Vinylic halides

Haloalkanes and Haloarenes

halogen atom is bonded to( an sp2-hybridised) carbon atom of

10.1 Classification

a carbon-carbon double bond = C).

Haloalkanes and haloarenes may be classified as follows:

10.1.1 On the Basis of Number of halogen Atoms

(b) Aryl halides

These are the compounds in which the halogen atom is bonded

to the sp2-hybridised carbon atom of an aromatic ring.

compounds having same type of halogen atoms are

. Haloarenes are the common as well as IUPAC names of aryl

further classified as

geminal halides (halogen atoms are present on the

halides. For dihalogen derivatives, the prefixes o-, m-, p- are

used in common system but in IUPAC system, the numerals

same carbon atom) and

10.2 Nomenclature

vicinal halides (halogen atoms are present on the

1,2; 1,3 and 1,4 are used.

adjacent carbon atoms).

10.1.2 Compounds Containing sp3 CX Bond
(X= F, Cl, Br, I) This class includes

Alkyl halides or haloalkanes (RX)

They are further classified as primary, secondary or tertiary

according to the degree of carbon to which halogen is attached
i.e carbon.

In common name system,

gem-dihalides are named as alkylidene halides

and

(b) Allylic halides

halogen atom is bonded to carbon atom(sp 3-hybridised) next

vic-dihalides are named as alkylene dihalides. In

IUPAC system, they are named as dihaloalkane

to carbon-carbon double bond (C=C) i.e. to an allylic carbon.

(c) Benzylic halides

halogen atom is bonded to carbon atom(an sp 3-hybridised)

Some common examples of halocompounds are mentioned in Table 10.1.

next to an aromatic ring.

STRUCTURE

COMMON

IUPAC NAME

NAME

10.1.3 Compounds Containing sp CX Bond

This class includes:

sec Butyl
CH3CH2CH(Cl)CH3 chloride

2 Chlorobutane

(CH3)3CCH2Br

1-Bromo-2,2-dimethylpropane

MUKESH SHARMA DPS JODHPUR

neo-Pentyl

(1)

bromide

Thionyl chloride is preferred because the other two

products are escapable gases. Hence the reaction

(CH3)3CBr

tert-Butyl bromide

2-Bromo-2-methylpropane

CH2 = CHCl

Vinyl chloride

Chloroethane

CH2= CHCH2Br

Allyl bromide

3-Bromopropane

o-Chlorotoluene

1-Chloro-2-methylbenzene or 2-cholorotoluene

Benzyl chloride

Chlorophenylmethane

CH2Cl2

Methylene chloride

Dichloromethane

CHCl3

Chloroform

Trichloromethane

CHBr3

Bromoform

Tribromomethane

CCl4

Carbon
tetrachloride

Tetrachloromethane

CH3CH2CH2F

n-Propyl fluoride

1-Fluoropropane

gives pure alkyl halides.

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.

. The order of reactivity of alcohols with a given

haloacid is 3>2>1. Because 3carbocation are
more stable than 2>1

The above method is not applicable for the

Intext Question

preparation of aryl halides because the carbon-

10.1 Write structures of the following compounds:

oxygen bond in phenols has a partial double bond

(i) 2-Chloro-3-methylpentane

character and is difficult to break being stronger than

(ii) 1-Chloro-4-ethylcyclohexane

a single bond

(iii) 4-tert. Butyl-3-iodoheptane

10.4.2 From Hydrocarbons

(iv) 1,4-Dibromobut-2-ene

(a) By free radical halogenation

(v) 1-Bromo-4-sec. butyl-2-methylbenzene.

10.3 Nature of C-X Bond

bromination of alkanes

the carbon- halogen bond of alkyl halide is polarised;

Rate of halogenation is fastest at benzylic and 30 and

carbons because of stability of free radicals

Major product will be at benzylic> allylyic>
0
0
30>2 >1 > vinylic > aryl

as X is MENA and C is LENA

It is a Free radical reaction chlorination or

the carbon atom bears a partial positive charge

whereas the halogen atom bears a partial negative
charge.

Example 10.3 Identify all the possible monochloro structural

carbon-halogen bond length increases from CF to

isomers expected to be formed on free radical

monochlorination of (CH3)2CHCH2CH3.

CI.

bond strengths decrease R-F> R-Cl> R-Br>RI

d i p o l e m o m e n t / d e b y e R-F> R-Cl> R-Br>RI

Solution In the given molecule, there are four different types

of hydrogen atoms. Replacement of these hydrogen atoms will
give the following

10.4 Methods of Preparation

10.4.1 From Alcohols. The hydroxyl group of an alcohol is
replaced by halogen on reaction with conc. halogen acids,
phosphorus halides or thionyl chloride.

MUKESH SHARMA

(CH3)2CHCH2CH2Cl

(CH3)2CHCH(Cl)CH3

(CH3)2C(Cl)CH2CH3

CH3CH(CH2Cl)CH2CH3

(b) By electrophilic substitution

DPS JODHPUR

For Aryl chlorides and bromides

(2)

bromine respectively

(ii) Addition of halogens:

in the presence of Lewis acid catalysts like iron or

Reaction is used for unsaturation test as red colour of bromine
is discharged in rection

iron(III) chloride.

Peroxide
CH3 CH CH2 HBr
CH3 CH2 CH2 Br

electrophilic substitution of arenes with chlorine and

Reactions with iodine are reversible in nature and

require the presence of an oxidising agent (HNO3,
HIO4) to oxidise the HI formed during iodination.

Example 10.4
Write the products of the following reactions:

Fluoro compounds are not prepared by this method

due to high reactivity of fluorine.
(c) Sandmeyers reaction
When a primary aromatic amine, is treated with sodium nitrite,
a benzene diazonium halide is formed

Mixing the diazonium salt with cuprous chloride or

Solution

cuprous bromide
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]

For iodine potassium iodide.is used in place of cuprous

Swarts reaction.
heating an alkyl chloride/bromide in the presence of a

iodide

metallic fluoride such as AgF, Hg2F2, CoF2 or SbF3. The

H3C-Br +AgF H3C-F + AgBr
10.4 Among the isomeric alkanes of molecular formula C 5H12,
identify the one that on photochemical chlorination yields

(d) From alkenes

(i) A single monochloride.

(i) Addition of hydrogen halides:

(ii) Three isomeric monochlorides.

(iii) Four isomeric monochlorides.
10.5 Draw the structures of major monohalo products in each

Propene yields two products, however only one

of the following reactions:

predominates as per Markovnikovs rule.

CH3=CH2 + H-I CH3CH2CH2I + CH3CHICH3
minor

major

Markovnikovs rule.
Group X [MENA] is added to doubly bonded carbon with
least hydrogen

In case of HBr if peroxide is added antimarkonikoffs

10.5 Physical properties

addition takes place which is also called Kharash

effect or peroxide effect e.g.

MUKESH SHARMA DPS JODHPUR

Melting and boiling points

(3)

Halides have higher boiling points than

(i) Nucleophilic substitution

hydrocarbons of comparable molecular mass because

(ii) Elimination reactions

of having stronger dipoledipole and van der

(iii) Reaction with metals.

Waals forces of attraction.

(i)

For the same alkyl group, the boiling points of alkyl

Nucleophilic substitution reactions

, a nucleophile reacts with haloalkane (the substrate).,

halides decrease in the order: RI> RBr> RCl> RF

halogen is called leaving group departs as halide ion.

The boiling points of isomeric haloalkanes decrease

it is called nucleophilic substitution reaction.

with increase in branching

For example, 2-bromo-2-methylpropane has the

lowest boiling point among the three isomers.
The products formed by the reaction of haloalkanes with some
common nucleophiles are given in Table 10.4.

NUCLEOPHILE(N SUBSTITUTION PRO

the para-isomers are high melting as compared to
their ortho- and meta-isomers. due to symmetry of

REAGENT

U-)

NaOH(KOH)

HO

H2O

H2O

ROH

NaOR

RO-

ROR ethers

NaI

I-

R-I

NH3

NH3

RNH2 amines

number of carbon atoms, halogen atoms and atomic

RNH2

RNH2

RNHR2

mass of the halogen atoms.

RRNH2

RRNH2

RNRR2

para-isomers that fits in crystal lattice better

Density

R-NU
ROH alcohols

The density of halides increases with increase in

.Solubility

The haloalkanes are only very slightly soluble in

KCN

RCN cynides

AgCN

RNC (isosynanide)

water.

when new attractions are set up between the

haloalkane and the water molecules ,these are not as

KNO2

O=N-O

R-O-N=O (isosynanide)

strong as the original hydrogen bonds in water. As a

result, the solubility of haloalkanes in water is low.

AgNO2

Haloalkanes dissolve in organic solvents because

RCOOAg

RCOO-

RCOOR (esters)

LiAlH4

RH (alkanes)

10.6 Arrange each set of compounds in order of

R-M+

R-

RR- (alakne)

increasing boiling points.

Table 10.4: Nucleophilic Substitution of Alkyl Halides (RX)R-X+Nu

much the same strength

Intext Question

(i) Bromomethane, Bromoform, Chloromethane,

R-NO2

ambident nucleophiles:-can act as a nucleophile

Dibromomethane.

through two different donor of electron [CN

(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.

:C=N], i.e., linking through carbon atom resulting in

10.6 Chemical Reactions

alkyl cyanides and through nitrogen atom leading to

10.6.1

isocyanides. Similarly nitrite ion also represents an

Reactions of Haloalkanes

The reactions of haloalkanes may be divided into the

following categories:

MUKESH SHARMA

DPS JODHPUR

(4)

ambident nucleophile with two different points of

linkage

Example 10.5
Haloalkanes react with KCN to form alkyl cyanides as
main product while AgCN forms isocyanides as the chief
product. Explain.
Solution

Step I ., greater the stability of carbocation, faster will be the

KCN is predominantly ionic and provides cyanide ions in

rate of reaction.

solution. Although both carbon and nitrogen atoms are in a

In case of alkyl halides, 3 alkyl halides undergo SN1

position to donate electron pairs, the attack takes place mainly

reaction very fast because of the high stability of 3

through carbon atom and not through nitrogen atom since C

carbocations.

C bond is more stable than CN bond. However, AgCN is

mainly covalent in nature and nitrogen is free to donate

We can sum up the order of reactivity of alkyl halides

towards SN1 and SN2 reactions as follows:

electron pair forming isocyanide as the main product.

Mechanism: This reaction has been found to proceed by two

different mechanims which are described below:
(a) Substitution nucleophilic bimolecular (SN2)
The reaction between CH3Cl and hydroxide ion to yield

methanol and chloride ion follows a second order kinetics, i.e.,

For the same reasons, allylic and benzylic halides show

high reactivity towards the SN1 reaction. The

the rate depends upon the conc.of both the reactants.

carbocation thus formed gets stabilised through

resonance

Primary halide > Secondary halide > Tertiary halide.

In both the mechanisms, for a given alkyl group, the

increasing order of reactivity is
R F << R Cl < R Br < R I

Example 10.6
(b) Substitution nucleophilic unimolecular (SN1)

In the following pairs of halogen compounds, which would

SN1 reactions are generally carried out in polar protic solvents

undergo SN2 reaction faster?

(like water, alcohol, acetic acid, etc.). The reaction between

tert-butyl bromide and hydroxide ion yields tert-butyl alcohol
and

Solution

Sn1follows the first order kinetics, i.e.,

It occurs in two steps.

In step I, CBr breaks to produce a carbocation

in step II The carbocation attacked by nucleophile to

A SN2 proceeds with complete sinversion

complete the substitution reaction.

a SN1 proceeds with racemisation.

(c) Stereochemical aspects of nucleophilic substitution

Optical activity,chirality, retention, inversion,racemization

DPS JODHPUR

MUKESH SHARMA

(5)

(i)optical activity: compounds rotate the plane polarized

Example 10.8

light are called optically active compounds.

Identify chiral and achiral molecules in each of the following

pair of compounds. (Wedge and Dash representations )

If the compound rotates the PPL to the right, i.e.,

clockwise direction, it is called dextrorotatory or the dform and its notation is (+)sign

If the light is rotated towards left the compound is said to

be laevo- rotatory or the l-form and a negative () sign

(+) and () isomers of a compound with same molecular

formula are called optical isomers and the phenomenon is

Solution

termed as optical isomerism.

(ii)Molecular asymmetry, chirality and enantiomers :
asymmetry, scientifically called chirality

The objects which are non- superimposable on their

(iii) Retention: Retention of configuration is the preservation

mirror image (like a pair of hands) are said to be chiral

of integrity of the3d arrangement of bonds to an asymmetric

and this property is known as chirality..

centre YCabc having the same relative configuration.

The chirality (asymmetry) of the molecule is responsible

for the optical activity in such organic compounds.

Carbon bonded with four different group tetrahedrally is

called chiral carbon

Compound with one chiral carbon always optically active

Compound with more than one chiral carbon may or may

the reaction that takes place when ()-2-methylbutan1-ol is heated with concentrated hydrochloric acid.

not optically active

Butan-2-ol has four different groups attached to the

tetrahedral carbon and as expected is chiral.

examples of chiral molecules such as 2-chlorobutane,

(iv) Inversion, retention and racemisation: There are three

2, 3-dihyroxypropanal, (OHCCHOHCH2OH),

outcomes for a reaction at an asymmetric carbon atom.

Enantiomers The stereoisomers which are related to each

Consider the replacement of a group X by Y in the following

other as non- superimposable mirror images are called

reaction;

Enantiomers

possess identical physical properties namely, melting

point, boiling point, solubility, refractive index, etc.

They only differ with respect to the rotation of plane

polarised light.

If one of the enantiomer is dextro rotatory, the other will

be laevo rotatory by equal angle of rotation.

called retention of configuration.

However, the sign of optical rotation is not necessarily

related to the absolute configuration(3d structure) of the

molecule.

If a 50:50 mixture of the above two is obtained then

the process is called racemisation and the product is

equal proportions will have zero optical rotation,

MUKESH SHARMA
A racemic mixture is represented by prefixing dl or ()

If (B) is the only compound obtained, the process is

called inversion of configuration.

Racemic mixture:- A mixture containing two enantiomers in

before the name, for example () butan-2-ol.

If (A) is the only compound obtained, the process is

optically inactive, as one isomer

(6) will rotate light in
the direction opposite to another.

conversion of enantiomer into a racemic mixture is

In SN2, in case of optically active alkyl halides, the

product formed as a result of SN2 mechanism has the

known as racemisation.

DPS JODHPUR

inverted configuration as compared to the reactant.

These reagents are obtained by the reaction of haloalkanes

with magnesium metal in dry ether.

In SN1 reactions are accompanied by racemisation.

Grignard reagents are highly reactive and react with any

hydrolysis of optically active 2-bromobutane, which

source of proton to give hydrocarbons. Even water,

results in the formation of ()-butan-2-ol.

alcohols, amines are sufficiently acidic to convert them to

corresponding hydrocarbons.

RMgX + H2O

It is therefore necessary to avoid even traces of moisture

from a Grignard reagent.

Wurtz reaction

2. Elimination reactions

When a haloalkane with -hydrogen atom is heated

10.6.2 Reactions of Haloarenes

with alcoholic solution of potassium hydroxide, there is

1. Nucleophilic substitution

elimination of hydrogen atom from -carbon and a halogen

Aryl halides are extremely less reactive towards nucleophilic

atom from the -carbon atom.

substitution reactions due to the following reasons:

, an alkene is formed as a product. Since -hydrogen atom

(i) Resonance effect : In haloarenes, the electron pairs on

is involved in elimination, it is often called -elimination.

halogen atom are in conjugation with -electrons of the ring

and the following resonating structures are possible.

Zaitsev rule 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

CCl bond acquires a partial double bond character due to

resonance..
(ii) sp2 hybridisation

major product.

the major alkene will be ,the which has the greater

number of alkyl groups attached to the doubly bonded
carbon atoms. Thus, 2-bromopentane gives pent-2-ene as

(iii)Instability of phenyl cation:

Replacement by hydroxyl group

the major product.

Ellimination versus substitution

it is a race that is won by the fastest runner. A

Which route will be taken up depends upon the nature of

alkyl halide, strength and size of base/nucleophile and
reaction conditions. Thus, a bulkier nucleophile will
prefer to act as a base and

depending upon the strength of base/nucleophile and a

The presence of an electron withdrawing group (-NO2) at

tertiary halide- SN1 or elimination depending upon the

ortho- and para-positions increases the reactivity of

stability of carbocation or the more substituted alkene.

haloarenes.

3. Reaction with metals

RMgX, Grignard Reagents.

DPS JODHPUR
MUKESH SHARMA

(7)

(iv) Friedel-Crafts reaction

The effect is pronounced when (-NO2) group is introduced at

ortho- and para- positions.
2. Electrophilic substitution reactions

ESR in haloarenes occur slowly to those in benzene i.e.

Halogen atom are deactivating because of their strong
electron withdrawing nature ,all arenium are unstable

-X is electron withdrawing group due to higher

Example 10.9 Although chlorine is an electron withdrawing

weightage of I effect over their +M effect [+R]

group, yet it is ortho-, para- directing in electrophilic aromatic

Despite of deactivating effect X are o, p- directing;

substitution reactions. Why?

therefore, i.e further substitution occurs at ortho- and

Solution

para- positions with respect to the halogen atom.

The o, p-directing influence of halogen atom is because

Due to resonance, the electron density increases more at
ortho- and para-positions than at meta-positions.

:
(i) Halogenation
Destabilization due to I is in all arenium equal, but
advantage of +R to stabilize arenium ion is in only during
attack at O- and P

.3. Reaction with metals

Wurtz-Fittig reaction

Fittig reaction

(Chloroform, CHCl3)
Stored in closed, dark-coloured container as it is
oxidised to an extremely poisonous gas, phosgene,
when exposed to light.

(iodoform, CHI3) Its antiseptic properties are due

to the liberation of free iodine

MUKESH SHARMA

DPS JODHPUR

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