UNIT HALOALKANES AND

HALOARENES

SYLLABUS :
Haloalkanes: Nomenclature, nature of C-X bond, physical and chemical properties, mechanism of substitution reactions.
Haloarenes:Nature of C-X bond, substitution reactions (directive influence of halogen for monosubstituted
compounds only) Uses and environmental effects of - dichloromethane, trichloromethane, tetrachloromethane,
iodoform, freons, DDT.
KEY CONCEPTS
INTRODUCTION
The haloalkanes (also known as halogenoalkanes or alkyl halides) are a group of chemical compounds, consisting
of alkanes, such as methane or ethane, with one or more halogens linked, such as chlorine or fluorine, making
them a type of organic halide. They are a subset of the halocarbons, similar to haloalkenes and haloaromatics.
They are known under many chemical and commercial names. As flame retardants, fire extinguishants, refrigerants,
propellants and solvents they have wide use.
Chlorine containing antibiotic, chloramphenicol, is very effective for the treatment of typhoid fever.
Iodine containing hormone, thyroxine, the deficiency of which causes a disease called goiter.
Synthetic halogen compounds, viz. chloroquine is used for the treatment of malaria.
Halothane is used as an anaesthetic during surgery.
Some haloalkanes (those containing chlorine or bromine) have been shown to have negative effects on the
environment such as ozone depletion. The most widely known family within this group is the chlorofluorocarbons
(CFCs).
Haloarene, or aryl halide, is an organic compound in which a halogen atom is bonded to a carbon atom which
is part of an aromatic ring.

10.1 CLASSIFICATION
On the basis of hydrocarbon part Halide classified as Halogen Derivatives

Alkyl halides Alkenyl halide Alkynyl halide Aryl halide

Mono halides Di-halides Tri-halides Tetra halides

Primary halide Secondary Halide Tertiary halide

STUDY MATERIAL: XII CHEMISTRY 1 HALOALKANES AND HALOARENES

10.1.1 On the Basis of Number of Halogen Atoms :
(a) Monohaloalkanes : Compounds having only one halogen group. C2H5X
(b) Dihaloalkanes: Compunds having two halogen groups. CH 2 X
|
CH 2 X
If two halogen atoms are bonded to the same carbon atom, they are known as gem dihalides.
If two halogen atoms are bonded to adjacent carbon atoms, they are known as vicinal dihalides.
(c) Polyhaloalkanes: Compounds having more than two halogen groups.
CH 2 X
|
CHX
|
CH 2 X
10.1.2 On the basis of the hybridisation of the carbon atom
Compounds containing sp3 C - X bond:
(a) Alkyl halides: These are classified as primary, secondary or tertiary according to the nature of the carbon
atom to which the halogen is attached. The halogen is bonded to a normal straight or branched chain
alkane.
H R' R'
R X R X R X
H H R"
Primary alkyl Secondary alkyl Tertiary alkyl
halide (1°) halide (2°) halide (3°)
(b) Allylic halides: In allylic halides, the halogen atom is bonded to an sp3 hybridised carbon atom next to the
carbon - carbon double bond.
X

CH2X

(c) Benzylic halides: In benzylic halides, the halogen atom is bonded to an sp3 hybridised carbon atom next
to the benzene ring.
R'
X
CH2X R''

(1°) R' = CH3, R'' = H (2°)

R' = R'' = CH3 (3°)
10.1.3 Compounds containing sp2 C - X bond:
(a) Vinylic halides : In vinylic halides, the halogen atom is bonded to an sp2 hybridised carbon atom of a
carbon carbon double bond.
X

STUDY MATERIAL: XII CHEMISTRY 2 HALOALKANES AND HALOARENES

 (b) Aryl halides: In aryl halides, the halogen atom is bonded to an sp2 hybridised carbon of an aromatic ring.
X X

H3C

10.2 NOMENCLATURE OF ALKYL HALIDES

Simple alkyl halides are named as substituents on the parent alkane, using chloro, bromo, iodo or fluoro to
denote the nature of the halogen.
1. First, select the longest continuous carbon chain; if the molecule contains a double or triple bond, the parent
chain must contain it.
2. Number the carbon chain in the direction to produce the lowest number for the first substituent encountered, or
to give the lowest number sequence at the first point of difference.
3. Number the substituents and write the name, listing substituents alphabetically.
Several simple examples are shown below:
H H3C CH3

Br Cl
I

Br
In the first example, the parent chain is a hexane and a bromine is attached to carbon #3. If we had started
numbering at the other end, the bromine would be in position #4; hence the name, 3-bromohexane.
In the second example, there are two potential five-carbon chains; in this case, the chain with the most substitu-
ents is selected as parent, (a pentane). Attached to the pentane at carbon #2 is a bromo group and at carbon
#3, an ethyl group; hence the name 2-bromo-3-ethylpentane.
In the third example, the iodine is attached to a cyclohexane ring and will therefore be named as a halocycloalkane;
the name is iodocyclohexane (no number required).
In the last example, the chlorine and two methyl groups are attached to a cyclopentane ring. The numbering
must begin at the carbon bearing the methyl groups since the sequence [1,1,2] is lower at the first point of
difference than the sequence [1,2,2], which you would have if the chlorine was attached to carbon #1; the
name is therefore 2-chloro-1,1-dimethylcyclopentane.
4. For dihalogen derivatives, the prefixes o-, m-, p- are used in common system but in IUPAC system, the
numerals 1, 2; 1, 3 and 1, 4 are used.
CH3
|
CH3CH2CH2Br H3C  CH  CH3 H3C  CH  CH 2 Cl
|
Cl
Comman name : n-Propyl bromide Isopropyl chloride Isobutyl chloride
IUPAC name : 1-Bromopropane 2-Chloropropane 1-Chloro-2-methylpropane
Br Br
Br

Br Br Br
Comman name : Bromobenzene m-Dibromobenzene sym-Tribromobenzene
IUPAC name : Bromobenzene 1,3-Dibromobenzene 1,3,5-Tribromobenzene
STUDY MATERIAL: XII CHEMISTRY 3 HALOALKANES AND HALOARENES
 CH3
|
H3C  C  CH 2 Cl H3C  CH  CH3
| |
CH3 Br
IUPAC name : 1-Chloro-2,2,-dimethylpropane 2-Bromopropane
5. The dihaloalkanes having the same type of halogen atoms are named as alkylidene or alkylene dihalides. The
dihalo-compounds having same type of halogen atoms are further classified as geminal halides (halogen atoms
are present on the same carbon atom) and vicinal halides (halogen atoms are present on the adjacent carbon
atoms). In common name system, gem-dihalides are named as alkylidene halides and vic-dihalides are named
as alkylene dihalides. In IUPAC system, they are named as dihaloalkanes.
H3C – CHCl2 H 2C  CH 2
| |
Cl Cl
Comman name : Ethylidene chloride Ethylene dichloride
(gem-dihalide) (vic-dihalide)
IUPAC name : 1,1-Dichloroethane 1,2-Dichloroethane

10.3 NATURE OF C-X BOND

(i) Nature of the C – X bond in haloalkanes :
In haloalkanes the C – X bond is formed by the overlap of sp3 hybrid orbital of carbon and 3p half filled
orbital of chlorine (sp3 – p overlap). In table the values of the bond length and bond energies of different
C – X bond have been given. From these values it is clear that C – F bond in these is very strong and
C – I bond is of a very weak nature.
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Bond Bond energy Kcal/mole Bond length (Å)
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
C–F 105.4 1.42
C – Cl 78.5 1.77
C – Br 65.5 1.90
C–I 57.5 2.10
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
The electronegativity of carbon (2.6) is less than the electronegativity of halogen atom therefore, the C – X
bond has a polar character. In this way, a partial negative charge on halogen atom and a partial positive
charge on carbon atom is developed.
 
 X
C ——
Because of this polarity in the bond, R – X show dipole moment (µ).
CH3Cl CH3Br CH3I
µ = 1.86 D 1.79 D 1.62D
(ii) Nature of the C – X bond in Vinyl halides and aryl halides
In vinyl halide halogen atom is attached to a sp2 hyrbidized carbon. Due to the following resonating struc-
tures the carbon-halogen bond acquires a partial double bond character.

– +
CH2 = CH — Cl : CH2 — CH = Cl :
:

STUDY MATERIAL: XII CHEMISTRY

:

4 HALOALKANES AND HALOARENES

 This result, the C – Cl bond length of vinyl chloride to decrease to 1.69Å from the single bond length of
1.77 Å. This decrease in the value of bond length supports to the presence of partial double bond charac-
ter in C – Cl bond. Similarly, in aryl halides (such as C6H5Cl) chlorine atom is attached to the sp2 hybrid-
ized carbon of benzene ring. Due to the resonance effect (+R) of the halogen atom, the carbon-halogen
bond acquires double bond character. This is clear from the following resonating structures of chloroben-
zene :
: Cl: +Cl: +Cl : +Cl:
:

:
In chlorobenzene the value of the C – Cl bond length is 1.60Å. This value is less to the single bond length
of 1.77Å. This decrease in the bond length supports to the existence of partial double bond character in
C – Cl bond.

LEARNING CHECK-1
Q.1 What are Alkyl Halides?
Q.2 What other types of Organohalogen compounds are there?
Q.3 What general symbolic formula is often used to represent alkyl halides?
Q.4 How are Alkyl Halides named in the common system of nomenclature?
Q.5 What would the IUPAC and common names be for the following compounds?
Br
H CH2 – F
(a) (b) (c) CH2Cl2
H H
Q.6 What is the order of Carbon-Halogen bond strengths?

10.4 METHODS OF PREPARATION

10.4.1 From Alcohols
(i) By action of dry H–X (Grove’s Process) :

R – OH + H – X 
2
Anhydrous ZnCl
R–X + H2O
300
Alcohol
The reactivity order of HX in the above reaction is : HI > HBr > HCl > HF
The reactivity order of alcohols in the above reaction is : 3° > 2° > 1° > MeOH
(ii) Action of PCl3 :

R OH Cl
R OH + P Cl 3R Cl + H3 PO3
R OH Cl Chloro alkane phosphorous acid
Alcohol

STUDY MATERIAL: XII CHEMISTRY 5 HALOALKANES AND HALOARENES

 (iii) Action of PCl5 :

R Cl Cl
O + P Cl R Cl + HCl + POCl3
H Cl Cl Chloro alkane
Alcohol
Bromine or iodine derivatives can not be obtained from the above reaction because due to larger size of
bromine or iodine, PBr5 or PI5 are unstable.
(iv) Action of Thionyl chloride (Darzen’s Process) : It is the best method for preparation of alkyl chloride
2R–OH + SOCl2   2R–Cl + SO2(g) + HCl(g)
pyridine

Alcohol Thionyl Alkyl

chloride chloride
(v) R – OH + NaBr + H2SO4 R – Br + NaHSO4 + H2O
(vi) R  OH 
red P/X 2
RX
X 2  Br2 , I2
Note :
* The reactions of primary and secondary alcohols with HX require the presence of a catalyst, ZnCl2. With
tertiary alcohols, the reaction is conducted by simply shaking with concentrated HCl at room temperature.
* Good yields of R—I may be obtained by heating alcohols with sodium or potassium iodide in 95% phosphoric
acid.
* The order of reactivity of alcohols with a given haloacid is 3° > 2° > 1°.
* The carbon-oxygen bond in phenols has a partial double bond character and is difficult to break being
stronger than a single bond.

10.4.2 From Hydrocarbons

(a) By free radical halogenation :
Free radical chlorination or bromination of alkanes gives a complex mixture of isomeric mono- and
polyhaloalkanes, which is difficult to separate as pure compounds. Consequently, the yield of any one
compound is low.
CH3CH 2 CH 2 CH3   CH 3CH 2 CH 2CH 2Cl  CH3CH 2CHClCH3
Cl2 /UV light
or heat
(b) By electrophilic substitution :
* Aryl chlorides and bromides can be easily prepared by electrophilic substitution of arenes with chlorine
and bromine respectively in the presence of Lewis acid catalysts like iron or iron(III) chloride.
CH3 CH3 CH3
Fe +
+ X2
dark
X X
o-Halotoluene p-Halotoluene
* The ortho and para isomers can be easily separated due to large difference in their melting points.
* Reactions with iodine are reversible in nature and require the presence of an oxidising agent (HNO3,
HIO4) to oxidise the HI formed during iodination.
* Fluoro compounds are not prepared by this method due to high reactivity of fluorine.
(c) Sandmeyer’s reaction :
* When a primary aromatic amine, dissolved or suspended in cold aqueous mineral acid, is treated with
sodium nitrite, a diazonium salt is formed.
STUDY MATERIAL: XII CHEMISTRY 6 HALOALKANES AND HALOARENES
 + –
NH2 NaNO2 + HX N2X

273-278 K
Benzene diazonium
halide
When benzene diazoniumchloride is treated with Cu2Cl2 in conc. HCl, the N2Cl group is replaced by
chlorine atom. This reaction is called Sandmeyer’s reaction.
+
N2Cl Cl
+ Cu2Cl2/HCl (conc.) 
Sandmeyer 's
+ N2
reaction
Benzene
Chlorobenzene
diazonium chloride
+ Br
N NCl
+ Cu2Br2/HBr 
Sandmeyer 's
 + N2
reaction
Bromobenzene
Iodobenzene can be prepared by reacting benzene diazonium chloride with KI solution.
+ I
N NCl

+ KI  + N2 + KCl
Iodobenzene
* Replacement of the diazonium group by iodine does not require the presence of cuprous halide and is done
simply by shaking the diazonium salt with potassium iodide.
(d) From alkenes
(i) Addition of hydrogen halides:
H H H H
| | | |
R – C  C – H + H – X  R – C  C – X
| |
H H
Alkene Mono haloalkane
From alkyne we can obtain only dihaloalkane.
CH3CH = CH2 + H – I  CH3CH2CH2I + CH3CHICH3
minor major
(ii) Addition of halogens: R – CH = CH2 + Cl2  R  CH  CH 2
| |
Cl Cl
Alkene Alkylene chloride
CH 2 CH 2 Br
|| CH3 – CH – CH 2
Ex. + Br2  | ; CH3–CH=CH2 + Br2  | |
CH 2 CH 2 Br
Br Br
1,2-Dibromoethane (colourless) 1,2-Dibromopropane
STUDY MATERIAL: XII CHEMISTRY 7 HALOALKANES AND HALOARENES
10.4.3 Halogen Exchange :
Finkelstein reaction : Alkyl iodides are often prepared by the reaction of alkyl chlorides/bromides with NaI
in dry acetone.
R – X + NaI  R – I + NaX [X = Cl, Br]
NaCl or NaBr thus formed is precipitated in dry acetone. It facilitates the forward reaction according to
Le Chatelier’s Principle.
Swarts reaction : The synthesis of alkyl fluorides is best accomplished by heating an alkyl chloride/bromide in
the presence of a metallic fluoride such as AgF, Hg2F2, CoF2 or SbF3.
H3C – Br + AgF  H3C – F + AgBr

10.5 PHYSICAL PROPERTIES

Melting and boiling points :
* Alkyl halide have higher bp’s and mp’s than alkanes having the same number of carbons because of
intermolecular forces of attraction (dipole-dipole and van der Waals) are stronger in the halogen derivatives.
* Methyl chloride, methyl bromide, ethyl chloride and some chlorofluoromethanes are gases at room
temperature. Higher members are liquids or solids.
* Bp’s and mp’s increase as the size of R increases.
* Bp’s and mp’s increase as the size of X increase.
* For the same alkyl group, the boiling points of alkyl halides decrease in the order: RI > RBr > RCl > RF.
This is because with the increase in size and mass of halogen atom, the magnitude of van der Waal forces
increases.
* The boiling points of isomeric haloalkanes decrease with increase in branching.
For example, 2-bromo-2-methylpropane has the lowest boiling point among the three isomers.
CH3
|
CH3CH 2 CH 2 CH 2 Br CH3CH 2CHCH3 CH3  C  CH 3
| |
Br Br
b.p./K 375 364 346
* The para-isomers are high melting as compared to their orthoand meta-isomers. It is due to symmetry of
para-isomers that fits in crystal lattice better as compared to ortho- and meta-isomers.

Density :
Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than water. The density increases with
increase in number of carbon atoms, halogen atoms and atomic mass of the halogen atoms

Solubility :
* The haloalkanes are only very slightly soluble in water.
* Haloalkanes tend to dissolve in organic solvents because the new intermolecular attractions between
haloalkanes and solvent molecules have much the same strength as the ones being broken in the separate
haloalkane and solvent molecules.

10.6 CHEMICAL REACTIONS

10.6.1 Reactions of Haloalkanes
The reactions of haloalkanes may be divided into the following categories:
(i) Nucleophilic substitution (ii) Elimination reactions (iii) Reaction with metals.

STUDY MATERIAL: XII CHEMISTRY 8 HALOALKANES AND HALOARENES

(1) NUCLEOPHILIC SUBSTITUTION
In this type of reaction, a nucleophile reacts with haloalkane (the substrate) having a partial positive charge
on the carbon atom bonded to halogen. A substitution reaction takes place and halogen atom, called
leaving group departs as halide ion. Since the substitution reaction is initiated by a nucleophile, it is called
nucleophilic substitution reaction.
  + – –
–
Nu : + — C – X C – Nu + X

–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Reagent Nucleophile Substitution Class of main
(Nu–) product R – Nu product
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
NaOH (KOH) HO– ROH Alcohol
H2O H2O ROH Alcohol
NaOR' R'O – ROR' Ether
NaI I– R–I Alkyl iodide
NH3 NH3 RNH2 Primary amine
R'NH2 R'NH2 RNHR' Sec. amine
R'R''NH R'R''NH RNR'R'' Tert. amine
KCN C  N: RCN Nitrile (cyanide)
AgCN Ag – CN: RNC Isonitrile
(isocyanide)
KNO2 O=N–O R–O–N=O Alkyl nitrite
AgNO2 Ag  O
  N  O R – NO2 Nitroalkane
R'COOAg R'COO – R'COOR Ester
LiAlH4 H RH Hydrocarbon
R'– M+ R'– RR' Alkane
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––

* Groups like cyanides and nitrites possess two nucleophilic centres and are called ambident nucleophiles.

(a) SN1 Reactions : These reactions complete in two steps. In the first step a carbocation is formed from
alkyl halide molecule. First step is a slow step so it is also the rate determining step. In the second step an
attacking nucleophile attacks this carbocation and forms the final product. In this reaction rate of reaction
is dependent on the concentration of alkyl halide molecule only, not on the concentration of nucleophile. So
the reaction is called unimolecular substitution reaction. Molecularity of reaction is two but the order of
reaction is one. All tertiary halides and sometimes secondary halides show this type of reaction. Polar
medium is necessary for the reaction.
CH3 CH3
|   |
Example : CH3  C  CH 3 + K  O H 
H  OH
 CH3 – C  OH  KX
| |
CH3 CH3
tertiary Butylhalide tertiary Butylalcohol

STUDY MATERIAL: XII CHEMISTRY 9 HALOALKANES AND HALOARENES

 Mechanism :

CH3 CH3
 
(a) CH3  CH  X 
Slow step
CH 3  C 
 X (Ter. butyl carbocation)
 
CH3 CH3

CH3 CH3
|  |
(b) CH3  C  O H 

Fast step
CH3  C  OH
| |
CH3 CH3
(ii) SN2 Reactions : These reactions are completed in a single step.
In these reactions an attacking nucleophile attacks from back side of the central carbon atom of alkyl
halide. This back side attack is known as ‘Walden Inversion’. When nucleophile attacks on central atom
then a transition state is formed in which the attacking nucleophile and halogen atom are both linked with a
half bond with the central atom. This stage is unstable stage, after sometime halogen atom attract bonded
electrons towards itself and releases in the form of halide ion while attacking nucleophile forms complete
bond with the central carbon. In this reaction, bond breaking and bond forming process both can take
place simultaneously and rate of reaction is dependent on the concentration of alkyl halide and concentration
of attacking nucleophile both. So the reaction is called as bimolecular substitution reaction. Molecularity of
reaction is two and the order of reaction is also two. In this reaction product is 100% opposite rotatory
than reagent. Polar medium is not necessary for this type of reaction.
All primary halides and sometimes 2° halide show this type or reaction.
Ex. CH3–X + K–OH  CH3–OH + KX

H H H

H C X + OH - HO C X HO C H + X¯

H H H H
transition state

Rate of reaction : Greater the stability of carbocation, greater will be its ease of formation from alkyl
halide and faster will be the rate of reaction. In case of alkyl halides, 3° alkyl halides undergo SN1 reaction
very fast because of the high stability of 3° carbocations. The order of reactivity of alkyl halides towards
SN1 and SN2 reactions is :
For SN2 reaction

Tertiary halide; Secondary halide; Primary halide; CH3X

For SN1 reaction

Examples of Nucleophilic substitution reaction :

(i) Hydrolysis :
(a) With aqueous KOH : Alkyl halides are hydrolysed to corresponding alcohols by boiling them with
aqueous alkali solution.
STUDY MATERIAL: XII CHEMISTRY 10 HALOALKANES AND HALOARENES
 R–X + K–OH  R – OH + K – X
Alcohol
(b) Using moist Ag2O :
2R–X + Ag2O + H2O  2R – OH + 2AgX
Alcohol
(ii) Ether Synthesis :
(a) Reaction with NaOR :
R–X + NaOR  R – O – R + NaX
Ether
The above reaction is called “Williamson's ether synthesis”.
(b) Using dry Ag2O :
2R–X + Ag2O  R – O – R + 2AgX
Ether
(iii) Reaction with Na2S :
R X Na
+ S R S R + 2NaX
R X Na
dialkyl sulphide
(iv) Reaction with KSH :
R–X + K–SH  R–SH + KX
Alkane thiol
(v) Reaction with KCN :
R – X + KCN  R – C N + KX
Alkane nitrile
Alkane nitrile is an important compound which gives following products.
(a) R – C  N 
LiAlH 4 /Re duction R – CH2 – NH2
Alkane amine
(b) R – C  N 
2 
H O
R  C  NH 2
partial hydrolysis ||
O
Alkane amide
H O
(c) R – C  N 
3  R COH + NH3
Complete hydrolysis ||
O
Carboxylic acid
(vi) Reaction with AgCN :
R–X + AgCN  R–N   C + AgX
Alkane isocynide
 C 
 R–NH2 +
Hydrolysis
R–N  HCOOH
Alkaneamine
H
|
 
Re duction
R–N 
 C R  N  CH3
secondary amine

STUDY MATERIAL: XII CHEMISTRY 11 HALOALKANES AND HALOARENES

 (vii) Reaction with KNO2 :
 
R–X + K  O – N=O  R–O–N=O + KX
Alkylnitrite
(viii) Reaction with AgNO2 :
O
R–X + Ag–O–N=O  R– N + AgX
O
Nitroalkane
(ix) Reaction with Na2SO3 (Strecker reaction) :
R–X + Na2SO3  RSO3Na + NaX
Alkyl sodium
sulphonate
(x) Reaction with silveracetate (Esterification) :
R X + Ag O – C – CH3  CH3 – C – O – R + AgX
|| ||
O O
Silveracetate Ester
(xi) Reaction with benzene ‘Friedel-Craft reaction’ :
H R
+ X–R 
AlCl3
180C
 + H–X
Alkyl benzene
Alkyl halide shows electrophilic substitution in the above reaction, which is exception in alkyl halide.

STEREOCHEMICAL ASPECTS :
Basic terms :
(a) Optical activity :
(i) Plane polarised light can be obtained by passing ordinary light through Nicol prism.

 

ordinary light Nicol prism Plane polarised

waves vibrating in all directions waves vibrating in one direction.

Plane rotated to the left Plane rotated to the right

(ii) When certain organic compounds in their solutions are placed in the path of a plane polarized lights have
the remarkable property of rotating its plane through a certain angle which may be either to the left or to the
right if the polarized light has its vibrations in the plane AB before entering such a solution, the direction on
leaving it will be changed to say A'B', the plane have been rotated through the angle as in a (fig.).
(iii) This property of a substance of rotating the plane polarized light is called optical activity and the substance
possessing it is said to be optically active.

STUDY MATERIAL: XII CHEMISTRY 12 HALOALKANES AND HALOARENES

 A A'
A'

solution or
B B' B'
(iv) Substance rotating the plane of polarised light to the left. This form is named as laevorotatory.
(Latin, laevous = left) or direction (–) form
(v) Substance rotating the plane of polarized light exactly to the same extent but to the right this form is named
dextrorotatory (Latin Dexter - right) or direction (+) – form.
(vi) An inactive form which does not rotate the plane polarized light at all. This mixture of equal amounts of (+)
and (–) — forms and hence it is optically inactive. It is named (±) - mixture or Racemic mixture.
(Latin, Racemic - mixture of equal compounds)

(b) Chirality center (Stereogenic centre, stereo centre or assymetric carbon)

A carbon bonded to four different groups is called a chirality center. The chirality center in each of the
following compounds is indicated by an asterisk. For example, the fourth carbon in 4-octanol is a chirality
center because it is bonded to four different groups (H, OH, CH2CH2CH3, and CH2CH2CH2CH3).
Notice that the difference in the groups bonded to the chirality center is not necessarily right next to the
chirality center the propyl and butyl groups are different groups. The starred carbon in 2,4-dimethylhexane
is a chirality center because it is bonded to four different groups – methyl, ethyl, isobutyl, and hydrogen.
CH3
* * | *
CH3CH 2 CH 2CHCH 2CH 2CH 2 CH3 CH3CHCH 2CH3 CH3CHCH 2 CHCH 2CH3
| | |
OH Br CH3
4-octanol 2-bromobutane 2,4-dimethylhexane
Notice that the only carbons that can be chirality centers are sp3 hybridized carbons, sp2 and sp hyrbidized
carbons cannot be chirality centers because they cannot have four groups attached to them.
All organic compounds containing on asymmetric carbon atom (lactic acid, amyl alcohol etc.) are optically
active.
OH CH3
|
CH3 COOH H C
5 2 – C* – CH2 OH
|
H H
lactic acid (Optically active) amyl alcohol (optically active)

Types of symmetry :
(i) Plane of symmetry or mirror plane : A imaginary plane which bisect a molecule such a way that one half
of the molecule is exactly the mirror image of the other half.

(ii) Centre of symmetry : A imaginary point in a molecule which divides the structures of molecule in to same
parts.

STUDY MATERIAL: XII CHEMISTRY 13 HALOALKANES AND HALOARENES

 Centre of symmetry
COOH

HOOC H

trans-cyclohexane-1, 4-dicarboxylic acid

Symmetrical molecule is always optically inactive.
Chirality : This term has been recently used to describe such molecules which have no elements of
symmetry, thus asymmetrical molecules are also called chiral molecules and optical activity is attributed to
certain chiral centres in them. An asymmetrical carbon is a chiral centre. An asymmetrical object cannot be
superimposed on its mirror image.
Chirality is lost when the two atoms bonded to an asymmetric carbon become similar thus while lactic acid
is optically active, propionic acid is not.

Chirality or molecular dissymmetry cause of optical Isomerism :

(i) The necessary condition for a molecule to exhibit optical isomerism is dissymmetry or chirality.
(ii) Thus all organic compound which contain asymmetric carbon (c* abde) are chiral and exist in two
tetrahedral forms.
(ii) Although the two forms (I and II) have the same structure, they have different arrangements of groups
a, b, d, e about the asymmetric carbon in fact, they represent asymmetric molecules they do not have
a plane of symmetry, they are related to each other as an object to its mirror image and are non
superimposable.
(iv) The two models or structures (I and II) actually stand for dextro or (+) and laevo or (–) isomers.
Since they are related to each other as mirror images, they are commonly called Enantiomers (Greek
word, enantio = opposite, morph - form) or enantiomers thus optical isomerism is now often referred
to as anenatiomers.
(v) Optical isomers or enantiomers due to the presence of an asymmetric carbon atom in a compound
differ only in the arrangement or configuration of groups of tetrahedral perspective.
(vi) Examples of compounds which exist as (+) and (–) enantiomers.
Mirror
COOH COOH

C C
H OH
CH 3 HO CH3

(I) (+) and (–) lactic acid (II)

Mirror

H H

C C
C6H5
C6H5
Cl CH3 CH3
Cl
(I) (+) and (–) -1-chloro-1-phenyl ethane (II)

STUDY MATERIAL: XII CHEMISTRY 14 HALOALKANES AND HALOARENES

 Criterion of enantiomerism :
(i) The compound which contain one or more asymmetric carbon atoms show enantiomerism.
(ii) But there are some known compound which have asymmetric carbon but due to presence of plane of
symmetry do not show enantiomerism.
(iii) Meso tartaric acid has two asymmetric carbons but is optically inactive.

COOH Plane of
| symmetry
H – C *– OH

H – C *– OH
|
COOH
Meso tarteric acid
Difference between Chiral and Achiral :
* In general, a molecule with no stereogenic centers will not be chiral. There are exceptions to this
* With one stereogenic center, a molecule will always be chiral.
* With two or more stereogenic centers, a molecule may or may not be chiral, e.g. Meso compound (contains
a plane of symmetry or a mirror plane)
* Achiral molecules contain a plane of symmetry but chiral molecules do not.
* A plane of symmetry is a mirror plane that cuts the molecule in half, so that one half of the molecule is a
reflection of the other half.

(c) Retention: Retention of configuration is the preservation of integrity of the spatial arrangement of bonds
to an asymmetric centre during a chemical reaction or transformation. It is also the configurational correlation
when a chemical species XCabc is converted into the chemical species YCabc having the same relative
configuration.
a Y– a
c c
b X b Y
CH3 CH3
Heat
H CH2 OH + H – Cl H CH2 Cl + H – OH
CH2 CH2
Ex :
CH3 CH3
(–)–2-Methylbutan-1-ol (+)-1-Chloro-2-methylbutane
(d) Inversion, retention and racemisation: There are three outcomes for a reaction at an asymmetric
carbon atom. Consider the replacement of a group X by Y in the following reaction;

C2H5 C2H5 C2H5

Y H Y H
H
H
CH3 Y CH3 Y CH3
B Y A
A+B

STUDY MATERIAL: XII CHEMISTRY 15 HALOALKANES AND HALOARENES

 If (A) is the only compound obtained, the process is called retention of configuration.
If (B) is the only compound obtained, the process is called inversion of configuration.
If a 50 : 50 mixture of the above two is obtained then the process is called racemisation and the product is
optically inactive, as one isomer will rotate light in the direction opposite to another.

Stereochemistry of SN1 reaction : The positively charged carbon of the carbocation is sp2 hybridised, and
the three bond connected to this carbon are in the same plane. In the 2nd step of the SN1 reaction, the
nucleophile can approach the carbocation from either side of the plane.

Br

(a) (b)

H2O H 2O

(a) (b)

+ H H +
-H + + -H
HO + O O + OH
H H
H H
Inverted Same configuration
configuration (retention)

The SN1 reaction of an alkyl halide in which the leaving group is attached to the chirality centre leads to the
formation of two stereoisomers; attack of the nucleophile on one side of the planar carbocation forms one
stereoisomer and attack on the other side produces the other isomer.
R' R' R'

 H 2O 
 H R   HBr
R H R H
Br HO OH
In the reaction of (S) – 2-bromobutane with water two substitution products are formed one product has the
same relative configuration. In an SN1 reaction the leaving group leaves before the nucleophile attacks. This
means that the nucleophile is free to attack from either side of the planar carbocation.

CH3 H3C CH3

 H 2 O S  
N 1 conditions 
R H H R R H
Br HO OH
(R)-2-butanol inverted (S)-2-butanol retended

Although one might expect that equal amounts of two isomers would form in an SN1 reaction but a greater
amount of the inverted product is obtained in most cases. Typically, 50 – 70% of the product of an SN1
reaction is the inverted produced. If the reaction leads to the formation of equal amounts of the two products,

STUDY MATERIAL: XII CHEMISTRY 16 HALOALKANES AND HALOARENES

 the reaction is said to take place with complete racemization, when more of the inverted product is formed, the
reaction is said to take place with partial racemization ions.

Stereochemistry of SN2 Reaction : An SN2 reaction the nucleophile attacks from the backside, that is, from
the side directly opposite the leaving group. This mode of attack causes a change in configuration of the carbon
atom that is the target of the nucleophile. As the displacement takes place, the configuration of the carbon atom
under attack inverts it is turned inside out in such a way that an umbrella is turned inside out in a strong gale.

R R R
 
HO Br HO C Br HO + Br
R' R'
R" R' R" H

Inversion of Configuration

(2) ELIMINATION REACTIONS

The E2 Reaction: There are two important mechanism for elimination. The reaction of ethyl bromide with
hydroxide ion is an example of an E2 reaction. It is a second-order reaction because the rate of reaction
depends on the concentration of both ethyl bromide and hydroxide ion.
CH3CH2Br + HO–  CH2 = CH2 + H2O + Br–
Rate = K [Alkyl halide] [Base]
The rate law tells us that alkyl bromide and hydroxide ion both are involved in the transition state of the rate
determining step of the reaction. The following mechanism agrees with the observed second order kinetic.
The E2 reaction is a concerted one step reaction. The proton and the bromide ion are removed in the same
step.
 
H O H
 H 2 O  Br 


Br
In an E2 reaction, a base removes a proton from a carbon adjacent to the carbon bonded to the halogen.
As the proton is removed, the electrons, the hydrogen shared with carbon moves forward to the carbon
bonded to the halogen. As there electrons move in the halogen leaves taking its bonding electrons with it.
The removal of the proton and the halide ion from alkyl halide is known as dehydrogenation.
The carbon to which the halogen is attached is called the -carbon. An adjacent is called a -carbon.
Because the reaction is initiated by the removal of proton from the -carbon, on E2 reaction is sometimes
called a -elimination reaction. It is also called  1,2-elimination reaction because the atoms being
removed from adjacent carbon.

  carbon
B
H R
R  BH  Br _
R Br R

  carbon
STUDY MATERIAL: XII CHEMISTRY 17 HALOALKANES AND HALOARENES
 2-bromopropane has two -carbon atoms from which a proton can be removed in an E2 reaction. Be-
cause the two carbons are identical, the proton can be removed from either one. The product is propene.
CH3
H3C  CH 3O 
 H3C  CH 3OH  Br
Br CH2
If there is possibility of formation of more than one alkene due to the availability of more than one -
hydrogen atoms, usually one alkene is formed as the major product. These form part of a pattern first
observed by Russian chemist, Alexander Zaitsev (also pronounced as Saytzeff) who formulated a rule
which can be summarised as “in dehydrohalogenation reactions, the preferred product is that alkene which
has the greater number of alkyl groups attached to the doubly bonded carbon atoms.” Thus, 2-bromopentane
gives pent-2-ene as the major product.
Br
 OH |
H3C  CH 2  CH  CH  CH3  H 3C  CH 2  CH 2  CH  CH 2
pent-2-ene (81%) |
H
2-Bromopentane

 OH
 H3C  CH 2  CH 2  CH  CH 2
Pent-1-ene (19%)
(3) REACTION WITH METALS : Most organic chlorides, bromides and iodides react with certain metals
to give compounds containing carbon-metal bonds. Such compounds are known as organo-metallic com-
pounds.
(i) With Na : (Wurtz reaction)
R – X + 2Na + X – R dry ether
 R – R + 2NaX
Alkane
(ii) With Mg : (Grignard reaction)
R – X + Mg  dry ether
 R – Mg – X
Grignard’s reagent
In the Grignard reagent, the carbon-magnesium bond is covalent but highly polar, with carbon pulling
electrons from electropositive magnesium; the magnesium halogen bond is essentially ionic.
 
R  Mg X
Grignard reagents are highly reactive and react with any source of proton to give hydrocarbons. Even
water, alcohols, amines are sufficiently acidic to convert them to corresponding hydrocarbons.
RMgX + H2O ––––RH + Mg(OH)X
It is therefore necessary to avoid even traces of moisture from a Grignard reagent. On the other hand,
this could be considered as one of the methods for converting halides to hydrocarbons.
(iii) With Zn dust : (Frankland reaction)
R X 2Zn X R  R–Zn–R + ZnX2
Dialkyl zinc
Dialkyl zinc is known as ‘Frankland’s reagent’.

STUDY MATERIAL: XII CHEMISTRY 18 HALOALKANES AND HALOARENES

 (iv) With Li :
R–Cl + 2Li  RLi + LiCl
dry ether

Alkyl lithium
(v) With Na-lead alloy :
4CH3 – CH 2 + 4 Na–Pb  (CH3  CH 2 ) 4 Pb  4NaCl  3Pb
| TEL
Cl (tetra ethyl lead)
Tetra ethyl lead is used as an antiknock agent.

10.6.2 REACTIONS OF HALOARENES

(1) Nucleophilic substitution :
(i) Resonance effect : The halogen atom is firmly attached with the benzene nucleus and acquires extra
stability due to resonance (+M) effect. Hence, the halogen atom cannot be easily replaced by other atoms
or group of atoms. So, aryl halides are less reactive than alkyl halides.
+ + +
Cl Cl Cl Cl

The halogen atom is replaced by other nucleophiles under forced conditions.

Difference in hybridisation of carbon atom in C—X bond :
In haloalkane, the carbon atom attached to halogen is sp3 hybridised while in case of haloarene, the carbon
atom attached to halogen is sp2-hybridised.
X H
sp2 hybrid carbon sp 3 hybrid carbon
C
R X
H
The sp2 hybridised carbon with a greater s-character is more electronegative and can hold the electron
pair of C—X bond more tightly than sp3-hybridised carbon in haloalkane with less s-chararcter. Thus,
C—Cl bond length in haloalkane is 177pm while in haloarene is 169 pm. Since it is difficult to break a
shorter bond than a longer bond, therefore, haloarenes are less reactive than haloalkanes towards
nucleophilic substitution reaction.
(iii) Instability of phenyl cation: In case of haloarenes, the phenyl cation formed as a result of self-ionisation will
not be stabilised by resonance and therefore, SN1 mechanism is ruled out.
(iv) Because of the possible repulsion, it is less likely for the electron rich nucleophile to approach electron rich
arenes.
Replacement by –OH group :
Cl OH

+ NaOH (aq)
300º C
High pressure
+ NaC

Chloro Phenol
benzene
The presence of an electron withdrawing group (– NO2) at ortho- and para-positions increases the reactivity
of haloarenes.
STUDY MATERIAL: XII CHEMISTRY 19 HALOALKANES AND HALOARENES
 .. ..
: Cl : OH : Cl : OH
NO2 NO2
(i) NaOH, 443 K (i) NaOH, 368 K
;
(ii) H (ii) H
NO2 NO2 NO2 NO2
..
: Cl : OH
O2N O2N NO2
NO2

Warm
H 2O
NO2 NO2

The effect is pronounced when (– NO2) group is introduced at ortho and para- positions. However, no
effect on reactivity of haloarenes is observed by the presence of electron withdrawing group at meta-
position.
(2) Electrophilic substitution reactions :
* Halogen atom besides being slightly deactivating is o, p directing; therefore, further substitution occurs
at ortho- and para positions with respect to the halogen atom.
* Due to resonance, the electron density increases more at ortho- and para-positions than at meta-
positions.
* The halogen atom because of its –I effect has some tendency to withdraw electrons from the benzene
ring. As a result, the ring gets somewhat deactivated as compared to benzene and hence the electrophilic
substitution reactions in haloarenes occur slowly and require more drastic conditions as compared to
those in benzene.
(i) Halogenation :
Cl Cl Cl
FeCl3, Room temp.
Cl
+ Cl2 Dark (Minor) + (Major)
Chloro o–Dichloro
benzene benzene Cl
p–Dichlorobenzene
(ii) Nitration :
Cl Cl Cl
NO2
+ HNO3   (Minor) + (Major)
H 2SO4conc.

fuming
Chloro o–Nitrochloro NO2
benzene benzene p–Nitrochlorobenzene
(iii) Sulphonation :
Cl Cl Cl
SO3H
+ H2SO4
Fuming
Chloro o-Chlorobenzene (Minor) + SO3H (Major)
benzene sulphonic acid p–Chloro benzene
sulphonic acid

STUDY MATERIAL: XII CHEMISTRY 20 HALOALKANES AND HALOARENES

 (iv) Friedel–Craft reaction :
Cl Cl Cl
AlCl3 CH3
+ CH3Cl
+
Chloro o-Chloro CH3
benzene toluene p–Chlorotoluene

(Minor) (Major)

Cl O Cl
Cl CH3
O +
||
+ H3C  C  Cl 
Anhyd. AlCl3
 2-Chloroacetophenone
(Minor) O CH3
4-Chloroacetophenone
(3) Reaction with metals : (Major)
Wurtz–Fittig reaction : Aryl halide and alkyl halide when heated together in the presence of sodium and
ether, yield homologues of benzene.

Cl + 2Na + ClCH2CH3 

ether
 CH2CH3 + 2NaCl

Ethylbenzene
When only aryl halides are heated with metallic sodium, the reaction is known as Fittig reaction and the
product is diaryl.

Cl + 2Na + Cl 
 —— + 2NaCl
ether

Diphenyl

LEARNING CHECK-2
Q.1 What types of forces effect the boiling points of Alkyl Halides?
Q.2 What is meant by the term polarizability?
Q.3 Despite their dipole moments, the boiling points of Alkyl Fluorides are lower than those of Alkanes of comparable
molecular weight. How can this be explained?
Q.4 What is the solubility of Alkyl Halides in water?
Q.5 What would be the mechanism of the substitution reaction between Methyl Bromide and Hydroxide ion?
Q.6 What would be the mechanism of the substitution reaction between tert-Butyl chloride and Methanol?
Q.7 By what other name is this stereochemical result known?
Q.8 What are the rate equations for the SN1 and SN2 mechanisms?
Q.9 What is an Aprotic solvent?
Q.10 What type of solvent favours SN1 and why?
Q.11 What is -elimination?
Q.12 What factors favour each mechanism in the competition between SN1 and E2?

Q.13 Identify the chiral molecule in the following pair: Cl

Cl

STUDY MATERIAL: XII CHEMISTRY 21 HALOALKANES AND HALOARENES

10.7 POLY HALOGEN COMPOUNDS
Carbon compounds containing more than one halogen atom are usually referred to as polyhalogen compounds.
10.7.1 Dichloromethane (Methylene chloride) :
Dihalogen derivatives of alkanes are obtained by replacing its two hydrogen atoms by two halogen atoms.
Dichloromethane is thus a derivative of methane in which two H-atoms of methane molecule are replaced by
two Cl atoms.
Industrial preparation : Dichloromethane is prepared on industrial scale by direct chlorination of methane (or
natural gas).
 Cl ,h  Cl ,h  Cl ,h  Cl ,h
CH 4 
2  CH3Cl 
2  CH 2 Cl2 
2  CHCl3 
2  CCl4
methane  HCl chloromethane  HCl dichloromethane  HCl trichloromethane  HCl tetrachloromethane
In this reaction, a mixture of different chloro derivatives is obtained. Dichloromethane is separated from this
mixture by fractional distillation.
Properties :
(i) Dichloromethane is a colourless, sweet-smelling, volatile liquid (b.p. 40°C)
(ii) It has low inflammability.
Uses : Dichloromethane is used (i) as an effective extraction solvent in pharmaceutical and food industries. (ii)
as a paint remover.

10.7.2 Chloroform (Trichloromethane) :

Physical Properties :
(i) Chloroform is a colourless, sweet smelling liquid.
(ii) Insoluble in water and soluble in organic solvent.
(iii) Vapours of chloroform are poisonous in nature. It cause temporary unconsciousness, so it is used as an
anasthetic agent.
(iv) Boiling point of CHCl3 is 61ºC.
(v) It is best solvent for fats, oil and wax.
(vi) Iodoform is yellow crystalline solid. It has melting point 119ºC.

Chemical properties :
(a) Oxidation : In presence of light it forms poisonous gas phosgene with atmospheric oxygen or with air.
1
CHCl3 + O
2 2   Cl  C  Cl  HCl
light
||
O
Chloroform Phosgene
Precautions :
(i) It is kept in a dark room in coloured bottles filled upto the brim.
(ii) For removal of phosgene we can used 1% ethanol solution which converts poisonous phosgene into
non–poisonous diethylcarbonate.

H O C2H5 O C 2H 5
Cl
O C + O C + 2 HCl

Cl H O C2H5 O C2H5
Phosgen Ethyl alcohol Diethyl carbonate (Non-spoisonous substance)
We use silver nitrate solution to check the impurity of phosgene in solution which will form white ppt. of AgCl
with HCl.

STUDY MATERIAL: XII CHEMISTRY 22 HALOALKANES AND HALOARENES

 (b) Reduction :
+2H
CH Cl + HCl
Zn/HCl (Alc.) 2 2

+4H
CHCl3 CH3Cl + 2HCl
Zn/HCl (aq.)

+6H
CH4 + 3HCl
Zn/H2O
Uses :
(a) As an anaesthetic agent. (CHCl3. Chloroform) and CHI3 as antiseptic.
(b) CHCl3 as solvent for fat, waxes, rubber etc.
(c) In preparation of chloroitone (a hypnotic agent) and nitrochloroform (an insecticide) tear gas.
(d) CHCl3 as an preservative for antomical specimen.
(e) As a lab reagent to identity pr. amine and for other analytical tests.

10.7.3 Triiodomethane (Iodoform) : It was used earlier as an antiseptic but the antiseptic properties are due to the
liberation of free iodine and not due to iodoform itself. Due to its objectionable smell, it has been replaced by
other formulations containing iodine.

10.7.4 Tetrachloromethane (Carbon tetrachloride) :

Uses :
(a) It is produced in large quantities for use in the manufacture of refrigerants and propellants for aerosol cans.
(b) It is used as feedstock in the synthesis of chlorofluorocarbons and other chemicals, pharmaceutical
manufacturing, and general solvent use.
Precautions :
(a) Exposure to carbon tetrachloride causes liver cancer in humans.
(b) Exposure to CCl4 can make the heart beat irregularly or stop. The chemical may irritate the eyes on
contact. When carbon tetrachloride is released into the air, it rises to the atmosphere and depletes the
ozone layer. Depletion of the ozone layer is believed to increase human exposure to ultraviolet rays, leading
to increased skin cancer, eye diseases and disorders, and possible disruption of the immune system.

10.7.5 Freons or CFC (Chloroflorocarbon) : Chlorofluoro derivatives of methane and ethane are called freons.
(i) Preparation of Freons :
CCl4 + HF 
5 SbCl
FCl3 + HCl
F–11
CFCl3 + HF 
5 SbCl
CF2Cl2 + HCl
F–12
C2Cl6 + 2HF 
SbCl5
C2F2Cl4 + 2HCl
Hexachloroethane F–112
(ii) Properties & uses of freons :
(a) Freons are colourless, odourless, unreactive and non-combustible liquids.
(b) They are also used as solvents.
(c) They have very low boiling points and are easily converted from gaseous state to liquid state, therefore
they are used as a coolant in A C. & Refrigerator.

STUDY MATERIAL: XII CHEMISTRY 23 HALOALKANES AND HALOARENES

 (d) They are used as a aerosole propellant in aeroplane & rockets.
(e) Most freon, even that used in refrigeration, eventually makes its way into the atmosphere where it
diffuses unchanged into the stratosphere. In stratosphere, freon is able to initiate radical chain reactions
that can upset the natural ozone balance.
(iii) Nomenclature of Freons :
The common name of freons is F-cba
where, c = number of carbon atoms – 1 , b =number hydrogen atoms + 1, a = total number of atoms of
fluorene

Example : CFCl3, C – 1 = 0, H + 1 = 1, F = 1  F-11

––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Formula C–1 H+1 F Name
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
CFCl3 1–1 = 0 0+1=1 1 F-11
CF2Cl2 1–1 = 0 0+1=1 2 F-12
C2F2Cl4 2–1 = 1 0+1=1 2 F-112
C2F3Cl3 2–1 = 1 0+1=1 3 F-113
C2F4Cl2 2–1 = 1 0+1=1 4 F-114
C2F5Cl 2–1 = 1 0+1=1 5 F-115
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––

10.7.6 p, p'-Dichlorodiphenyltrichloroethane(DDT) :
The first chlorinated organic insecticides.It is manufactured by heating a mixture of chloral and chlorobenzene
in the presence of concentrated sulphuric acid.

Cl H Cl
+ O = CH – CCl2 Conc. CH – CCl3 + H2O
Cl H Chloral H2SO4
Cl

DDT
DDT is not metabolised very rapidly by animals instead it is deposited and stored in the fatty tissues.

ADDITIONAL EXAMPLES

Example 1 :
The structure of an alkyl halide has a great effect on its reactivity. Because of this alkyl halides are often
classified into four groups. What are they?
Sol. Alkyl halides are classified as methyl, primary, secondary, or tertiary. The designation refers to the number of
alkyl groups attached to the Carbon bearing the Halogen.
R R
| |
X  CH3 X  CH 2  R X  CH  R
Methyl
XCR
Primary Secondary |
R
Tertiary

STUDY MATERIAL: XII CHEMISTRY 24 HALOALKANES AND HALOARENES

Example 2 :
What is the direction of the polarity of a Carbon Halogen bond?
Sol. Fluorine, Chlorine and Bromine are all more electronegative than Carbon. The electronegativity of Iodine is
similar to that of Carbon, but it is much more polarizable due to its large size. As a result, the Carbon Halogen
bond is polarized with a slight negative charge on the Halogen atom and a slight positive charge on the Carbon.

—C—X

Example 3 :
Is there any correlation between bond strength and bond length in the C – X series?
Sol. Yes, the Carbon-Halogen bond length increases as you go down the Halogen family due to the increasing size
of the Halogen atom. This increase in bond length may result in poorer orbital overlap, and hence contribute to
the lowering in bond strength.

Example 4 :
Fluorine is the most electronegative of the Halogens, yet Chloromethane has the largest dipole moment of the
halomethanes. How is this possible?
Sol. The size of a molecule’s dipole moment depends primarily on the magnitude of the partial charges and the
distance of separation. For the halomethanes, the dipole moment would be expected to increase with the
electronegativity of the Halogen and also increase with increasing bond length. Since these two trends run
counter to one another, Chloromethane ends up having the largest dipole moment of the series.

Example 5 :
Van der Waals forces depend to a large extent on the size of a molecule, yet the comparably sized compounds
Ethane and Bromomethane have widely different boiling points (– 89°C and 4°C, respectively.) Why is this?
Sol. The magnitude of Van der Waals forces is also dependent on the polarizability of a molecule’s electrons. The
more polarizable the electrons, the easier it is the create an induced dipole. The unshared pairs of electrons on
Bromine are much more polarizable than the shared electrons in the C – H sigma bonds of Ethane.

Example 6:
What are Freons?
Sol. Freons are Chlorofluorocarbons that were manufactured and used in refrigeration systems, as propellants, and
as cleaning solvents. They are suspected of causing significant damage to the Earth’s ozone layer.

Example 7 :
The densities of liquid Alkyl Halides are greater than those of hydrocarbons of comparable molecular weight.
Why is this?
Sol. Halogens have a larger mass to volume ratio than similarly sized Alkyl groups. For example, a Bromine atom is about
the same size as a methyl group but weighs significantly more (79 amu compared to a Methyl groups 15 amu).

Example 8 :
What happens when an Alkyl Halide is mixed with water?
Sol. Because of the insolubility of the Alkyl Halides, two layers will form. Monoalkylfluorides and Chlorides are less
dense than water and will float on top. Alkylbromides and iodides are denser than water and will sink to the
bottom. Polyhalogenation increases the density, so compounds such as CH2Cl2 and CHCl3 sink to the bottom.

STUDY MATERIAL: XII CHEMISTRY 25 HALOALKANES AND HALOARENES

Example 9 :
Arrange the following molecules in order of increasing boiling point :
(a) CH3CH2CH2Cl (b) (CH3)2CHCl (c) (CH3)2CHCH2Br
(d) CH3CH2CH2F (e) CH3CH2CH2CH2CH2Br
Sol. From lowest to highest boiling point: d, b, a, c, e. (remember, increased size = increased boiling point, increased
Halogen weight/size = increased boiling point, and increased branching = lower boiling point).

Example 10 :
What is the IUPAC system for naming Alkyl Halides?
Sol. First the longest alkyl chain is found (the parent chain.) The parent chain is then numbered from the direction
that will give the first substituent encountered (alkyl or Halogen) the lowest number. Halogen substituents are
indicated by using the prefixes Fluoro-, Chloro-, Bromo-, and lodo. The position of each substituent is indicated
by using the number of the Carbon to which it is attached. The substituents are listed in alphabetical order at the
beginning of the name. Ifa double bond exists in the parent chain then the parent chain is numbered from the end
that gives the lowest numbers to the Carbons of the double bond.
CH3CH2CH2 H
Cl CH 3 C=C
| |
CH3CH 2 CH 2 CH 2CH 2CH 3 H CH3CH2CH2CH2CH2Br
4-chloro-2-methyl hexane
(E)-10-bromo-4-decene
Example 11 :
The Trihalogenated Methanes are given different common names than the other Alkyl Halides. What are they
called?
Sol. They are known as the Haloforms, the best known of which is Chloroform, CHCl3.

Example 12 :
What is the name for saturated Hydrocarbons in which all of the Hydrogens have been replaced by Halogens?
Sol. They are known as Perhaloalkanes.
CF3CF2CF2CF2CF2CF3 Perfluorohexane

Example 13 :
What is the SN2 mechanism?
Sol. SN2 is a one step mechanism in which a nucleophile attacks a substrate such as an Alkyl Halide and directly
kicks out the leaving group:

Nu : X Nu :X

Example 14 :
What is the SN1 mechanism?
Sol. SN1 is a two step mechanism. In the first step, a substrate such as an Alkyl Halide dissociates into a carbocation
and a leaving group. In the second step, the carbocation reacts with the nucleophile, which donates a pair of
electrons to the carbocation to form a covalent bond. The first step of the reaction is slow and is the rate
determining step. The second step is usually very fast.

–
Step 1 : X + + X Slow step

STUDY MATERIAL: XII CHEMISTRY 26 HALOALKANES AND HALOARENES

 Step 2 : + + : Nu Nu + Nu

Attack can occur from either side.

Example 15 :
What is the stereochemistry of the SN2 reaction?
Sol. SN2 reactions that occur at Chiral Centers proceed with complete inversion of stereochemistry. The tetrahedral
Carbon is turned inside out like an umbrella in a strong wind.

Example 16 :
What is the stereochemistry of the SN1 reaction?
Sol. SN1 reactions proceed with almost complete loss of stereochemistry (there is sometimes a very slight preference
for inversion). The loss of stereochemistry is due to the fact that the carbocation intermediate is sp2 hybridized,
and therefore flat. The nucleophile can approach form either face, giving a mixture of Enantiomers.

Example 17 :
Why do primary Alkyl Halides react by an SN2 mechanism?
Sol. The SN2 mechanism requires direct attack by a ucleophile on the Carbon bearing the Halogen. In a typical
primary Alkyl Halide, the approach to this Carbon is clear and the reaction may proceed smoothly. An SN1
mechanism, however, requires the formation of a carbocation intermediate. For a primary Alkyl Halide, the
intermediate would be an extremely unstable primary carbocation. The SN1 mechanism is therefore unfavourable,
and the substitution proceeds by SN2.

Example 18 :
What is the order of stability of carbocations?
Sol. If only saturated carbocations are considered, then the order is 3° > 2° > 1° > CH3+. If benzylic and allylic
cations are also considered, then the order is:
3 alkyl   2 alkyl 
3 allylic    2 allylic   1 allylic 
3 benzylic   2 benzylic  1 benzylic  > 1° alkyl > CH3 .
+
   
Example 19 :
What is the easiest way to summarize the competition between SN1 and SN2?
Sol. SN2 Reaction Rate

R3CX R2CHX RCH2X CH3X

SN1 Reaction Rate

Another good way to summarize the competition is to remember that SN2 reactions are controlled by steric
factors and SN1 reactions are controlled by electronic factors.

STUDY MATERIAL: XII CHEMISTRY 27 HALOALKANES AND HALOARENES

 CONCEPT MAP
* Mohohalogen compounds hybridisation. These compounds cal formed during the reaction by
* Halogens derivatives of hydrocar-
cotaining Csp3 – X bond are of two types : resonance.
bons : The compounds in which one
In these compounds, the halogen • Haloalkanes (vinylic halides) * Preparation of halogen derivatives
or more hydrogen atoms in the mol-
atom is linked to a carbon showing e.g., CH2 = CH – X of arenes :
ecule of an alkane or arene are
sp 3 hybridisation. These com- • Haloarenes (Aryl halides) The chloro and bromo derivatives
repalced by the same number of
pounds are further classified as e.g., C6H5 – X of arenes can be obtained by elec-
halogen atoms are called halogen
• Haloalkanes (only halides) * Order of reactivity of hydrogen in trophilic substitution with chlorine
derivatives of alkanes or arenes.
e.g., CH3 – CH2 – CH2 – CH2 X the free radical halogenation of hy- or bromine in the presence of Fe, or
Depending upon the number of
• Allylic halides, drocarbons. FeCl3 as catalyst.
hydrogen atoms replaced by halo-

STUDY MATERIAL: XII CHEMISTRY

e.g., CH2 = CH – CH2 – X Benzylic Allylic > Tertiary > Sec- The iodination of arenes can be
gen atoms, such compounds are
• Benzylic halides, ondary > Primary > Vinylic  Aryl brought about by iodine and HIO3.
called as mono, di, tri, tetra, etc. halo
e.g., C6H5 – CH2X The hight reactivity of benzylic and * Preparation of haloalkanes from
derivatives for one, two, three, four
* Mohohalogen compounds allylic hydrogens is due to the sta- alcohols :
etc.
cotaining Csp2 – X bond bilization of the respective free radi- The – OH group of the alcohols
* Monohalogen compounds : The
In these compounds, the halogen can be sustituted by a halogen
halogen containing compounds
containing carbon is sp2 atoms with the help of hydrogen ha-
having one halogen atom in their
lides (HX), phosphorus halides
molecules are called mohohalogen
(PCl3 , PCl5) or thionyl chloride

28
compounds.
HALOALKANES AND (SOCl2). Haloarenes cannot be ob-

tained from phenols because due

HALOARENES
to resonance, the carbon-oxygen
alled diazonium salts. Diazonium • Monohalo < Dihalo < Trihalo * Reactivity of C – X bond : Due to
bond in phenols develops a double
salts provide a very direct method < Tetrahalo high polarity, the C – X bond is very
bond character and is not cleaved
for the preparation of halogen de- • CH3X < RCH2X < RCH2CH2X reactive. The reactivity of
easily.
rivatives of arenes. < RCH2CH2CH2X haloalkanes follows the order
* Swarts reaction : This method is
C6H5N2+Cl–  C6H5 Cl + N2 (g) The boiling points of isomeric Iodoalkane > Bromoalkane >
used for obtaining fluoro deriva-
* Boiling points of halogen deriva- dihalobenzens are very nearly the Chloroalkane
tives of alkanes by heating their
tives : The boiling points of halo- same. Tertiary haloalkane > Secondary
chloro or bromo derivatives with
gen derivatives are higher than * Melting points : The p-isomer of a haloalkane > Primary haloalkane
metallic fluorides such as AgF,
those of the corresponding hydro- dihalobenzene is much higher (by Haloarenes are less reactive than
CoF3, SbF3, etc.
carbons. 70-100 deg) than the corresponding haloalkanes due to stabilization by
CH3Br + AgF CH3F + AgBr (s)
The boiling points order : o- and m- isomers. This is because, resonance.
* Diazonium salts : The salts of the
• Fluoro < Chloro < Bromo < Iodo p-isomers being more symmetrical
type C6H5N2+Cl–
• Primary haloalkane > Secondary fit into the lattice more closely.
(benzenediazonium chloride) are
haloalkane > Tertiary haloalkane

HALOALKANES AND HALOARENES


* Nucleophilic substitution reactions
of halogen derivatives : Halogen de-
rivatives of alkanes and arenes un-
dergo nucleophile substitution reac-
tions.
The nucleophilic substitution can
occur by two mechanisms – SN1 and
SN2
In SN1 mechanism, the reaction pro-
STUDY MATERIAL: XII CHEMISTRY
ceeds through the attack of a nu-
cleophile on the carbocation formed
due to heterolytic cleavage of the C
– X bond.
In SN2 mechanism, the nucleophilic
attacks the partially positive carbon
atom from a direction opposite to the
C – X bond. This leads to the re-
lease of X– and the nucleophile gets
29
* Elimination reactions of halogen
derivatives : Haloalkanes show -
elimination reactions in which one
molecule of hydrogen halid is elimi-
nated from the molecule and a
double bond is developed between
the two (and ) carbons.
When a HX molecule can be elimi-
nated in more than one way, then
the formation of the most substi-
tuted alkene is favoured. This is
called Saytzeff’s rule.
* Reaction of haloderivatives with
metals : Halo derivatives react with
active metals forming organometal-
HALOALKANES AND HALOARENES
CONCEPT MAP
attached to the carbon atom.
* Primary haloalkane usually react
by SN2 mechanism.
* Tertiary haloalkane usually react
by SN1 mechanism.
* Secondary haloalkane, primary
allylic and primary benzylic halo
derivatives may react by either or
both the mechanisms depending
on the nature of the nucleophile
and the solvent.
The presence of an electron-with-
drawing group (– NO2, – CN, etc.)
at the ortho or para position to the
halogen atom in haloarenes in-
HALOALKANES AND
HALOARENES
lic compounds. The Grignard’s re-
agent (R – Mg – X) is one of the
most versatile organometicallic
compound.
Haloalkanes and haloarenes when
heated with sodium metal in dry
ether give higer alkanes.
* Polyhalogen compounds : The or-
ganic compounds containing more
than one halogen atom in their mol-
ecules are generally called
polyhalogen compounds. Some of
the polyhalo compounds are com-
mercially very important.
creases the reactivity of the
haloarenes. The reactivity of such
haloarenes increases with the num-
ber of electron-withdrawing groups
on the ring .
* A SN2 reaction proceeds with ste-
reochemical inversion while a SN1
reaction proceeds with racemiza-
tion.
* Optically active molecule :
It is a molecule that cannot super-
imposed on its mirror image. It is
also called chiral molecule.
* Asymmetric carbon : It is a carbon
that is bonded to four different
NOTE
* The order of reactivity is
(a) RI > RBr > RCl > RF
(b) Allyl halide > Alkyl halide
> Vinyl halide
(c) Aralkyl halide > Aryl halide
* SN1 reaction : Mainly 3° alkyl ha-
lides undergo this reaction and
form racemic mixture.
SN1 is favoured by polar solvent
and low concentration of nucleo-
phile.
groups. It is also called chiral car-
bon.
* Enantiomers : These are optical iso-
mers that are mirror images.
* Diastereoisomers : These are opti-
cal isomers that are not mirror im-
ages.
* Racemic mixture : A mixture of equal
quantities of the d- and l-forms of
an optically active compound. This
is denoted by the prefix dl (eg., dl-
lactic acid). A racemic mixture shows
no optical activity.
Meso compound : It is a compound
that has more than one asymmetric
carbon and that is super imposable
on its mirror image.
* SN2 reaction : Mainly 1° alkyl ha-
lides undergo this substitution.
Walden inversion takes place. SN2
reaction is preferred by non-polar
solvents and high concentration of
nucleophile.
* Ambident nucleophiles
R – X + KCN
R – CN (major) + R – NC (minor)
R – X + AgCN
Ag – CN (major) + R – CN (minor)
 ANSWERS TO LEARNING CHECK  1
(1) An Alkyl Halide is any compound containing a Halogen atom bonded to an sp3 hybridized Carbon.
(2) There are two other general classes of organohalides, Aryl Halides and Vinyl Halides. Aryl Halides are compounds
which have a Halogen directly bound to an aromatic ring, while Vinyl Halides have the Halogen bonded to the
sp2 hybridized Carbon of a double bond.
(3) The general formula R – X is often used to represent alkyl halides. The R represents an alkyl group, while the
X represents a halogen atom.
(4) The common names of the Alkyl Halides consist of the common name of the Alkyl group followed by the name
of the halide as a separate word. They are essentially named as though they were salts.
H3C CH 3
|
CH – I H3C  C  CH 2  F
CH 3CH 2 CH 2 CH 2Cl |
Butyl chloride H3C CH 3
Isopropyl iodide Neopentyl fluoride

(5) (a) Bromocyclohexane and Cyclohexyl Bromide, (b) 3-Fluoropropene and Allyl Fluoride,
(c) Dichloromethane and Methylene Chloride
(6) C – X bond strength decreases as you go down the Halogen family. The C – F bond is the strongest
(109 k cal / mol in Fluoromethane), followed by the C – Cl bond (84 kcal / mol in Chloromethane), the C – Br
bond (70 k cal / mol), and finally the weakest, the C – I bond (56 k cal / mol).
ANSWERS TO LEARNING CHECK  2
(1) The forces between the molecules of a liquid Alkyl Halide consist of a combination of dipole-dipole, dipole-
induced dipole, and induced dipole-induced dipole attractions.
(2) Polarizability refers to how easily an atom’s or molecule’s electron distribution is distorted by a nearby electric
field. Tightly held electrons are not very polarizable, whereas loosely held electrons are.
(3) Unlike Bromine, Fluorine is very small and holds on to its electrons very tightly. As a result it has very low
polarizability and the van der Waals forces are extremely weak - much weaker than in comparable sized
Alkanes. The dipole-dipole forces between Alkyl Fluoride molecules can’t make up for this.
(4) All Alkyl Halides are insoluble in water.
(5) Methyl Bromide and Hydroxide ion react by an SN2 mechanism.
(6) This reaction would occur by an SN1 mechanism.
(7) Walden inversion.
(8) SN1 : rate = k [substrate] ; SN2 : rate = k [substrate] [nucleophile]
(9) A solvent that does not hydrogen bond. Such solvents do not have Hydrogen bonded to an electronegative
element.
(10) Polar protic solvents favour the SN1 reaction. In the rate-determining step of the SN1 reaction, a carbocation
and an anion are usually formed. Anything which stabilizes these two ions will lower the energy of the transition
state and increase the rate of the reaction. Polar protic solvents are very capable of solvating both positive and
negative ions, thus lowering their energy.
(11) -Elimination is a reaction in which a small molecule such as HCl or H2O is eliminated from a molecule to form
a double bond. The components of the molecule are removed from adjacent Carbons. In Alkyl Halides, the
molecule that is eliminated is HX, with the Hydrogen being lost from a Carbon  to the Halogen atom.
(12) E2 is favoured by strong bases (hydroxide and alkoxide). SN1 is favoured when poor nucleophiles/bases are
used (water, alcohols, etc.).
*
(13)
Cl

STUDY MATERIAL: XII CHEMISTRY 30 HALOALKANES AND HALOARENES