Haloalkanes and Haloarenes

Module 32.1: Nomenclature- Nature of C-X bond, Physical and Chemical

properties, SN1 and SN2 mechanism
Introduction:
The halogen derivatives of aliphatic hydrocarbons (alkanes) are called haloalkanes and
halogen derivatives of aromatic hydrocarbons are called haloarenes.
These are obtained when the hydrogen atom of an alkane or an arene is replaced by a
halogen atom [F, Cl, Br or I]. The general formula is CnH2n+1X for haloalkanes and for
haloarenes the general formula is Ar – X.
Haloalkane is represented by RX, where R is an alkyl group. Monohalogen
derivatives of alkanes are called haloalkanes or alkyl halides. Haloarenes is represented
by ArX where Ar is aryl group and X is a halogen atom.
The halogen derivatives of hydrocarbons are classified on the basis of nature of
hydrocarbon from which they are obtained as:
(i) Alkyl halides (Halo alkanes): Halogen derivative of alkanes
(ii) Alkenyl halides (Halo alkenes): Halogen derivative of alkenes (Not included in syllabus)
(iii) Alkynyl halides (Halo alkynes): Halogen derivative of alkynes (Not included in syllabus)
(iv) Aryl halides (Halo arenes): Halogen derivative of arenes. (see aromatic part)
Alkyl halides are further classified as:
(i) Mono halides: These involve replacement of one H atom by halogen atoms i.e., CnH2n+1 X.
Ex: CH3CI: methyl chloride or chloromethane
C2H5CI: ethyl chloride or chloroethane
(ii) Di halides: These involve replacement of two H atoms by halogen atoms i.e., CnH2nX2
(iii) Tri halides: These involve replacement of three H atoms by halogen atoms i.e., CnH2n-1X3
Ex: CHX3: trihalo methane or haloform
(iv) Tetra halide: These involve replacement of four H atoms by halogen atoms i.e., CnH2n-2X4
Ex: CCI4: Carbon tetrachloride of tetra chloromethane.
Monohalides or Alkyl halides:
(1) General formula CnH2n+1X
Ex: CH3X, C2H5X etc.,
(2) Mono halides are further classified as:
(A) Primary halides: Halogen atom attached on 1o carbon or methyl carbon
Ex: CH3X : halomethane or methyl halide
CH3CH2X : haloethane or ethyl halide
CH3CH2CH2X : 1-halopropane or n-propyl halide
(B) Secondary halides: Halogen atoms are attached on 2o carbon atom
CH3CHXCH3 : 2-halopropane or sec. propyl halide or isopropyl halide
CH3CHXCH2CH3 : 2-halobutane or sec. butyl halide
(C) Tertiary halides : Halogen atoms are attached on 3o carbon atom

Aryl halides (haloarenes) are halogen derivatives of aromatic hydrocarbons, which are
derived by replacing hydrogen atom attached to the aromatic ring by a halogen atom.
Therefore, in haloarenes the halogen atom [F, Cl, Br or I] is directly attached to the
aromatic ring. For example
Nomenclature of mono haloalkanes and mono haloarenes:
Two methods are in use
1. Common or trivial system:
The monohalogen derivatives of alkanes are alkyl halides. Their names are written by
naming the alkyl group attached to halogen first and then adding the word halide.
Example:

The names of the alkyl groups and the halides are written in two separate words. The
prefixes n-, iso-, sec-, tert-, etc., are also used for alkyl groups to represent the type of
carbon chain in the compound.
n – prefix:
CH3CH2CH2CH2–Cl CH3CH2CH2CH2CH2–Br
n – Butyl chloride n – Pentyl bromide
The prefix ‘n-’is used for alkyl group having continuous chain of carbon atoms with no
branching.
Iso - prefix:

The prefix ‘iso–‘is used for those alkyl groups where one methyl group is attached to a
carbon that is next to the end C–atom.
Neo – prefix:
The prefix ‘neo–‘ is used for those alkyl groups which have two methyl groups attached
to a carbon that is next to the end C–atom.
Example:

Aryl halides:
Aryl halides are named by adding the prefix ‘halo’ [fluoro, chloro, bromo iodo etc.]
before the name of the aromatic hydrocarbon. In case of di – substituted compounds,
the relative positions of the substituted groups, (1, 2); (1, 3); and (1, 4) are indicated by
the prefix ortho (o -), meta (m -) and para (p -) respectively. When more than two
substituents are present, their positions are indicated generally by numerical indices.
For example:

2. IUPAC System:
The mono halogen derivatives of alkanes are named as haloalkanes. While writing the
names, the word ‘halo’ is prefixed to the name of the alkane corresponding to the
longest continuous carbon chain that has the halogen atom. In case of branched chain
alkanes, the following rules are followed.
The longest continuous chain containing the carbon that is attached to halogen group is
selected as the parent alkane.
The carbon atom is numbered in a way that the carbon atom carrying the halogen atom
gets the lowest number.
The positions of the halogen atom and the other alkyl groups are indicated by suitable
numerical prefixes i.e. 1, 2, 3 etc. Other common rules of alkanes are followed.
For example:

The common and the IUPAC names of a few alkyl halides are given below:
Nature of C – X bond:
Halogens are more electronegative elements than carbon. Due to the difference in the
electronegativity values the carbon - halogen bond of alkyl halide shows polarity. The
partial positive charge is present on carbon atom and partial negative charge is present
on halogen atom after polarisation.

The size of halogen atom increases as we go down the group in the periodic table;
fluorine atom is the smallest and iodine atom is the largest in the VIIA group.
Consequently the carbon – halogen bond length also increases from C – F to C – I. As the
bond length increases the bond enthalpy decreases.

Bond Bond length (in pm) Bond enthalpies (in kJ mol-1)

CH3 – F 139 452
CH3 – Cl 178 351
CH3 – Br 193 293
CH3 – I 214 234

Preparation methods of Monohalides (Monohalides)

1. From alcohols:
This is the most widely used method for the preparation of Haloalkanes. Here, the
hydroxyl group (-OH) of alcohol is replaced by the halogen atom (X) on reaction with
concentrated halogen acids, phosphorus halides or thionyl chloride.
(a) Action of halogen acids:
Chloroalkanes are produced by passing the dry HCl gas through the alcohol in the
presence of anhydrous ZnCl2. (This method is known as Groove’s process)
ZnCl2
R OH HCl R Cl H2O
anhydrous

(ZnCl2 is needed for primary and secondary alcohols)

 ZnCl2 or H2SO4
R OH HBr R Br H2O

(ZnCl2 or H2SO4 is needed for primary alcohols)

R OH HI R I

The reactivity order for alcohols is: tertiary > secondary > primary alcohol
The reactivity order of halogen acids is: HI > HBr > HCI
(ZnCl2, is a Lewis acid it readily coordinates with the oxygen atom of the alcohols. As a
result, the C– O bond weakens and breaks to form Carbocation. This reacts with chloride
ion to form chloroalkanes. Thus, anhydrous ZnCl2 helps in the cleavage of the C– O bond.)
Note: Haloalkanes are also obtained by heating the solution of alcohol with sodium
halide or potassium halide in the presence of concentrated mineral acid.

ROH + KBr + H2SO4 RBr + KHSO4 + H2O

ROH + KI + H2SO4 RI + KHSO4 + H2O

(b) By the action of phosphorus halides:

Alcohols react with phosphorus halides to form alkyl halides.

3 R-OH + PCl3 ⟶ 3R-Cl + H3PO3

R-OH + PCl5 ⟶ R-Cl + POCl3 + HCl

3C2H5OH + PCl3 ⟶ 3C2H5Cl + H3PO3

C2H5OH + PCl5 ⟶ C2H5Cl + POCl3 + HCl

Note: PBr3 and PI3 are less stable and thus for the preparation of bromide and iodides
PBr3 and PI3 are usually generated in situ by the reaction of red phosphorus with Br2 and
I2 respectively (P + Br2 or P + I2).
(c) Action of thionyl chloride or Darzen’s method:
Alcohols react with thionyl chloride in the presence of pyridine to form alkyl chlorides.
(This method is preferred because SO2 and HCl are gases and they easily escape.)

C2H5OH + SOCl2  C2H5Cl + SO2 + HCl

Pyridine

Note: SOBr2 is less stable & SOI2 does not exist and thus bromides & iodides are not
prepared by this method

2. From alkanes (By direct halogenation of alkanes):

Alkanes react with Cl2 or Br2 in the presence of light to form corresponding alkyl halides.
U.V. Light
R H X2 R X HX
or heat

3. From alkenes:
(a) By the addition of hydrogen halides (HX) on alkenes:
Haloalkanes can be prepared by the addition of hydrogen halides to alkenes.
(The addition follows Markownikov’s rule, except for the addition of HBr in the
presence of peroxides.)
R CH CH R HX R CH CH R

H X

CH2=CH2 + HCl CH3-CH2Cl

CH3CH=CH2 + HCl CH3CHClCH3 + CH3CH2CH2Cl

Major Minor
(b) Addition of halogens:
Addition of bromine in CCl4 to an alkene gives vicinal dibromides. (This test used is
used for the detection of unsaturation in a molecule)
CCl4
H2C CH2 Br2 Br H2C CH2 Br
4. Borodine-Hunsdicker reaction: Alkyl chlorides and alkyl bromides are obtained by
the action of CI2 or Br2 in CCI4 on silver salt of the fatty acids. This reaction proceeds
through free radical mechanism.

Note:
1. Hunsdiecker reaction is used to reduce the length of carbon chain (descent of series).
2. The yield of alkyl halide is primary > secondary > tertiary
3. Only bromides are obtained in good yield in this reaction. The chlorides can also be
obtained by this reaction but the yield is poor. Iodides however cannot be obtained
because Iodine form esters with silver salts. This reaction is called Birnbaurn-Simonini
reaction.
2RCOOAg + I2 → RCOOR + CO2 + 2AgI
5. By halogen exchange:
Alkyl iodides are usually prepared by the reaction of alkyl chlorides/ bromides with
NaI in dry acetone. The halogen exchange reaction is called Finkelstein reaction.
Acetone
R X NaI R I NaX

(X = Cl / Br)

Acetone
CH3CH2Cl NaI CH3CH2I NaCl

This method is also used to prepare fluorides.

2CH3CI + Hg2F2 → 2CH3F + Hg2CI2

Physical properties:
Alkyl halides are colorless when pure. However bromides and iodides get color on
standing or on exposure to light. They have pleasant odour. Many volatile halogen
compounds have sweet smell. Lower alkyl halides are gases but higher alkyl halides are
either liquids or solids. Alkyl halides are more polar and have higher molecular masses
when compared to the parent hydrocarbons. Because of these two reasons they have
stronger inter molecular forces of attraction and possess high boiling points and melting
points compared to parent hydrocarbons. For a given R, the order of melting points and
boiling points would be RI > RBr > RCl > RF. Among isomeric alkyl halides the boiling
points decrease with increase in branching. As the branching increases the adjacent
molecules are not able to come close to be attached strongly. For butyl bromide C4H9 Br
we have the following structures and the corresponding boiling points are shown.

The density of these compounds increases with increase in number of carbon atoms in
the chain, the number of halogen atoms and the atomic masses of halogen atoms.

Compound Density ( g ml-1 ) Compound Density ( g ml-1)

n – C3H7 Cl 0.89 CH2Cl2 1.336
n – C3 H7 Br 1.335 CHCl3 1.489
n – C3 H7 I 1.747 CCl4 1.595

The halogen compounds are only slightly soluble in water. In order to make a haloalkane
dissolve in water, energy is required to overcome the intermolecular attractions between
the haloalkane molecules and break the hydrogen bonds between water molecules. Less
energy is released when new attractions are set up between the haloalkanes and the
water molecules; these are not as strong as the original hydrogen bonds in water. As a
result, the solubility of haloalkanes in water is low. However 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.
Chemical nature of Alkyl halides:
(a) The alkyl halides are highly reactive due to the high electronegativity difference
between carbon & halogen atom which provides polarity in C+δ - X- δ bond & thus carbon
atom of C-X bond is easily attacked by a nucleophile to show nucleophilic substitution.
R-X + :Nu → R-Nu + X:
The nucleophilic substitution may follow SN1 or SN2 mechanism. In addition to
nucleophilic substitution alkyl halides also show elimination reactions.
(b) Furthermore the reactivity order of alkyl halide is:
R-I > R-Br > R-CI > R-F
The reactivity does not follow the polarity order of bond. On the contrary it has been
explained in terms of increasing bond length of C-X bond (maximum in C-I) which gives
rise to lower bond energy and thus less stability to C-X bond.
(c) The reactivity orders for given alkyl halide also shows the order:
3o halide > 2o halide > 1o halide
This has been explained in terms of +ve inductive effect of alkyl groups which increases
the polarity of C-X bond & thereby making it more reactive.
(d) Primary alkyl halides undergo reactions by SN2 mechanism. The presence of bulky
groups in primary halides (inspite of more +ve I.E.) cause steric hindrance & bring them
less reactive towards SN2 mechanism.
CH3X > C2H5X > C3H7X

Chemical properties of Alkyl halides:

The reactions of alkyl halides may be broadly divided into the following categories.
1. Nucleophilic substitutions 2. Elimination reactions 3. Reaction with metals
1. Nucleophilic substitutions on alkyl halides
Halogen atom of alkyl halides is easily replaced by other nucleophiles to give a large
variety of SN reactions.
a) Reaction with aqueous KOH: Haloalkanes react with aqueous potassium hydroxide to
form alcohols. The halogen atom is substituted by –OH group.

aq KOH,
KOH
R X R OH KX

b) Reaction with Moist Ag2O or AgOH: Haloalkanes react with moist silver oxide in ether
form alcohols. The halogen atom is substituted by –OH group.

Ag2O in water or AgOH

R X R OH

Moist Ag2O
CH3CH2Cl CH3CH2OH AgCl

c) Reaction with Sodium Alkoxides: Haloalkanes react with sodium alkoxides to form
ethers. This reaction is called a Williamson Ether synthesis.
NaOR'
R X R OR' NaX

C2H5Cl + NaOC2H5 ⟶ C2H5 – O – C2H5 + NaCl

Diethyl ether
Haloalkanes can also be converted into ethers by heating with dry Ag2O.

dry Ag2O
2 R X R OR 2 AgX

d) Reaction with NaCN/KCN: Haloalkanes react with alcoholic solution of potassium cyanide
to form alkyl cyanides as main product. The halogen atom is substituted by –CN group.

KCN (alcohol)
R X R CN R NC
alkyl cyanide isocyanide
(main product)
 [

C2H5Cl + KCN 
 Δ
C2H5CN + C2H5NC + KCl
Ethyl cyanide
(Major product)
e) Reaction with AgCN: Haloalkanes react with alcoholic solution of silver cyanide to form
alkyl isocyanides. These are called carbylamines and have extremely unpleasant smell.
AgCN (alcohol)
R X R NC R CN
isocyanide alkyl cyanide
(main product)

C2H5Cl + AgCN ⟶ C2H5NC + C2H5CN + AgCl

(Carbylamine)
(Major product)

f) Reaction with NH3: A primary amine is formed when a haloalkane is heated with alcoholic
ammonia solution in a sealed tube at 383K. The halogen is substituted by –NH2 group.

NH3 (alc)
R X R NH2

C2H5Cl + NH3 ⟶ C2H5 NH2 + HCl

Ethyl amine

However, when haloalkane is in excess, a mixture of primary, secondary and tertiary

amines is formed, as one or both the hydrogen atoms of the amino alkane [Primary
amine] can be substituted by alkyl groups.

C2H5NH2 + C2H5Cl ⟶ (C2H5)2NH + HCl

(C2H5)2NH + C2H5 Cl ⟶ (C2H5)3N + HCl

The tertiary amines which result, can also form quaternary ammonium salt by combining
with another molecule of alkyl halide.

(C2H5)3N + C2H5Cl ⟶ (C2H5)4N+ Cl–

A quaternary ammonium chloride
g) Reaction with KNO2: Haloalkanes react with potassium nitrite to form alkyl nitrites.
KNO2 (alcohol)
R X R O N O
alkylnitrite
(main product)

h) Reaction with AgNO2: Haloalkanes react with silver nitrite to form nitro alkanes.
AgNO2
R X R NO2 R ONO
Nitro alkane alkylnitrite
(main product)

i) Reaction with H2O: Haloalkanes react with water to produce alcohols.

H2O
R X R OH
Alcohol

j) Reaction with KSH: Haloalkanes react with potassium hydrosulfide to form thiols.

Alc KSH
R X R SH
thiol

k) Reaction with NaSR: Haloalkanes react with NaSR to form thio ethers.

NaSR'
R X R SR'
thio ethers

l) Reaction with Acetylides: Haloalkanes react with sodium acetylides to form higher alkynes.

CH CNa
R X CH C R
alkyne

m) Reaction with RCOOAg: When haloalkanes are heated with alcoholic solution of the
silver salt of a carboxylic acid, esters are formed.

R'COOAg
R X R'COOR AgX
ester

CH3CH2Br CH3COOAg CH3COOC2H5 AgBr

Note: The two products formed on reaction of R-X with KNO2 and AgNO2 as well as with
KCN and AgCN are due to tautomerism in these molecules.

2. Elimination reactions
Reaction with Alc KOH (Dehydrohalogenation):
Haloalkanes react with alcoholic KOH undergo elimination of hydrogen halide (HX) to
form alkenes.

Alc. KOH,
CH3CH2Cl H2C CH2
HCl

3. Reaction with Metals

a. Reaction with magnesium [formation of Grignard reagent]:
When a solution of an alkyl halide, in dry ether, is treated with magnesium metal, an
alkyl magnesium halide is formed.
Dry ether
R X Mg R MgX

𝒅𝒓𝒚 𝒆𝒕𝒉𝒆𝒓
C2H5Cl + Mg → C2H5MgCl
b. Reaction with sodium (Wurtz reaction):
Alkyl halides react with sodium metal in dry ether to give alkanes with double the number
of carbon atoms present in the alkyl halides. This reaction is called Wurtz reaction.
Dry ether
2R X 2 Na R R 2 NaX

Example: Ethyl chloride reacts with sodium metal in dry ether gives n – butane.

Zn
2R X R R ZnX2
Frankland reaction

b. Reaction with other metals:

4. Other reactions
a. Reduction: Haloalkanes are reduced to alkanes by many reagents like.
i. Zn + HCl, Sn + HCl
ii. Lithium aluminium hydride [LiAlH4] or Sodium borohydride [NaBH4]
iii. H2 in the presence of nickel or palladium
Reducing agent
R X 2H R H HX

Reducing agent
CH3CH2Cl CH3CH3
b. Friedel-Craft’s reaction: Alkyl halides react with benzene in presence of anhydrous
AICI3 to form alkyl benzenes.
R
AlCl3
R X HCl

CH2CH3
AlCl3
CH3CH2Cl HCl

c. Action of halogen: Haloalkenes react with Cl2 or Br2 in presence of UV light or at higher
temperature undergo halogenation to form poly halogenated compounds.

Note: C2CI6 (hexachloroethane) is a solid and is known as artificial camphor.

d. Action of heat: 3000 C

RCH2CH2X RCH CH2 HX

Types of nucleophilic substitution reactions:

The nucleophilic substitution reactions can be classified into two types. SN1 and SN2
reactions.
SN1 reaction mechanism [studied as substitution nucleophilic, first order reaction]:
SN1 stands for unimolecular nucleophilic substitutions reaction. SN1 reactions generally
carried out in polar protic solvents.
Example: The reaction between tert- butyl bromide and hydroxide ion gives tert- butyl
alcohol and follows the first order kinetics.
Mechanism:
Step-1:

Step-2:

SN1 Reaction takes place in two steps. In the first step Ionization of C-X bond takes
to give the carbocation intermediate.
First step is slow and is the rate – determining step. As the nucleophile is not
involved in the rate - determining step, the rate of reaction depends only upon the
concentration of alkyl halide (R-X) and is therefore, a first order reaction.

i.e. Rate = K [R-X]

In the second step nucleophile combines with the carbocation to give the
substituted product.
The order of reactivity depends upon the stability of carbocation formed in the
first step. Since the 30 carbocation is most stable, the ionization of tertiary alkyl halide is
favored. The order of reactivity of alkyl halides for SN1 reaction is
Tertiary > secondary > primary

SN2 reaction mechanism [studied as substitution nucleophilic, second order reaction]:

SN2 stands for bimolecular nucleophilic substitutions reaction.
Example: The reaction between methyl bromide and hydroxide ion gives methyl alcohol
and follows the second order kinetics.
 SN2 reaction takes place in a single step. This reaction proceeds through the
formation of transition state. No carbocation intermediate is formed. Formation of
carbon - external nucleophile bond and cleavage of carbon - halogen bond takes place
simultaneously.

Since, both alkyl halide and nucleophile are involved in the transition state, the
rate of reaction depends upon the concentration of both the alkyl halide and the
nucleophile. Therefore it is a second order reaction.

i.e. Rate = K [R-X] [Z-]

The transition state form of tertiary alkyl halide is less stable due to steric hindrance. i.e.
crowding of alkyl groups. The order of reactivity alkyl halides for SN2 reaction is

Primary > Secondary > Tertiary

Thus the reactivity of SN1 versus SN2 is:

Ethyl chloride is used:

i. as a refrigerant
ii. as a local anesthetic
iii. as a solvent
iv. as ethylating agent in the preparation of tetraethyl lead [TEL]
v. in the preparation of Grignard’s reagent
Assignment questions:

1. Explain the classification of haloalkanes

2. Give a brief account on the nomenclature of haloalkanes.
3. Discuss the mechanisms of nucleophilic substitution reactions in alkyl halides
4. Write the methods preparation and properties of alkyl halides.
5. Arrange the following in the increasing order of their boiling points.
i. Bromo methane; bromoform; chloromethane;
ii. n – Propyl chloride; isopropyl chloride; n – Butyl chloride

Give your explanation.

SAQs:

1. The alkyl halide among the following

a. CnH2n+1 X
b. CnH2n-1 X
c. CnH2n X
d. CnH(2n-2) X

Solution: a)

2. Identify a secondary alkyl halide from the following.

a. (CH3)3 CCH2Br
b. (CH3)3 CBr
c. (CH3)2 CHCl
d. CH3(CH2)3CH2I

Solution: c)

3. Which of the following is isopropyl chloride?

b) CH3-CHCl – CHBr- CH3

c) CH3-CHCl- CH3

Solution: c)
4.

a. 1 – chloro, 2 – methyl pentane

b. 2, 2 – di methyl, 3 – chloro propane
c. 1 – chloro, 2, 2 – di methyl propane
d. 1 – chloro, 2 – methyl isobutane

Solution: c)

5. The correct structure of 2 – bromo, 3 – methyl butane is

Solution: b)

6. The C – X bond in an alkyl halide is

a. an ionic bond
b. a polar covalent bond
c. a non – polar covalent bond
d. a coordinate covalent bond

Solution: b)
LAQs:

1. Explain the nature of C – X bond.

Solution:

Nature of C – X bond:

Halogens are more electronegative elements than carbon. Due to the difference in the electron
negativity values the carbon – halogen bond of an alkyl halide is polarized. The partial positive
charge is on carbon atom and partial negative charge is present on halogen atom.

The size of halogen atom increases as we go down the group in the periodic table; fluorine atom is
the smallest and iodine atom is the largest in the VII group. Consequently the carbon – halogen
bond length also increases from C – F to C – I. As the bond length increases the bond enthalpy
decreases.

Bond Bond length (in pm) Bond enthalpies (in kJ mol-1)

CH3 – F 139 452
CH3 – Cl 178 351
CH3 - Br 193 293
CH3 – I 214 234

2. Discuss the physical properties of haloalkanes

Solution:

Physical properties:

Alkyl halides are colorless but bromides and iodides get color on standing or on exposure to light.
They have pleasant odour. Lower alkyl halides are gases but higher alkyl halides are either liquids or
solids. Alkyl halides are more polar and have higher molecular masses when compared to the parent
hydrocarbons. Because of these two reasons they have stronger inter molecular forces of attraction
and possess high boiling points and melting points compared to parent hydrocarbons. For a given R,
the order of melting points and boiling points would be RI > RBr . RCl > RF. Among isomeric alkyl
 halides the boiling points decrease with increase in branching. As the branching increases the
adjacent molecules are not able to come close to be attached strongly. For C4H9 Br we have the
following structures and the corresponding boiling points are shown.

The density of these compounds increases with increase in number of carbon atoms in the chain,
the number of halogen atoms and the atomic masses of halogen atoms.

Compound Density ( g ml-1 ) Compound Density ( g ml-1)

n – C3H7 Cl 0.89 CH2Cl2 1.336
n – C3 H7 Br 1.335 CHCl3 1.489
n – C3 H7 I 1.747 CCl4 1.595
The halogen compounds are only slightly soluble in water. In order for a haloalkane to dissolve in
water, energy is required to overcome the intermolecular attractions between the haloalkane
molecules and break the hydrogen bonds between water molecules. Less energy is released when
new attractions are set up between the haloalkanes and the water molecules; these are not as
strong as the original hydrogen bonds in water. As a result, the solubility of haloalkanes in water is
low. However 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.

Problem set:

1. The correct order of density in the following sets of compounds.

a. CH3Cl > CH2Cl2 > CHCl3 > CCl4
b. CH3Cl < CH2Cl2 < CHCl3 < CCl4
c. CH3Cl > CCl4 > CHCl3 > CH2Cl2
d. CH3Cl > CCl4 > CH2Cl2 > CHCl3

Solution: b)
2. Which of the following alkylhalides is preferentially hydrolyzed by SN1 mechanism?
a. CH3Cl
b. C2H5Cl
c. n -C3H7Cl
d. (CH3)3CCl
Solution: d)
3. The order of reactivity of alkyl halides towards nucleophilic substitution is;
a. RI > RBr > RCl > RF
b. RI < RBr < RCl < RF
c. RI > RBr > RCl > RF
d. RI < RBr > RCl < RF
Solution: a)
4. The reaction CH3Br + OH- → CH3OH + Br- ,follows _____mechanism:
a. SN1
b. SN2
c. SE1
d. SE2

Solution: b)

5. The reaction described below is:

a. SE 1
b. SN2
c. SN1
d. SE 2

Solution: b)

6. Pick up the correct statement about alkyl halides: they

a. have H – bonding
b. are soluble in water
c. do not behave as solvents
d. do not contain any polar bond.
Solution: c)
7. Write the mechanism of SN1 reaction of alkyl halides

Solution:

SN1 reaction [studied as substitution nucleophilic, first order reaction]:

This type of reaction proceeds in two steps as:

8. Write the common name and IUPAC name of the following compound.

Solution:

t – butyl chloride => common name.

2- chloro – 2 – methylpropane => IUPAC name.

Exercise questions:

1. Write structures of the following compounds:

a.2-Chloro-3-methylpentane
b. 1-Chloro-4-ethylcyclohexane
c. 4-tert. Butyl-3-iodoheptane
d. 1,4-Dibromobut-2-ene
e.1-Bromo-4-sec. butyl-2-methylbenzene
2. Write structures of different dihalogen derivatives of propane.
3. Which of the following pairs would you expect to react by an SN2 mechanism? Explain your answer.

4. Which one of the following has the highest dipole moment?

a.CH2Cl2
b. CHCl3
c. CCl4

5. Which compound in each of the following pairs will react faster in SN2 reaction with OH−?

a.CH3Br or CH3I
b. (CH3)3CCl or CH3Cl

6. Arrange the compounds of each set in order of reactivity towards SN2 displacement:

3 – Bromo – 2 – methylbutane, 1 – Bromopentane, 2 – Bromopentane

7. Write down the preparation methods of alkyl halides

8. Discuss the chemical properties of alkyl halides.
Solutions:

1.
2.

There are four different dihalogen derivatives of propane. The structures of these derivatives are
shown below.

3.

In option c) both the alkyl halides are 10 – alkyl halides. We know 10 – alkyl halides follow SN2
mechanism.

4.

μ = 1.60D
In case of CH2Cl2, the resultant of the dipole moments of two C−Cl bonds is strengthened by the
resultant of the dipole moments of two C−H bonds. As a result, CH2Cl2 has a higher dipole moment
of 1.60 D than CHCl3 i.e., CH2Cl2 has the highest dipole moment.

μ = 1.08D

In CHCl3, the resultant of dipole moments of two C−Cl bonds is opposed by the resultant of dipole
moments of one C−H bond and one C−Cl bond. Since the resultant of one C−H bond and one C−Cl
bond dipole moments is smaller than two C−Cl bonds, the opposition is to a small extent. As a result,
CHCl3 has a small dipole moment of 1.08 D.

μ = 0D

CCl4 is a symmetrical molecule. Therefore, the dipole moments of all four C−Cl bonds cancel each
other. Hence, its resultant dipole moment is zero.

Hence, the given compounds can be arranged in the increasing order of their dipole moments as:

CCl4 < CHCl3 < CH2Cl2

 5.

a. In the SN2 mechanism, the reactivity of halides for the same alkyl group increases in the order.

R−F << R−Cl < R−Br < R−I

This happens because as the size increases, the halide ion becomes a better leaving group.

Therefore, CH3I will react faster than CH3Br in SN2 reactions with OH−.

The SN2 mechanism involves the attack of the nucleophile at the atom bearing the leaving group.
But, in case of (CH3)3CCl, the attack of the nucleophile at the carbon atom is hindered because of
the presence of bulky substituents on that carbon atom bearing the leaving group. On the other
hand, there are no bulky substituents on the carbon atom bearing the leaving group in CH 3Cl.
Hence, CH3Cl reacts faster than (CH3)3CCl in SN2 reaction with OH−.

6.

An SN2 reaction involves the approaching of the nucleophile to the carbon atom to which the leaving
group is attached. When the nucleophile is sterically hindered, then the reactivity towards S N2
displacement decreases. Due to the presence of substituents, hindrance to the approaching
nucleophile increases in the following order.

1 – Bromopentane < 2 – bromopentane < 2 – Bromo – 2 – methylbutane

Hence, the increasing order of reactivity towards SN2 displacement is:

2 – Bromo – 2 – methylbutane < 2 – Bromopentane < 1 – Bromopentane