12.

Explain why: () Dipole moment of chlorobenzene is lower than that of cyclohexylchloride

are immiscible with water.
Gi) Alkyl halides though polar,
(a) Grignard reagents should be prepared under anhydrous conditions.
-sp hybridised sp hybridised
Chlorobenzene Cyelohexyl chloride
The polarity of C-CI bond in chlorobenzene is less than that of same bond in cyclohexyl
chloride because of carbon atom involved in chlorobenzene is more electronegative (greater
s-character) as compared to the carbon atom in case of cyclohexyl chloride (lesser s-character).
Therefore, the dipole moment of chlorobenzene is less with respect to cyclohexyl chloride.
Gi) In water, H2O molecules are linked to each other by intermoleculer hydrogen bonding.
Although alkyl halides also contain polar C-X bonds, they cannot break the hydrogen bonding in
H0 molecules. This means that there is hardly any scope for association between molecules of
alkyl halidesand water. They therefore, exist as separate layers and are immiscible with each
other. For more details, consult text part.
(i) Grignard reagents (R-Mg-X) should be prepared under anhydrous conditions because these
are readily decomposed by water to form alkanes.
X
R-Mg-X +H20 R-H + M
Grignard reagent Alkane
OH
That is why ether used as solvent in the preparation of Grignard reagent is completely anhydrous
Innature.
Cive the uses of freon-12, D.D.T., carbon tetrachloride and iodoform?
 methylbutane (1°) dimethylpropane (1°)
methylbutane (1°)
. Out of CH,CH,Cl and CJH,CHCICH, which is more easily hydrolysed by aqueous KOH ?
The compound CH,CH,Cl is a primary aralkyl halide while CgH,CH(CI)CgHs is secondary in
nature. The hydrolysis of both these compounds with aqueous KOH (polar) is likely to proceed by
S' mechanism due to following reasons.
(a The carbocations formed in both the cases as a result of ionisation are resonance stabilised
due to the presence of phenyl groups at the a-position(s).
) As water is a polar solvent, it is expected to favour ionisation of the two halogen substituted
compounds leading to Sy mechanism.
The carbocations that are formed as a result of ionisation in the slow steps are shown:
CgHs-CH-ci
ionisation
CHy-H, +Cr (slow step)
Benzyl chloride 1°-Carbocation
 DINESH COMPAN
PANION CHEMISTRY-
11.7

onisation
CH C CH CH-CH-C,Hs +Cl
skr

1-Chioro- 1.1 diphenv imethane 2-Carbocation

The casc of hydroly s1s depends upon the relative stability of the carbocation that are form
rmed
cases Thc secondary carbocation is more stable since the positive charge on the carboc
delcalised on two phenyl groups that are present at the a-positions. On the other hand, ther
one pheny l group in primary carbocation available for charge delocalisation.
Thus, we may conclude that CgH$CHCIC;H$ is more easily hydrolysed by aqueous K
compared to CH,CHC
0.18. pdichlorobenzene has higher m.p. and lesser solubility than these of o- and m-ise
Discuss.
As. The three isomers are position isomers which differ in the relative
positions of the chi
aloms in the ring

CI
Ci

o-Dichlorobenzene
ci
m-Dichlorobenzene
As
know. p-isomer more symmetrical as compared to the
we is p-Dichlorobenzene
in the
ery stal lattice, the p-1s0mers are more closed packed as other isomers. This meas
As result, it has a higher meltung point and
a compared to the other is0u
isomers. For more details, consult section lower
l1.13. solubility as compared to and ortho
 Aniline Phenyl isocyanide
The reaction is known as carbyl amine reaction.
20. The treatmentof alkylchlorides with aqueousKOH leadsto the formation ofalcoho
in presence of alcoholic KOH, major products. Explain. (Pb. Board 2
Ans Inaqueous medium i.e., water,alkenes
KOH willare
be completely dissociatedto give OH ions. D
being a strong
alcohols. nucleophile,
At the same
will bring
time, the OH ions willabout
be the substitution
highly
of
hydratedalso. alkyl
halides tof
They willnotbe
to abstract proton H)ionsfrom
will the -carbon atom to form alkenes. I n other words
aqueous medium, OHF behave and elimination leading to alik
a
weak base
will not be feasible.
In alcoholic KOH, the solution willalso contain ethoxideions (C2HsO") in additionto 0
ions. They being a stronger base hanOH 1ons, will abstract a H* ion from the B-car
atom giving alkene as the product as a result ofdehydrohalogenation.
 1187
M EA
S NO
HALDARENES

Matching Type Questions

given in Column I and Column II in the following questions.

Match theitems
in
in Column I with
Colum the effects given in Column I.
compounds
given
1unds given Column III
Column I
Match (i) Malaria
(a) Chloramphenicol

(ii) Anaesthetic
(b) Thyroxine (iii) Typhoid fever
(c) Chloroquine
(iv) Goiter
(v) Blood substituent
( d ) C h l o r o f o r m

I and Colum
umn ..
Column Column III
the items of
Match Column (i) vic-dibromides
(a) S' reaction

fire extinguisher
(11) gem-dihalides
Chemicals in i ) Racemisation
(b) of alkenes
Bromination
(c) (iv) Saytzeff rule
(d) Alkylidene halides
(v) Chlorobromocarbons
of HX from alkylhalide
(e)
Elimination
in cOumn I with tne classes of compounds given in
of compounds given
hthe structures
Column ll. Column II
Column I
i) Aryl halide
(a) CH3-CH-CH3

(ii) Alkyl halide

(b) CH=CH-CH2-X

(ii) Vinyl halide

(iv) Allyl halide

(d) CH2=CH-X II.
in Column I with the types of reactions given in Column
Match the reactions given Column I
Column I
CI
CI Cl
substihuion
Fe/Ch () Nucleophilic aromatic

Cl
aromatic substituion
CH-CH=CH HBr (ii) Electrophilic
+
CH3-CH-CH3
Br
CH-CH-1 CH-CH-OH
(ii) Saytzeff elimination
OH
 CI OH PANIUN LHEMISTRY
(d) NaOH-
(iv) Electrophilic aduit
NO NO2
()CHCH,CHCH alc.KOH CHCH=CHCH3 (v) Nucleophilic substinti,
Br
48. Match the structures
given in Column I with the names in
Column II.
Column I
Column II
Br
(a)
(i) 4-Bromopent-2-ene

(b) Br
(ii) 4-Bromo-3-methylpent

()Br (iii) 1-Bromo-3-methylbut-2e

(d) Br
49. Match the reactions
(iv) 1-Bromo-2-methylpent-2e
given in Column I with the names
Column I given in Column II.
Column I
(a) X RX R

(i) Fittig reaction

b) 2 + 2Na h e r
+2NaX (ii) Wurtz Fittig reaction
N2X
Cu2 N2
(iii) Finkelstein reaction

(d) C2HsCI + Nal dry acetone

C2Hsl + NaCI (iv) Sandmeyer reaction
 A NH A L D A R E N E S
11.89
and penta) are preferred thionyl chloride for the
.Phosphorus chlorides (tri
over
AerTion of alkyl chlorides from alcohols.
preparation
Phosphorus chlorides give pure alkyl halides.
halides decrease in the order RI > RBr> RCI
K e a s o n
Aerton:

. The boiling points of alkyl :

> RE.
of alkyl chlorides, bromides and iodides are considerably
The boiling points
than that of the hydrocarbon of comparable molecular mass.
K e a s o n
higher
ian: KCN reacts with methyl chloride to give methyl isocyanide
Asertie
:CN is an ambident nucleophile.
Reason
lcertion ert-Butyl bromide undergoes Wurtz reaction to give 2, 2, 3, 3-tetramethylbutane.
sodium in dry ether to give hydrocarbon
In Wurtz reaction, alkyi halides react with
Rrason
containing double the number of carbon atoms present in the halide.
Assertion: Presence of a nitro group para position increases the reactivity of
at ortho or
haloarenes towards nucleophilic substitution.
Reason Nitro group, being an electron withdrawing group decreases the electron density
over the benzene ring.
Asertion: In monohaloarenes, further electrophilic substirution occurs at ortho and para
positions.
Keason :Halogen atom is a ring deactivator.
Assertion Aryl iodides can be prepared by reaction of arenes with iodine in the presence
of an oxidising agent.
Keason :Oxidising agent oxidises l2 into HI.
uSertion It is difficult to replace chlorine by -OH in chlorobenzene in comparison to
that in chloroethane.
a0 Chlorine-carbon (C-CI) bond in chlorobenzene has a partial double bond
character due to resonance.
Assertion
Reason Hydrolysis of ( ) -2- bromooctane proceeds with inversion of configuration.
Assertion his reaction proceeds through the formation of a carbocation.
:
Nitration of benzene leads to the formation of m-nitro benzene.
Reason -NO; group is a m-directing group.
nSwers
 rlchlorides and bromídes can be easily preparedby electrophilic substitution of arenes
h chlorine and brominerespectively in the presenceof Lewis acid catalysts. But why does
ofaryl iodides requires presence
oreparationconsult of an oxidising agent
?
Foranswer, section 11.12

Out of o- andp-dibromobenzene, which one has higher meltingpoint Br Br

and why ? Br
The strucrure of p-dibromobenzene is moresymmetrical as compared to
dibromobenzene. As a result, in the crystal lattice molecules of
pisomer are more closely packed as compared to the orthoisomer.
Quiteobviously,
TTib
the melting point of the in S.loootiom
f 4 a aamnaunde uill vooat focta p-isomer
is higher.
uith tho OU ion 9
Br
 Why has iodoform appreciable antiseptic property ?
When iodoform (CHI3) comes in contact with skin, it slowly decomposes to evolve io
which is responsible for its antiseptic property.
Contact with skin
CHl
Iodoform (Antiseptic nature)
Haloarenes
the
are less reactive than haloalkanes and haloalkenes. Explain.
and
or comparison of the reactivity of haloarenes haloalkanes,
consult section 11.14.
aloarenes are also less reactive than haloalkenes or vinyl halides. Although C-X bond in haloalken
s aso
partial double character due to resonance or conjugation, but the extent of resonance

HC=CH: H2-CH=:
is
nes more. As a result, the cleavage of the C-X bond in haloarenes is more difficult as
Opared to haloalkenes. These are therefore,
less reactive.
 11.92 DINESH COMPANION CHEMISTRY-0
Discuss the role of Lewis acids arvl bromides and chloridesinthed
in the preparation ofelectrophile (X*) which is involvedd
Ans. Lewis acids (FeCl3 or FeBr3) help in generating the
electrophilic attack o n the ring. details, a nconsult
For d h section
will
11.12.
not react with a_ mixtura af N
ompound (A/. .
chloride is
hydrolys more readily than n-propyl chloride. Why?
ed with aqueous KOH.
is carried chloride can be
Allyl hydrolysed more readily than
droly sis in the reaction is stabilised.
because allyl carbocation formed
resonance
e chloride
propy
CH,=CH-CH2-Cl CH=CH-CH CHCH=CH2
(Resonance stabilised)
Alkyl chloride

formed is
(CH3-CH2-CH2) expected to be
not

In case of n-propyl chloride, the carbocation

chloride is comparatively very difficult.
Therefore, hydrolysis of n-propyl
sabilised. even traces of
moisture during the use of a Grignard reagent?
to avoid
Why is it necessary
reactive. Even in the presence
of traces of water, it gets
Grignard reagent (RMgX)
is highly
(alkane)
bydrolysed to form a hydrocarbon
R-MgX + H20- R - H
+ Mg (OH)X
Alkane Basic mag.halide.
anhydrous conditions. Normally
used in completely
synthesised as well as
15 therefore, ether is used for this purpose.
Completely anhydrous first step in Sy
mechanism?
which is a slow step.
solvents help in the in the first step
ow do polar carbocation
intermediate is
formed
intermediate by solvation.
mechanism, a carbocation
huN the
KOH help in stabilising
such section l1-7.
vents as aqueous details, consult
T mechanism. For
more
y 1avour S' o fd o u h l e bond in a molecule. n o n he detected either with
 icypopdic (Vajor
the nature ofC-A bond in the haloarenes.
Discuss
section 11.14.
Foranswer, consult
How can you obtain iocoethane from ethanol when no other iodine containing reagent
except Nal is available in the Laboratory ?
Nal does not react directly with ethanol. In order to solve the problem, ethanol is first converted
into chloroethane by reacting with HCI (g) in the presence of anhy. ZnCl2. This is then reacted
wvith Nal to form iodoethane by halogen exchange reaction.
CaHOH + HCI (g)ZnClh (anhy CH
Nal

Ethanol Iodoethane
From which end, it acts as a stronger nucleophile
Cyanide ion acts as an ambident nucleophile.answer.
in aqueous medium ? Give reason for your it will lead to the formation of
acts as a stronger nucleophile from the carbon end because
l
-Cbond which is more stable than C-N bone,
:C=N:+R-X R--C=N: + X
Alkyl halide Alkyl cyanide
For more 11.7.
details, consult section
 LongAnswer Type Questions
Some alkylhalides undergo substitution whereas some undergo elimination reactions on
with bases. Discuss the structural features of alkyl halides with the help of
treatment
amples which are responsible for this difference.
e note that primary alkyl halides generally prefer to take part in the substitution reactions
OWing SN mechanism while tertiary alkyl halides prefer to participate in elimination
nddby following E mechanism. However, other factors are also significant. For examples
nddetails, consult section 11.7.
esponsih containing compounds are useful in daily life. Some compounds of this class are
destructio or exposure of fnora and fauna to more and more of UV light which causes
shouldh o a great extent. Name the class of these halocompounds. opinion, what
In your
u o n e to minimise harmful effectsof these compounds.
Ans. Halogen compounds are extremely useful in daily life and
so in
regarded as synthetic tools for the synthesis of a variety of orgar
anic industry.
Similarly, compounds such as chloroform, iodoform westron, westroso
have found utility in industry. But at the sametime, class of conPer compOunds Al
o and Perirts
of compounas kwwnin t
chlorofluorocarbons (CFCs) which are otherwise quite useful as
harm to our environment. They have played a major role refrigra
in depletindns,
tetrachloride is a culprit to some extent. The depletion of
ozone laver hone 0zO1 have tre
animals to the harmful ultraviolet radiations
lay
(U.V.
skin. early catract, sunburns, skin cancer etc. SKinradiations). These rad
cancer is diation exposed barg,
Australia where the effect of UV radiations is very comm l
very high. For
For details, concul a
halogen compounds). consult section,
Measures to reduce the harmful effects of
these compounds.
We have studied that the major cause of
which are formed as a environmental pollution is the
result of the
processes and release of to
words. chemists are
mainly
reactions carried at tOxic
various levl..
products that are source ofresponsible for polluting the
atmosphere els.
forced them toalthough they alsa
our comfort. This has
1990, a new 0
has been introduced. change their Outbo
concept called Green
"the
production of substances
chemistry By green
of daily
chemicals nor release the
same to the
use by chemical
reactions which chemistn
neither emln
altogether a new fieldatmosphere".
No doubr, this is
made to carry the but some success has
and with sound reactions in the presence of ultra been achieved. Efforts tave
waves (called voilet
which neither sonochemistry).sunlight (known as
need toxÍc solvents nor release Microwaves have been used to photochenis
engines have been fitted with such carry rEa
hydrocarbons and catalytic converters vapours into the
oxides of which atmosphere. Auto
form
poisonous nitrogen into the prevent the release of the
have checked substances such as atmosphere. These vagun
the
layer. Similarly, some release of tormaldehyde,
chemicals acrolein and
are the real
culprits since a
antibiotics such as enzymes have been
into the
environment peroxyacetyl nitrate.
which cause
This
mes
Green Chemistry ampicillin and
to check
employed as
amoxycillin. biocatalysts in the depletion or
(a) Dry
cleaning of pollution are mentioned
A few
noteworthy measuresmanufacture oc
ClC CCl). It clothes. A commonly used
= under ne
other
detergents pollutes water
which and is also dry cleaning
better results.
These
contain liquid carbon carcinogenic. Thissolventhas
is
tetrachlor0
stains from clothes. days,
(b)
hydrogen peroxide dioxide.
is These do not been replaceu
Bleaching of
paper. being used in the pollute water ai
poisonous fumes theChlorine gas was used
in laundries for 101
purpose. atmosphere. AtAt earlier for
(c) Synthesis of
chemicals. present, hydrogen bleaching of aper. It relea*
pape
employed
with oxygen. The
for the
preparation
lonic
catalyststhe in
form
peroxide
pero
1S also used for
of
isacetaldehyde (ethanal)ot Pd* and
of Pa2+
yield of ethanal
excellent (about from ethen Cu2t salts
by carrying have a
CH2 =
CH2 90 cnene
Ethene
+
O2PICu"in waler OXu
This is just the
CH,CHO
Ethanal
beginning and the
particularly the chemists
minimise pollution. All will be Successtulresultsin are
countries encouraging. We
developing new
a
major role in are
giving
from pollution. checking pollution. It is the importance to the
technia. are
sure our
scieni
duty off every study to well
individual
individual toto kchnology as
chemica
keep which h
the
environmnentfree
 S A N UNRLU

lex
reactive towards nucleophilic substitution reactions than alkyl halides ?
nalides

ary7
enhance the reactivit
ctivity of aryl halides?
hy
ae
we ennreactive towards nucleophilic substitution because C-X bond in aryl halides
An'
halhdesa r e
How
bond character due to resonance. Therefore, its cleavage is very difficult as
where C-X bond is not involved in any resonance. For more details,
narerl to alky yl halides aryl halides can be increased in two ways.
14. Reactivity of conditions.
under more drastic
the reactions
0ut the reactions

sull se carrying
out

listed.
are
By examfples

Afew

ONa OH

5K500atm HOH
NaOH
+ (-NaOH)

Sod. phenate Phenol

Chlorobenzene

C NH2

+2NH3+ Cu0
43TK/60atm +CuClzt H02

Aniline
Chlorobenzene

Br CN

+ CuCN 473 K +CuBr

Pyridine)
Bromobenzene Cyanobenzene

deactivated with the help of electron

Benzene ring can be
2 By deactivating the ring :
substitution may be carried
such as nitro(- NO;) groups so that nucleophilic
wIndrawing groups
under milder conditions. For example.
OH
OH

443 K
+NaOH
NaOH 0258/500 aum

Calorobenzene Phenol NO2

NO2 4-Nitrophenol
4-Chloronitrobenzene

OH
C OH NO
NO2 OgN
NO ,NO2 O,NN warm
+ HO
H,0
NO2
NO
24 Dinitrochlorobenzene NO2
,4-Dinitrophenol
NO
2,46-Trinitrochlorobenzene
2,4.6-Trinitropbenol
ANES AND HALDARENES
11.103
be
kvl
Alkyl ehlorides can prepared by refluxing alcohol with thionyl chloride in the presence
is pyridine used ?
of pyridine. Why
Thionyl
chloride is the chlorinating agent in the reaction.
-C-OH + SOCh -Ç-CI+ SO2 + HCI
salt Thus, it removes one of the products andd
PVridine is a tertiary base and forms a with HCI.
the above reaction in the forward direction.
facilitates
Cl-
+HCI
Pyridine hydrochloride
Pyridine
nctive than cyclonentyl çhloride towards reaction?
 11.104 DINESH COMPANION CHEMISTRY
hy does not ammonolysis of alkyl halides yield pure amines ?
Alkyl halides react with ammonia to form a of
mixture primary, secondary
obtained
quaternary ammonium salts. Therefore, pure amines are not obtained as
as aa resuaya
resut of ry amin
22
For details. consult Section I1.7. the
2-Bromopentane is treated with alcoholic KOH solution. What is the major r
his reaction ? What is the name of the reaction ?
major product fon
Ans.
rule. pent-2-ene
h e reaction is known as B-elimination and the major product is pent-2-ene accordir
according to Sj
KOH (alc)
CH3-CH-CH2-CH2-CH3
Br
CH-CH=CH-CHz-CH3+KBr
2-Bromopentane Pent-2-ene
Q.23 Explain why
displacement of
cyanide ion and
amide ion is not observed in nuche
substitution reaction. Ducleo
Ans. Both cyanide ion (CN) and amide ion
(NH2) are powerful nucleophiles and
to displace them by other nucleophiles in the nucleophilic substitution reactions.it is ns
Q. 24. Whyis chloroform not used
Chloroform is not used as anaesthetic
as these days ? is
Ans.
anaesthetic because of
VWhat the commonly used anaesthe
its slow oxidation to poisonous
phosgene.
Halothane (CF3CHCIBr) is the commonly used
25. Which compound in the follawinenairs will ren
anaesthetic these days.
 SANDHALDARENES 11.105

Bmlainwhy reaction of HCIwith CF%CH = CH2 proceeds according to Antimarkownikov's rule.

effect. Therefore, when
orine (F) being a highly electronegative element hasa a strong -Icarbocation
H from acid (electrophile) attacks the substrate, primary is preferably
product.
formed. This reacts with the anion to give the desired

-CH-CH,+HEi-F-CH-CH,F_-CH,-CH,C
 But-1-ene 2-Bromobutane
solution of aqueous
of
KOH bydrolyses CH,CHCICH,CH, and CH,CH,CH,CH,c. Which one
more easily
these is (D.S.B. 2010; C.B.S.E.Foreign 2011)
hydrolysed ?
CHCHCICH2CH3 is moreeasily hydrolysed. Actually, hydrolysis follows Sw mechanisnmtowards
which
secondary alkyl halide is more reactive.
Q.46. Account for the following:
Chloromethane reacts with KCN to form ethanenitrile as the mei
to form methyl isocyanide as the chief product.
(C.B.S Samyl.
Ats. KCN (KC=N) is mainly an ionic compound and provides cyanide ion
attack. On the other hand, silver cyanide (Ag-C=N:)sor
CH-CI +C=NCH-C=N+ C
Chloromethane Ethanenitrile
nanure and only
nitrogen atom is free to donate the electron pair for the nucleomkil.
results in the formation of methyl
isocyanide.
CH-C +Ag-C=N
Chloromethane
CH3--NSC + AgCl
Q.47. Benzylic
Methyl isocyanide
halides show high reactivity towards Sy reactions. Why ?
Ans. S reactions as we all know,
proceed
carbocation intermediate is formed.
in two steps. In the slow step (rate
Therefore. benzyl halides show In benzyl halides, the benzyl carbocation is determinig
high reactivity towards SN' reaction. resonane
CH2-X CH
Slow
+X
CH2 CH CH2
CH2 CH
Q. 48. Complete the following reaction:
HBr
 56 Methylcyclobexene
A. Why do haloalkanes dissolve in
Haioalkanes are covalent organic
1-Iodo-1-methylcyclohexane
solvents ?
which are of similar (D.S.B. IN
nature.compounds with little polarity. They dissolve in organic
Q. 57.
What is a racemic sola
As. An equimolar mixture
mixture
? Give an example.
of two enantiomers (D.S.B.
racenic mixture. of an
optically active
compound is know
CH3
CaHs
C-Br ++
CH/l CHs
H H
"c-Br
-.
 Bromma onexalie
yclohexyl mag.
bromide Cyclohexanol
Although chlorine is an electron
electrophilic aromatic substitution.withdrawing group, yet it is ortho and para directing in
Explain why it is so. (D.S.B. 2012)
For answer. consult section 11.14 (chemical properties of
Which one of the following haloarenes).
compounds is more easily hydrolysed by aqueous KOH and
why ? CH3CH2CICH2CH3 or CHGCH,CH,CI. (A.I.S.B. 2012)
CH CH CH,CI is hydrolysed more easily since it is a primary alkyl halide while the other
alkyl halide is of secondary nature. The hydrolysis proceeds by Sn2 mechanism.
What is meant by chirality of a compound ? Give an example. (A.I.S.B. 2012)
The compound which is non-superimposable on its mirror image is known as chiral compound
and this property is called chirality. For details, consult section 10.8.
What happens when bromine attacks on CHh=CH-CH2-C=CH? (A.I.S.B. 2012)
If excess of bromine is added, a tetrabromo derivative is formed.
Br
4
Br2 (Excess)
CH,-CH-CH2-C=CH CH-CH-R,CH
SB Pent-1-en-4-yne Br Br Br
2. 2, 4, 5-Tetrabromopentane
(D.S.B. 2012
R What are ambident nucleophiles ? Give
an
example.
S.B ror answer consult Q. 8. (N.C.E.R.T. Exercise) ?
h the follewing pairs of compounds
hotween