z
| | |
NH2–
 or
X

more acidic hydrogen is removed, i.e., an electron attracting ‘Z’ favours removal of ortho
hydrogen while an electron donating ‘Z’ favours removal of para hydrogen.

Illustration 2: Predict the products in the following reactions.

Cl
Cl
a) KNH2
NH3
A

Cl

KNH2
b) B
NH3

Cl
Cl

c) KNH2
NH3 C
Cl

Rankers-JEE by Saurabh Maurya

Solution: a) Cl Cl Cl
| Cl | |
 
NH2
NH2
b) Cl Cl Cl
| | |
 
NH2
| |
Cl NH2
c) Cl Cl Cl
| | |
 
NH2
Cl NH2

Exercise 3: Find the product in the following reaction

Cl

+ CH3CN 3   Product

NH , NaNH2
(a)

Cl
Me OMe
(b) KNH2
 Product
Liq. NH 3

Answers to Exercise
Exercise 1: A4 - benzyl chloride

Exercise 2: i) Sn/HCl, ii) NaNO2 + HCl, 0 – 5C, iii) CuCN (iv) H2O

Exercise 3: No reaction

Rankers-JEE by Saurabh Maurya

Solved Problems
Subjective

Problem 1: Identify A,B,C,D,E and F in the following series of reaction.

Br2 aq.KOH Na
 A    B  C
hv
alc. KOH
NBS C
D  
 E  F

Solution: Br OH ONa
Br2
 aq.KOH
hv   
 Na

A B C
alc. KOH

NBS
 

Br
ONa Br

Williamson
    —O—
+ synthesis
C E F

Problem 2: Give the major product (with proper explanation) when following halogen
compounds are treated with sodium ethoxide.
CH2Br
(a) CH3—CH—CHCH3 (b) CH3
Br CH3

(c)
—CH3

Cl

Solution: ) CH —CH—CH—CH 
slow

 CH3—CH—CH—CH3
3 3
S 1 +
N
Br CH3 CH3
2° carbonium ion (A)
OC2H5

1,2 hydride shift O C2H5
       CH3—CH2—C—CH3   CH3—CH2—C—CH3

CH3 CH3
3° carbonium ion major

Rankers-JEE by Saurabh Maurya

 no shift O C2H5
A    ,   CH5CH——CH—CH3

OC2H5 CH3
minor
Note: There can be elimination from 2° and 3° carbonium to give alkene.
H 
CH3—CH—CH—CH
 3   CH3—CH=C—CH3

CH3 CH3
(A) (due to elimination)
slow —CH3
—CH3  


2° carbonium ion (A)
Cl

(A)
1,2 hydride shift
     
  —CH3
3°carbonium ion (B O C 2 H5
O C2H5
(B)   CH3
OC2H5 —CH3
major

OC2H5
minor
CH2Br slow CH2
CH3 CH3
1° carbonium
1,2 methyl shift CH2CH3
O C2H5 CH2CH3
 
(1° carbonium on)
OC2H5
major

Problem 3: What are the products of the following reactions?

CH3
(a) CH3CH2—C—Cl + O CH 
3

CH3
CH3

(b) CH3—C—O– + CH3—X

CH3

Solution: CH3 CH3

(a) CH3—C—Cl +O CH3  CH3—C=CH2

CH3

Rankers-JEE by Saurabh Maurya

 O CH3 (nucleophile) can't attack 3° carbon having high electron - density
hence elimination takes place giving.
CH3 CH3
–
(b) CH3—C—O + CH3X  CH3—C— OCH3

CH3 CH3
Nucleophilic attack on methyl carbon is possible giving ether (Williamson
synthesis).

Problem 4: Heating many alkyl chlorides or bromides in water effects their conversion into
alcohol through SN1 reaction. Order each of the following sets compounds with
respect to solvolytic reactivity.
Br
Br
(a) Br Br
I II
III
Br
(b) Br
Br
I II III
Cl Cl
Cl
(c)

Solution: (a) I  II  III

(b) III  II  I
( —CH2CH2 is more electron repelling than —CH2)

(c) III  I  II (allylic)

Order is based on stability of carbocation, formed as the intermediate, which
is
1°  2°  3°  allylic

Problem- 5: When alkyl halides are treated with aqueous AgNO3, silver halide precipitate
and an alcohol is formed. From what you know about the S N1 reaction, propose
a mechanism for the following conversion.

Ag
I 

—OH
H2O and OH

Solution: Step I:
CH2 CH 2
Ag
I  
1° carbonium ion
Step II:

Rankers-JEE by Saurabh Maurya

 CH 2 CH3
H  1,2 hybride shift 
 
I II
H2O
CH3
OH
or
Step II:

CH2
alkyl shift
   H2O
 
(ring expansion)  —OH

Problem 6: 2-Bromopentane, when treated with alcoholic KOH yields a mixture of three
alkenes A,B and C. Identify A,B and C. Which is predominant?
(Assume reaction proceeds through E2 mechanism)

Solution:
C2H5 O K 
CH3—CH2—CH2—CH—CH3  CH3—CH2—CH2—CH=CH2
(alcoholic KOH)
1-pentene (A)
Br and CH3—CH2—CH=CH—CH3
2-pentene
cis (B) and trans (C)
By Saytzeff rule, substituted alkenes are more stable, hence B or C is
predominant than A. Out of cis and trans, trans is more stable. Hence C is
predominant.

Problem 7: Identify end product of the following

CBr4 + MeLi +  ?

Solution: CBr4 + MeLi  MeBr + LiCBr3

(halogen-metal exchange)
LiCBr3  LiBr +:CBr2
Br
+ :CBr2 
electrophilde
Br
7,7-dibromo [4,1,0] bicycloheptane
(carbene)

Problem 8: Vinyl chloride does not give SN reaction but allyl chloride gives. Explain.

Solution: In vinyl chloride C—Cl bond is stable due to resonance (as in

chlorobenzene).
– 
CH2=CH——Cl  CH2—CH=Cl

Rankers-JEE by Saurabh Maurya

 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, SN reaction is easier since allyl carbonium ion formed after
removal of Cl– is tabilised by resonance.

CH2  CH  CH2Cl  CH2  CH  C H2  Cl 
allyl carbonium ion
 
CH2  CH  C H2  C H2  CH  CH2

Problem 9: When CH3—CH=CH–CH2Cl reacts with alcoholic KCN, a mixture of isomeric

products is obtained. Explain.

Solution: It can undergo SN1 and SN2 reaction. By SN2 reaction only one product is
formed . But by SN1 reaction, intermediate is carbonium ion.
S 2 Cl
CH3—CH=CH—CH2Cl + CN– N CH3—CH=CH—CH2
slow CN
slow SN1 fast
 CH3—CH=CH—CH2CN
CH3—CH=CH—CH2CH3—CH—CH=CH2 (A)
CN– CN–
CH3—CH=CH—CH2CN; CH3—CH—CH=CH2

CN
(A)
(B)
Thus we get two isomeric products suing SN1 reaction.
Problem 10: C4H8Cl2 (A) on hydrolysis forms C4H8O (B) which forms an oxime, but does not
reduce Fehling solution. B also gives iodoform test. Identify A and B and
explain reactions.
Solution: (A) by hydrolysis forms (C) replacing two —Cl by one O. Thus A has two Cl
atoms at same carbon i.e., gem positions.
We assign therefore following structures and compare their properties to
match the given properties.
CH3 CH3CH2CH2CHCl2 CH3CH2CCl2CH3
CHCHCl2
CH3 I II III
H O H2O
H2O 2

CH3 CH3CH2CH2CHO
CHCHO CH3CH2COCH3
CH3
I II III
I II III
(a) Formation of oxime is possible is possible is possible
(b) Fehling's solution is reduced is reduced is not reduced
(c) Iodoform test is not given is not given is given
Thus III is the only correct structure.
Cl

CH3—CH2—C—CH3

Cl

Rankers-JEE by Saurabh Maurya

Objective

Problem1: The following method cannot be considered suitable for the preparation of
alkyl halide:
(A) Halogenation of alkane (B) ROH and PX3
(C) ROH and HX (D) Alkene and HX

Solution: High temp. 400°

(1) R – H + X2  R – X + HX
UV light

This is most drastic method as it required High temperature or catalyst

CuCl2, FeCl3, FeBr3 etc.
(2) ROH + PX3  3RX + H3PO3
(3) ROH + HX  R – X + H2O
H
|
(4) R – C = C – H + HX  R – C = C – H
| | | |
H H X H
(2), (3) & (4) are very feasible process
 (A)
Problem 2: Sec. Butyl chloride will undergo alkaline hydrolysis in the polar solvent by
hydrolysis.
(A) SN2 (B) SN1
(C) SN1 and SN2 (D) None of the above

Solution: As already mentioned before that polar medium sec. Alkyl halide undergo
SN1 mechanism.
 (A)

Problem 3: Reduction of alkyl halide with nascent hydrogen leads to the formation of:
(A) Parent alkane (B) Alkene
(C) Alkyne (D) None of the above

Solution: R – X 
H
R–H
 (A)
4H
CH3Br  A  CH3CH2NH2
KCN
Problem 4:
I.U.P.A.C. name of A
(A) Methyl cyanide (B) Methyl isonitrile
(C) Acetonitrile (D)Ethane nitrile

Solution: CH3Br  CH3CN 

KCN
 CH3CH2NH2
4H

CH3CN  Ethane nitrile

Problem 5: In the chlorination of isobutane, which product will be formed in excess:

(A) (CH3)2 CHCH2Cl (B) (CH3)3CCl
(C) Both of above (D) None of the above

Rankers-JEE by Saurabh Maurya

Solution: H CH3 CH3
| | |
H3C – C – CH3  CH3 – C  CH3 – C – Cl
Cl

| | |
CH3 CH3 CH3
 (B)

Product – I   C2H5Br  Product - II

ag KOH alc KOH
Problem 6:
(A) Product – I is obtained by the elimination reaction
(B) Product – II is obtained by the substitution reaction
(C) The molecular formula of Product – I is C2H4, while the molecular
formula of Product – II is C2H6O
(D) Product – I is the isomer of dimethyl ether, while Product-II is the
dehydrated compound of Product - I

Solution: C2H5Br   C2H5OH (Product-I)

aq KOH

(Nucleophilic substitution reaction)

C2H5Br   C2H4 (Product – II)
alc KOH

(elimination reaction)
C2H5OH (Product-I) isomer is CH3OCH3
C2H5OH    C2H4
dehy dration

 (D)

Problem 7: In CH3 – CH2 – CH2 – Br, C – Br bond is formed by the overlapping of

3 3
(A) 2sp – 2pz (B) 2sp – 3pz
3 3
(C) 2sp – 2pz (D) 2sp – 4pz

Solution: In the compound CH3 – CH2 – CH2 – Br

As we known Br lies 4th period so Bromine has 4 pz orbital. This 4 pz
orbital overlap with sp3 hybrid orbital of C adjacent to it.
 (D)

Problem 8: In two separate experiments equal quantities of an alkyl halide, C4H9Cl were
treated at the same temperature with equal volume of 0.1 molar and 0.2
molar solutions of NaOH respectively. In the two experiments, the times
taken for the reaction of exactly 50% of the alkyl halide were the same. The
most likely structure of halide is:
(A) CH3CH2CH2CH2Cl (B) CH3CH(Cl) CH2 CH3
(C) (CH3)2 CHCH2Cl (D) (CH3)3 CCl

Solution: CH3
| (After
CH3 – CH2 – CH2 – CH2Cl  H3C – C rearrangement)
|
CH3
CH3 CH3
| |
OH
CH3 – C CH3 – C – Cl
| |
CH3 CH3

Rankers-JEE by Saurabh Maurya

 As we already mentioned that Hydrolysis of 3° alkyl halide is independent
of nucleophilic concentration.
 (D)

Problem 9: Alkyl halide react with an alcoholic solution of ammonia to give a mixture
of:
(A) 1° and 2° amine (B) 1°, 2°, 3° & quaternary
(C) 1°, 2° & 3° amines (D) 1° & 3° amine

Solution: Alcoholic solution of ammonia is heated in a scaled tube at 100°C


RI  RNH2 
NH3 RI
(R)2NH 
RI
(R)3NH 
RI
(R)4 N I
1° amine 2° amine 3° amine 4° salt
 (B)

Problem 10: For the reaction

R – Br  R – O – N = O the suitable reagent is
(A) NaNO2 + HCl (B) HNO2
(C) AgNO2 (D) KNO2

Solution: R – Br  R – O – N = O
Alkyl halide Alkyl nitrites

Alkyl nitrites are prepared by the action of alkyl halide and potassium
nitrite only but in case of silver nitrite the main product is nitro alkane
although a small amount of alkyl nitrite is also formed.
R – Br + KNO2  R – O – N = O + KBr
(D)

Rankers-JEE by Saurabh Maurya

Assignments
Subjective

LEVEL-I

1. What happen when neopentyl alcohol reacts with anhydrous hydrogen bromide?

2. Which hydrocarbon is consistent with the following formation? Molecular mass = 72

gives a single monochloride and two dichlorides on photochlorination

3. RCI is treated with Li in ether to form R – Li, R – Li reacts with water to form
isopentane. R – Cl also reacts with sodium to form 2, 7–dimethyl octane. What is the
structure of R – Cl.

4. An organic compound (A) C7H15Cl on treatment with alcoholic caustic potash gives a
hydrocarbon (B) C7H14. (B) on treatment with ozone and subsequent hydrolysis gives
acetone and butyraldehyde. What are (A) and (B).

5. (a) Give simple test to distinguish among hexane and CH3 – CH = CHCl

(b) Give simple test to distinguish among CH3 – CH = CHCl, CH3CH2CH2Cl and
CH2 = CH – CH2Cl.

6. A chloroderivative ‘X’ on treatment with zinc and hydrochloric acid gave a

hydrocarbon with five carbon atoms in the molecule. When X is dissolved in ether
and treated with sodium, 2, 2, 5, 5-tetramethyl hexane is obtained. What is
compound X.

7. An alkyl halide (X) of formula C6H13Cl, on treatment with potassium tertiary butoxide
gives two isomeric alkenes (Y) and (Z) of formula C6H12. Both alkenes on
hydrogenation give 2, 3-dimethylbutane. Predict (X), (Y) and (Z).

8. With alcoholic potash, C3H7Br (A) gives C3H6 (B). (B) on oxidation gives C2H4O2,
carbon dioxide and water. With hydrobromic acid (B) gives (D), an isomer of (A).
Identify the compounds (A) to (D).

9. Give common and IUPAC names for C4H9Br isomers and classify them as to
whether they are 1°, 2° or 3°.

10. A halide, C5H11X, on treating with alc. KOH gives only pentene-2, What is the halide?

Rankers-JEE by Saurabh Maurya

 LEVEL - II
1. A primary alkyl halide (A), C4H9Br, reacted with alcoholic KOH to give compound (B).
Compound (B) reacted with hydrogen bromide to give (C), an isomer of (A). When
(A) was treated with sodium, it gave a compound (D), C8H18, which was different
from the compound produced when n-butyl bromide was reacted with sodium. Draw
the structural formula of A and write equations for all reactions.

2. Treatment of 2-bromobutane with hot alcoholic 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. Both (B) and (C) gave
the same single product (D) on ozonolysis. What are the structural formulae of (A),
(B), (C) and (D)?

3. Consider following reaction, and predict the products.

CH3 OH

CH –– CH3  ?
H
Heat

4. C6H6+ CH2= CHCH2Cl  

1. AlCl3
(C9H10)
2. BH3 , THF H2 O 2 , OH 
3.HF, 

\5. The alkyl halide C4H9Br (A) reacts with alcoholic KOH and gives an alkene (B), which
reacts with bromine to give dibromide (C). (C) is transformed with sodamide to a gas
(D) which forms a precipitate when passed through an ammonical silver nitrate
solution. Give the structural formulae of the compounds (A), (B), (C) and (D) and
explain reactions involved.

6. A chloro compound (A) showed the following properties.

a) Decolorized bromine water
b) Absorbed hydrogen catalytically
c) Gives a precipitate with ammonical cuprous chloride
d) when vaporized 1.49 g of (A) gave 448 ml of vapours at STP. Identify (A) and
write down the reactions involved.

7. An organic compound (X) on analysis gives 24.24% C, 4.04% H. Further sodium

extract of 1.0 g of (X) gives 2.90 g of AgCl with acidified AgNO3 solution. The
compound (X) may be represented by two isomeric structures (Y) and (Z). (Y) on
treatment with aqueous KOH solution gives a dihydroxy compound, while (Z) on
similar treatment gives ethanal. Find out (X), (Y) and (Z).

8. 0.369 g of a bromoderivative of a hydrocarbon (A) when vaporized occupied

67.2 ml at NTP. (A) on reaction with aqueous NaOH gives (B). (B) when passed over
alumina at 250°C gives an isomer of (A). When (D) is treated with conc.
H2SO4 and the product is diluted with water and distilled, (E) is obtained. Identify (A)
to (E) and explain the reactions.

Rankers-JEE by Saurabh Maurya

9. Dehydrobromination of compounds (A) and (B) yield the same alkene (C). Alkene (C)
can regenerate (A) and (C) by the addition of HBr in the presence and absence of
peroxide respectively. Hydrolysis of (A) and (B) give isomeric products (D) and (E)
respectively, 1,1–diphenyl ethane is obtained on reaction of (C) with benzene in
presence of H+. Give structures of (A) to (E) with reasons.

10. An organic compound (A), C5H9Br which readily decolourises bromine water and
KMnO4 solution gives (B), C5H11Br on treatment with Sn/HCl. The reaction of (A) with
NaNH2 Produces (C) with evolution of ammonia. (C) neither reacts with sodium nor
forms any metal acetylide but reacts with Lindlar catalyst to give (D) and on reaction
with Na/liq. NH3 produces (E). Both the compounds (D) and (E) are isomeric. Give
structures of (A) to (E) with proper reasoning.

Rankers-JEE by Saurabh Maurya

 LEVEL - III

1. An organic compound (A), C4H9Cl on reacting with aqueous KOH gives (B) and on
reaction with alcoholic KOH gives (C) which is also formed by passing vapours of (B)
over heated copper. The compound (C) readily decolourises bromine water.
Ozonolysis of (C) gives two compounds (D) and (E). Compound (D) reacts with
NH2OH to give (F) and the compound (E) reacts with NaOH to give an alcohol (G)
and sodium salt (H) of an acid. (D) can also be prepared from propyne on treatment
with water in presence of Hg2+ and H2SO4. Identify (A) to (H) with proper reasoning.
2. An organic compound (A), C5H9Br which readily decolourises bromine water and
KMnO4 solution gives (B), C5H11Br on treatment with Sn/HCl. The reaction of (A) with
NaNH2 produces (C) with evolution of ammonia. (C) neither reacts with sodium nor
forms any metal acetylide but reacts with Lindlar catalyst to give (D) and on reaction
with Na/liq. NH3 produces (E). Both the compounds (D) and (E) are isomeric. Give
structures of (A) to (E) with proper reasoning.

3. 2-Pentanol can be converted into 2-ethoxy pentane by two paths:

CH3

K CH3CH2CH2 ————— OH

Path I H
(d-) Path II TsCi

CH3 CH3
CH3CH2CH2———OH CH3CH2CH2———OTs
H H
C2H5OTs C 2H5 O K 
CH3 CH3
CH3CH2CH2———OC2H5 C2H5O———CH2CH2CH3
H H
(d-)
(l-)
 
Tosyl (Ts) is p-MeC6H4 SO 2 , Me— — SO 2
In path I, configuration at chiral C is retained but in path II, configuration is inverted.
Explain
4. Explain briefly the formation of the products giving the structures of the
intermediates.
a) CH CH2 CH H2C
HCl

H2C H2C
H2C OH H2C Cl

CH2
+ CH – CH2 – Cl+ etc
CH2
CH3 CH3

CH CH CH HC
HCl
(only)
H2C H2C
H2C OH H2C Cl

Rankers-JEE by Saurabh Maurya

 b) O

H3C C – OC2H5
O
CH
O
C – OC2H5 –
NaOEt Br (i) HO
CH2
(ii) H+ H3C – CH – C – OH
C – OC2H5
CH2 – C – OH
O
O
5. In study of chlorination of propane four products (A,B,C,D) of molecular formula
C3H6Cl2 were obtained. On further chlorination of the above products A gave one
trichloro product, B gave two whereas C and D gave three each. When optically
active C was chlorinated one of the trichloro propanes was optically active and
remaining two were optically inactive. Identify the structures of A, B, C and D, and
explain formation of products.

6. Treatment of sulfanilic acid with bromine gives 2,4,6- tribromo aniline, treatment of
4- hydroxy –1,3 – benzene sulfonic acid with nitric acid gives picric acid, outline the
mechanism or pathway of the above two reactions.

7. Write the pathway CH3

of the following H3C CH3 Br
C CH3
reaction
(AlBr3)
+ Br2  + HBr + H3C—C = CH2

8. Identify the products and also explain about their formation

(a) CH2Br (b) CH2Br
SN1 SN2
+ H2O C2H5OH
HCOOH soln + NaOC2H5

(c) CH2CH3
Catalyst Br2
A alc KOH NaNH2 B
heat

9. i) Arrange the following compounds in order of reactivity towards SN2 reactions

a) 1- bromobutane, 1-bromo –2,2 – dimethyl propane, 1-bromo-2-methylbutane,
1-bromo –3-methyl butane
b) 2 – bromo –2- methyl butane, 1- bromopentane, 2- bromo pentane
ii) How can you convert n – butyl bromide into the following products
(a) Pentane nitrile (b) Lithium di-n-butyl Copper (c) n – butyl amine
10. When a mixture of Toluene and CBrCl3 was irradiated with u-v light benzyl bromide
and CHCl3 were obtained as products in equimolar amounts, what is the mechanism
for the above reaction. Apart from the above products HBr and C2Cl6 were obtained
in small amounts. Account for these observations.

Rankers-JEE by Saurabh Maurya

Objective
LEVEL – I

1. The reactivity order of halide ion in alkyl halide is

(A) F– > Cl– > Br  > I– (B) Cl– > F– > Br  > I–

– –
(C) I > Br > Cl > F –
(D) Br  > I– > Cl– > F–

2. The order of polarity of CH3I, CH3Br and CH3Cl molecules follows the order:
(A) CH3Br > CH3Cl > CH3l (B) CH3I > CH3Br > CH3Cl
(C) CH3Cl > CH3Br > CH3I (D) CH3Cl > CH3I > CH3Br

3. The shape of CH3Cl molecule is

(A) Pyramidal (B) Linear
(C) Tetrahedral (D) Trigonal pyramidal

4. A magnesium alkyl halide is known as

(A) Griganard’s reagent (B) Genton’s reagent
(C) Twitchell’s reagent (D) Schweizer’s reagent

5. The reaction between ethyl bromide and sodium in dry ether to form butane is called
(A) Friedel – Craft’s reaction (B) Wurtz reaction
(C) Cannizzaro reaction (D) Williamson’s reaction

6. Formation of alkane by the action of Zn on alkyl halide is called

(A) Wurtz reaction (B) Kolbe’s reaction
(C) Cannizzaro’s reaction (D) Frankland’s reaction

7. Methyl chloride reacts with silver acetate to yield

(A) Acetic acid (B) Methyl acetate
(C) Acetyl chloride (D) Acetaldehyde

8. Pick up the correct statement about alkyl halides

(A) They show H-bonding
(B) They are soluble in water
(C) They are soluble in organic solvents
(D) They do not contain any polar bond

9. The compound having no dipole moment is

(A) CH3Cl (B) CCl4
(C) CH2Cl2 (D) CCl3

10. Which one is known as a tear gas

(A) CCl3NO2 (B) COCl2
(C) CH3COCl (D) Chloropikrin

11. Heating together of sodium ethoxide and ethyl iodide will give:
(A) ethyl alcohol (B) acetaldehyde
(C) diethyl ether (D) acetic acid

Rankers-JEE by Saurabh Maurya

12. 20 % aqueous solution of sodium chloride containing ethyl alcohol on electrolysis
gives
(A) ethyl alcohol (B) chloral
(C) acetaldehyde (D) chloroform

13. The reagent used in the conversion of 1–butanol to 1–bromobutane is

(A) CHBr3 (B) Br2
(C) CH3Br (D) PBr3

14. In Wurtz reaction of alkyl halides with sodium, the reactivity order of these halides is
(A) RI > RBr > RCl (B) RCl > RBr > RI
(C) RBr > RI > RCl (D) None

15. Which alkyl halide has maximum reactivity

(A) CH3CH2Br (B) CH3Br
(C) CH3CH2CH2Br (D) CH3CH2CH2CH2Br

Rankers-JEE by Saurabh Maurya

 LEVEL – II

1. Sodium ethoxide reacts with ethyl iodide to yield

(A) CH3CH3 (B) C2H5OCH3
(C) C2H5OC2H5 (D) None

2. When ethyl iodide is treated with alcoholic caustic potash, we get

(A) Ethyl alcohol (B) Ethane
(C) Ethylene (D) Acetylene

3. The correct order of melting and boiling points of the primary (1°), secondary
(2°) and tertiary (3°) alkyl halides is
(A) P > S > T (B) T > S > P
(C) S > T > P (D) T > P > S

4. Preparation of alkyl halides in laboratory is least preferred by

(A) Halide exchange
(B) Direct halogenation of alkanes
(C) Treatment of alcohols
(D) Addition of hydrogen halides to alkenes

5. The product of reaction of alcoholic AgNO2 with ethyl bromide are

(A) ethane (B) ethene
(C) nitro ethane (D) ethyl nitrite

6. In elimination reactions, the reactivity of alkyl halides is in decreasing order

(A) T  S  P (B) P  S  T
(B) S  P  T (D) none of these

7. In elimination reactions, i.e., in the formation of alkenes, reactivity of the

halides in alkyl halides follows the order:
(A) I– > Br  > Cl– (B) Cl– > Br  > I–
(C) Br  > Cl– > I– (D) None

8. The SN1 reactivity of ethyl chloride is

(A) More or equal to that of benzyl chloride
(B) Less than that of benzyl chloride
(C) More or equal to that of chlorobenzene
(D) Less or equal to that of chlorobenzene

9. For the reaction,

C2H5OH + HX   C2H5X, the order of reactivity is
ZnX 2

(A) HI > HCl > HBr (B) HI > HBr > HCl
(C) HCl > HBr > HI (D) HBr > HI > HCl

Rankers-JEE by Saurabh Maurya

10. The reaction
Cl

CH3—CH KOH (aq.) CH3—CH—OH+Cl–

CH3 CH3
(A) Reduction (B) Oxidation
(C) Neutralisation (D) Nucleophilic substitution

11. In SN1 reaction, the first step involves the formation of

(A) Free radical (B) Carbanion
(C) Carbocation (D) Final product

12. The order of reactivity of alkyl halides depends upon:

(A) nature of alkyl group only
(B) nature of halogen atom only
(C) nature of both alkyl group and halogen atoms
(D) none of these

13. When a solution of Silver nitrate is added to pure carbon tetrachloride

(A) a pale yellow precipitate is formed (B) curdy white precipitate is formed
(C) no precipitate is formed (D) none of the above

14. The reaction,

Alcohol + HCl Alkyl halide + H2O
is reversible. For the completion of the reaction ……… is used.
(A) anhydrous zinc chloride (B) concentrated H2SO4
(B) excess of water (D) Calcium chloride

15. The product obtained on treatment of ethyl chloride with potassium cyanide is
reduced by sodium and alcohol to give
(A) propyl amine (B) ethyl amine
(C) diethyl amine (D) acetic acid

Rankers-JEE by Saurabh Maurya

Answers
LEVEL-I

1. When neopentyl alcohol react with anhydrous hydrogen bromide, the main product is
t-amyl bromide (72 percent), together with primary and secondary bromides. The
rearranged bromides are the result of 1,2–shifts (methyl and hydride). The ‘driving
force’ of the rearrangement is probably due to the stabilities of carbonium ions being
3 > 2 > 1.

2. (CH3)4C, (CH3)3C CH2Cl

(CH3)3C CHCl2 and (CH3)2C(CH2Cl)2

CH3—CH—CH2—CH2—Cl
3.
CH3

4. (A) (CH3)2CClCH2CH2CH2CH3 (B) (CH3)2C=CHCH2CH2CH3

5. a) Hexane and methyl vinyl chloride are distinguished by adding bromine in CCl4 to
each. The red brown bromine colour persists in alkane but disappears in methyl
vinyl chloride.
b) CH2 = CH – CH2Cl is an allylic chloride (The Cl is very reactive). This
reacts rapidly with AgNO3 in the cold to give a white ppt. of AgCl. CH3CH2CH2Cl
gives white ppt. when warmed with AgNO3 as it is comparatively less reactive.
CH3 – CH = CHCl is inert and does not form white ppt. with AgNO3
CH3 CH3 CH3
6.
CH3 – C – CH2 – CH2 – C – CH3 – CH3 is formed from CH3 – C – CH2Cl
(X)
CH3 CH3 CH3 CH3

On reduction with Zn and HCl CH3 – C – CH3

CH3

7. (CH3)2CH—C(CH3)2 (X) ; CH3—C = C—CH3 (Y) ; CH3—CH—C = CH2 (Z)

Cl CH3 CH3 CH3 CH3

8. (A) CH3CH2—CH2Br (B) CH3CH = CH2
(C) CH3COOH (D) CH3CHBrCH3
9. CH3CH2CH2CH2Br CH3CH2CHBrCH3
CH3

CH3—C—Br
CH3

CH3—CH—CH2Br CH3

10. (I) CH3CH2CH2CHXCH3 (II) CH3CH2CHXCH2CH3

Rankers-JEE by Saurabh Maurya

 LEVEL-II

1. (A) CH3 (B) CH3

CH3—CH—CH2Br CH3—C = CH2

(C) CH3 (D) CH3 CH3

CH3—C—CH3 CH3—CH2—CH—CH2—CH—CH3
Br

2. (A) CH3—CH2—CH = CH2 (B) CH3—CH=CH—CH3 (cis)

(C) CH3—CH=CH—CH3 (trans) (D) CH3CHO

3. CH3 OH CH3

CH – CH3 CH3 CH3
CH – CH3
+ H+  
H O  H

2
+
CH3 CH3

4. CH2 – CH = CH2
CH2 – CH2 – CH2 – OH

+ CH2 = CH – CH2Cl 

3

AlCl   
BF3 , THF HF, –H2O
H2 O 2 , OH

5. (A) CH3CH2CH2CH2Br (B) CH3CH2—CH = CH2

(C) CH3CH2CHBrCH2Br (D) CH3CH2C  CH

6. (A) CH2Cl C CH

7. CH2Cl (X)
CH3CHCl2 (Z)
CH2ClCH2Cl (Y)

8. (A) C3H7Br (B) C3H7OH

(C) C3H7OC3H7 (D) C3H6
(E) CH3—CH(OH)—CH3
9. (A) C6H5CH2—CH2Br (B) C6H5CHBrCH3
(C) C6H5CH = CH2 (D) C6H5CH2CH2OH
(E) Isomer of D

10. (A) CH3—CH = CBrC2H5 (B) CH3—CH2—CHBr — C2H5

(C) CH3—CC C2H5 (D) CH3CH = CHC2H5 (cis)
(E) CH3CH=CHC2H5 (trans)

Rankers-JEE by Saurabh Maurya

 LEVEL-III

1. (A) CH3 (B) CH3

CH3—C—Cl CH3—C—OH

CH3 CH3
(C) (CH3)2C = CH2 (D) (CH3)2C = O
(E) HCHO (F) (CH3)2 C= NOH
(G) CH3OH (H) HCOONa

2. (A) CH3—CH = CBrC2H5 (B) CH3—CH2—CHBr — C2H5

(C) CH3—CC C2H5 (D) CH3CH = CHC2H5 (cis)
(E) CH3CH=CHC2H5 (trans)

3. In both, paths the nucleophile is an alkoxide anion. In path I, nucleophile has

chiral centre and reaction takes place without breaking any bond, thus
configuration in final products is retained.

CH3 CH3
C2H5 O Ts
CH3CH2CH2———O K  CH3CH2CH2——— OC2H5
– +
path I
H H
nucleophile with chiral carbon

In path II, ethoxide (nucleophile) attacks chiral centre backside in an SN2 reaction
with inversion of configuration in ether.

CH3 CHO CH3

C2H5OK 
2 5

CH3CH2CH2———OTs      CH3CH2CH2—-------OTs
path II
H H leaving group

inversion

CH3
C2H5O————CH2CH2CH3
H

4. CH +
CH2 CH CH2 CH CH2Cl
+ –
H Cl
H2C OH
CH2 H2C CH2 H2C CH2
Or
CH CH3 CH CH3
–
Cl
H2C CH
+ H2C CH

Cl or

Rankers-JEE by Saurabh Maurya

 + Cl–
–CH2 —CH2Cl
CH3 CH3 CH3
CH CH CH CH
CH CHCl
+
+ -
H Cl
H2C OH
CH2 H2C CH2 H2C CH2
(more stable)
Cl
|
5. A = CH3  C  CH3
|
Cl
B = C H2  CH2  C H2
| |
Cl Cl
C = CH3  C H  CH2Cl
|
Cl
D =CH3CH2CHCl2

CH2OH
8. a)

CH2—OCH2CH3
b)

CH = CH2 C CH
c)
A= B=

9. a) Br

CH3CH2CH2—CH2BrCH3—CH—CH2—CH2Br>
CH3 CH3

CH3CH2—CH—CH2BrCH3—C—CH2Br

CH3
b) 1°  2°  3°
(ii) (a) nC4H9Br  KCN

 Pentane nitrile
Li
(b) nC4H9Br  lithium di-n butyl copper
CuI
nC4H9Br   NH3
 nC4H9NH2
c) excess

Rankers-JEE by Saurabh Maurya

Objective

LEVEL - I

1. C 2. C

3. C 4. A

5. B 6. D

7. B 8. C

9. B 10. A, D

11. C 12. D

13. D 14. A

15. B

LEVEL - II
1. C 2. A

3. A 4. B

5. C, D 6. A

7. A 8. B

9. A 10. D

11. C 12. C

13. C 14. A

15. A

6
Rankers-JEE by Saurabh Maurya