Unit 10

Chapter 10
Haloalkanes & Haloarenes

32.1 Introduction
32.2 Nomenclature of Halogeno-compounds
32.3 Physical Properties of Halogeno-compounds
32.4 Preparation of Halogeno-compounds
32.5 Reactions of Halogeno-compounds
32.6 Nucleophilic Substitution Reactions
32.7 Elimination Reactions
32.8 Uses of Halogeno-compounds
1
Introduction
Haloalkanes are organic compounds having one or more

halogen atoms replacing hydrogen atoms in alkanes
Haloarenes - halogen is attached directly to a benzene
(aromatic) ring
Haloalkanes are classified into primary, secondary and
tertiary, based on the number of alkyl groups attached to
the carbon atom which is bonded to the halogen atom
2
Classification
On the Basis of Number of Halogen Atoms:

classified as mono, di, or polyhalogen (tri, tetra-, etc.) E.g.
Monohalocompounds further be classified according to the hybridisation of

the carbon atom to which halogen is bonded, as discussed below.
3
Compounds Containing sp3 CX Bond (X= F, Cl, Br, I)
This class includes
(a) Alkyl halides or haloalkanes (RX)
Halogen atom is bonded to an alkyl group (R) with general formula C nH2n+1X.
They are further classified as primary, secondary or tertiary according to the
nature of carbon to which halogen is attached.
(b) Allylic halides

Halogen atom is bonded to an sp3-hybridised C-atom next to carbon-carbon
double bond (C=C) i.e. to an allylic carbon.
(c) Benzylic halides

These are the compounds in which the halogen atom is bonded to an sp3-
hybridised carbon atom next to an aromatic ring.
4
Compounds Containing sp2 CX Bond
This class includes:
(a) Vinylic halides
These are the compounds in which the halogen atom is bonded
to an sp2-hybridised carbon atom of a carbon-carbon double
bond (C = C).
(b) Aryl halides

These are the compounds in which the halogen atom is bonded
to the sp2-hybridised carbon atom of an aromatic ring.
5
Introduction
Halobenzenes are organic compounds in which the halogen

atom is directly attached to a benzene ring
e.g.
not a halobenzene, because the

chlorine atom is not directly attached
to the benzene ring
6
Nomenclature of Halogeno-compounds
Naming haloalkanes are similar to those for naming

alkanes
The halogens are written as prefixes: fluoro- (F), chloro-

(Cl), bromo- (Br) and iodo- (I)
e.g.
7
When the parent chain has both a halogen and an alkyl

substituent, the chain is numbered from the end nearer the first
substituent regardless of what substituents are
e.g.
8
Common name: The common names of alkyl halides are derived by
naming the alkyl group followed by the halide.
Dihaloalkanes having same type of halogen atoms named as alkylidene or
alkylene dihalides.
Dihalo-compounds having same type of halogen atoms 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).
gem-dihalides are named as alkylidene halides and vic-dihalides are named

as alkylene dihalides. In IUPAC system, they are named as dihaloalkanes.
9
In case of halobenzenes, the benzene ring is numbered so as

to give the lowest possible numbers to the substituents
e.g.
10
Example 32-1
Draw the structural formulae and give the IUPAC names
of all isomers with the following molecular formula.
(a) C4H9Br
Solution:
(a) Answer
11
Example 32-1
Draw the structural formulae and give the IUPAC names of all isomers with
the following molecular formula. (b) C4H8Br2
Solution:
(b)
Answer
12
STRUCTURAL ISOMERISM IN HALO-ALKANES
Different structures are possible due to...

Different positions for the halogen and branching of the carbon chain
1-chlorobutane
2-chlorobutane
2-chloro-2-methylpropane 1-chloro-2-methylpropane
13
Check Point 32-1

Draw the structural formulae and give the IUPAC names for
all the structural isomers of C5H11Br.
Answer
14
15
Physical Properties of Halogeno-compounds
Melting Boiling
Density at
Name Formula point point
20C (g cm3)
(C) (C)
Chloro-derivatives:
Chloromethane CH3Cl 97.7 23.8
Chloroethane CH3CH2Cl 136 12.5
1-Chloropropane CH3(CH2)2Cl 123 46.6 0.889
1-Chlorobutane CH3(CH2)3Cl 123 78.5 0.886
1-Chloropentane 99 108 0.883
CH3(CH2)4Cl
1-Chlorohexane 83 133 0.878
CH3(CH2)5Cl
(Chloromethyl)benzene 39 179 1.100
Chlorobenzene C6H5CH2Cl 45.2 132 1.106
C6H5Cl
16
Melting Boiling Density at

Name Formula point point 20C (g cm
(C) (C) 3
)
Bromo-derivatives:
Bromomethane CH3Br 93.7 3.6
Bromoethane CH3CH2Br 119 38.4 1.460
1-Bromopropane CH3(CH2)2Br 109 70.8 1.354
1-Bromobutane CH3(CH2)3Br 113 101 1.279
1-Bromopentane 95 129 1.218
CH3(CH2)4Br
1-Bromohexane 85 156 1.176
CH3(CH2)5Br
(Bromomethyl)benzene 3.9 201 1.438
Bromobenzene C6H5CH2Br 30.6 156 1.494
C6H5Br
17
Melting
Boiling Density at
Name Formula point
point (C) 20C (g cm3)
(C)
Iodo-derivatives:
Iodomethane CH3I 66.5 42.5 2.279
Iodoethane CH3CH2I 108 72.4 1.940
1-Iodopropane CH3(CH2)2I 101 102 1.745
1-Iodobutane CH3(CH2)3I 103 130 1.617
1-Iodopentane 85.6 155 1.517
CH3(CH2)4I
1-Iodohexane 181 1.437
CH3(CH2)5I
(Iodomethyl)benzene 24.5 decompose 1.734
C6H5CH2I
18
BoilingPoint
Boiling Pointand
andMelting
MeltingPoint
Point
19
Boiling Point: Increases with molecular size due to
increased van der Waals forces
Haloalkanes have higher b.p. and m.p. than alkanes

dipole-dipole interactions present between haloalkane molecules
m.p. and b.p. increase in the order:
RCH2F < RCH2Cl < RCH2Br < RCH2I
larger, more polarizable halogen atoms increase the
dipole-dipole interactions between the molecules
No. of carbon m.p. and b.p.
20
Density
Density
Relative molecular mass
density
closer packing of the smaller molecules in the

liquid phase
Bromo and iodoalkanes are all denser than water at

20C
21
Solubility
Solubility
Although C X bond is polar, it is not polar enough to

have a significant effect on the solubility of haloalkanes
and halobenzenes
Immiscible with water
Soluble in organic solvents
22
Solubility
Solubility
For a haloalkane to dissolve in water, energy is required to overcome the

attractions between the haloalkane molecules and break the H-bonds
between water molecules.
Less energy is released when new attractions are set up between haloalkane
and water molecules as these are not as strong as the original H-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.
23
BondLength
Bond Length
Since the size of halogen atom increases as we go down the
group in the periodic table, fluorine atom is the smallest and
iodine atom, the largest. Consequently the carbon-halogen
bond length also increases from CF to CI.
Carbon-Halogen (CX) Bond Lengths, Bond Enthalpies and Dipole Moments
24
Preparation of Halogeno-compounds
Preparationof
Preparation ofHaloalkanes
Haloalkanes
Substitution of Alcohols
Prepared by substituting OH group of alcohols

with halogen atoms
Common reagents used: HCl, HBr, HI, PCl3 or PBr3
The ease of substitution of alcohols:

3 alcohol > 2 alcohol > 1 alcohol > CH3OH
This is related to the stability of the reaction

intermediate (i.e. stability of carbocations)
25
Reaction with Hydrogen Halides
Dry HCl is bubbled through alcohols in the presence

of ZnCl2 catalyst
For the preparation of bromo- and iodoalkanes, no

catalyst is required
26
The reactivity of hydrogen halides: HI > HBr > HCl
e.g.
27
Reaction with Phosphorus Halides
Haloalkanes can be prepared from the vigorous reaction
between cold alcohols and phosphorus(III) halides
28
Addition of halogen or HX to Alkenes & Alkynes
Addition of halogens or hydrogen halides to an alkene or

alkyne can form a haloalkane
e.g.
Addition of Br2 in CCl4 resulting in discharge of reddish brown colour of
Br2 (important method for the detection of double bond) due to synthesis of
vic-dibromides, which are colourless.
29
Propene yields two products, however only one predominates

as per Markovnikovs rule.
30
Halogen Exchange
Alkyl iodides prepared by reaction of alkyl chlorides /
bromides with NaI in dry acetone (Finkelstein reaction).
NaCl or NaBr formed is precipitated in dry acetone facilitates
forward reaction according to Le Chateliers Principle.
Alkyl fluorides best synthesized by heating alkyl

chloride/bromide with metallic fluoride such as AgF, Hg2F2,
CoF2 or SbF3 (Swarts reaction).
31
Preparationof
Preparation ofHalobenzenes
Halobenzenes
Halogenation of Benzene
Benzene reacts readily with chlorine and bromine

(electrophilic substitution) in the presence of Lewis acid
catalysts (e.g. FeCl3, FeBr3, AlCl3)
32
TheHalogenation of Benzene
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 HI
formed during iodination.
Fluoro compounds are not prepared by this method due to high
reactivity of fluorine.
33
Sandmeyers Reaction
When a primary aromatic amine suspended in cold aq. mineral acid, is
treated with sodium nitrite, a diazonium salt is formed. Mixing the solution
of freshly prepared diazonium salt with cuprous chloride or cuprous
bromide results in the replacement of the diazonium group by Cl or Br.
Replacement of diazonium gp by iodine not require cuprous halide and is
done simply by shaking the diazonium salt with potassium iodide.
34
Check Point 32-2

State the major products of the following reactions:
(a) CH3CHOHCH2CH3 + PBr3
(b) CH3CH = CH2 + HBr
(c) CH3C CH + 2HBr
(a) CH3CHBrCH2CH3
(d) (b) CH3CHBrCH3
Answer
(c) CH3CBr2CH3
(d)
35
Reactions of Halogeno-compounds
Halogens have a greater electronegativity than

carbon so carbon-halogen bond is polar
Carbon atom bears a partial positive charge
Halogen atom bears a partial negative charge
The carbon is thus open to attack by nucleophiles
36
Characteristic reaction:
Nucleophilic substitution reaction

Nucleophile uses its lone pair to provide electrons for a new bond
Halogen is displaced - carbon can only have 8 electrons in its outer shell
the result is substitution following attack by a nucleophile
Mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION
Alcohols, ethers, esters, nitriles & amines formed by

substituting OH, OR, RCOO, CN and NH2 gps resp.
37
NUCLEOPHILIC SUBSTITUTION - RATE OF REACTION
Basics An important reaction step is breaking of the carbon-halogen (C-X) bond
The rate of reaction depends on the strength of the C-X bond
C-I 238 kJmol-1 weakest - easiest to break
C-Br 276 kJmol-1
C-Cl 338 kJmol-1
C-F 484 kJmol-1 strongest - hardest to break

Experiment Water is a poor nucleophile but it can slowly displace halide ions
C2H5Br(l) + H2O(l) > C2H5OH(l) + H+ (aq) + Br(aq)

If aqueous silver nitrate is shaken with a halogenoalkane (they are immiscible)
The displaced halide combines with a silver ion to form a precipitate of a silver
halide. The weaker the C-X bond the quicker the precipitate appears.
This form of nucleophilic substitution is known as S N2.
38
Another characteristic reaction:
Elimination reaction
Haloalkane Base Alkene
Bases and nucleophiles are the same kind of reagents
Nucleophilic substitution and elimination reactions

always occur together and compete each other
39
Nucleophilic Substitution Reactions
Reactionwith
Reaction withSodium
SodiumHydroxide
Hydroxide
Reagent Aqueous* sodium (or potassium) hydroxide
The reactions proceed in 2 different reaction

mechanisms:
bimolecular nucleophilic substitution (SN2)
40 unimolecular nucleophilic substitution (SN1)

Bimolecular Nucleophilic Substitution (SN2)
Example: CH3 Cl + OH CH3OH + Cl

Initial Initial
Experiment Initial rate
[CH3Cl] [OH]
number (mol dm3 s1)
(mol dm ) (mol dm )
3 3
1 0.001 1.0 4.9 107

2 0.002 1.0 9.8 107
3 0.001 2.0 9.8 107
4 0.002 2.0 19.6 107
Results of kinetic study of reaction of CH3Cl with OH
Rate = k[CH3Cl][OH]
Order of reaction = 2
both species are involved in rate determining step
41
Reaction mechanism of the SN2 reaction:
The nucleophile attacks from the backside of the

electropositive carbon centre
In the transition state, the bond between C and O is

partially formed, while the bond between C and Cl
is partially broken
42
Transition state involve both
the nucleophile and substrate
second order kinetics of the
reaction
Energy profile of the reaction of CH3Cl and OH-

by SN2 mechanism
43
Stereochemistry of SN2 Reactions
The nucleophile attacks from the backside of the

electropositive carbon centre
The configuration of the carbon atom under attack

inverts
44
Unimolecular Nucleophilic Substitution (SN1)
Example:
Kinetic study shows that:
Rate = k[(CH3)3CCl]
The rate is independent of [OH]
Order of reaction = 1
only 1 species is involved in the rate
determining step
45
Reaction mechanism of SN1 reaction involves 2 steps

and 1 intermediate formed
Step 1:
Slowest step (i.e. rate determining step)
Formation of carbocation and halide ion
46
Step 2:
Fast step
Attacked by a nucleophile to form the product
47
Rate determining step involves the
breaking of the C Cl bond to
form carbocation
Only 1 molecule is involved in the
rate determining step
first order kinetics of the
reaction
Energy profile of the

reaction of (CH3)3CCl
and OH- by SN1
mechanism
48
Stereochemistry of SN1 Reactions
The carbocation formed has a trigonal planar structure
The nucleophile may either attack from the frontside

or the backside
49
For some cations, different products may be formed by
either mode of attack
e.g.
The reaction is called racemization
50
The above SN1 reaction leads to racemization
formation of trigonal planar carbocation intermediate
51
The attack of the nucleophile from either side of the planar

carbocation occurs at equal rates and results in the formation
of the enantiomers of butan-2-ol in equal amounts
52
Factors Affecting the Rates of SN1 and SN2 Reactions
Most important factors affecting the relative rates of SN1

and SN2 reactions:
1. The structure of the substrate
2. The concentration and strength of the nucleophile

(for SN2 reactions only)
3. The nature of the leaving group
53
The Structure of the

Substrate
1. SN2 reactions
The reactivity of haloalkanes in SN2 reactions:

CH3X > 1 haloalkane > 2 haloalkane > 3 haloalkane
Steric hindrance affects the reactivity

bulky alkyl groups will inhibit the approach of
nucleophile to the electropositive carbon centre
energy of transition state activation energy
54
Steric effects in the SN2 reaction
55
2. SN1 reactions
Critical factor: the relative stability of the carbocation

formed
Tertiary carbocations are the most stable

3 electron-releasing alkyl groups stabilize the
carbocation by releasing electrons
Methyl, 1, 2 carbocation have much higher energy

activation energies for SN1 reactions are very large and
rate of reaction become very small
56
The Concentration and Strength of the

Nucleophile
Only affect SN2 reactions
Concentration of nucleophile rate
57
Relative strength of nucleophiles can be correlated
with two structural features:
(I) A negatively charged nucleophile (e.g. OH) is
always a stronger nucleophile than a neutral
nucleophile (e.g. H2O)
(II)In a group of nucleophiles in which the

nucleophilic atom is the same, the order of
nucleophilicity roughly follows the order of
basicity:
e.g. RO > OH >> ROH > H2O
Strength rate
58
The Nature of Leaving Group
Halide ion departs as a leaving group
For the halide ion, the ease of leaving:

I > Br > Cl > F
This is in agreement with the order of bond enthalpies

of carbon-halogen bonds
Bond enthalpy (kJ mol

Bond 1
) C I bond is
CF +484 weakest I is
the best leaving
C Cl +338 group
C Br +276
CI +238
59
Uncharged or neutral compounds are better

leaving groups
e.g. The ease of leaving of oxygen compounds:
H2O >> OH > RO
Strongly basic ions rarely act as leaving group

e.g.
60
When an alcohol is dissolved in a strong acid, it can

react with a halide ion
the acid protonates the OH group, and the

leaving group becomes a neutral water molecule
e.g.
61
Comparision of Rates of Hydrolysis of

Haloalkanes and Halobenzene
1. Experiment 1 : Comparison of the rates of hydrolysis

of 1-chlorobutane, 1-bromobutane and 1-iodobutane
(a) Objective
To study the effect of the nature of the halogen leaving

group on the rate of hydrolysis of haloalkanes
62
(b) Procedure
Put 2 cm3 of ethanol and 1 cm3 of 0.1 M aqueous silver nitrate into
each of three test tubes
Place them in a water bath at 60C
After 5 mins, add 5 drops of 1-chlorobutane the test tube A, 5 drops of

1-bromobutane to B and 5 drops of 1-iodobutane to C
Shake each test tube and observe for 10 mins
63
(c) Result and Observation
A precipitate of silver halide is formed in each of the

three test tubes
Test tube A Test tube B Test tube C
AgCl(s) AgBr(s) AgI(s)
64
(d) Discussion
Water molecule is the nucleophile of the reaction
Haloalkanes react with water by nucleophilic substitutions
The halide ion departs as the leaving group
The ease of leaving of halide ions decreases: I > Br > Cl
The order of precipitates appeared tends to follow the order

of ease of leaving of the halide ions, which subsequently
form precipitates with Ag+ ions from AgNO3
Ag+(aq) + X(aq) AgX(s)
65
2. Experiment 2: Comparison of the rates of hydrolysis of

primary, secondary and tertiary haloalkanes and
halobenzene
(a) Objective
To study the effect of the structure of haloalkanes on

the rate of hydrolysis of them and to compare the
rates of hydrolysis of haloalkanes and halobenzene
66
(b) Procedure
Put 2 cm3 of ethanol and 1 cm3 of 0.1 M aqueous silver nitrate into
each of four test tubes
Add 5 drops of 1-chlorobutane the test tube D, 5 drops of
2-chlorobutane to E, 5 drops of 2-chloro-2-methylpropane to F and
5 drops of chlorobenzene to G
Shake each test tube well and observe for 10 mins
67
(c) Result and Observation
Except test tube G, a white precipitate of silver chloride

was formed in each of test tubes D, E and F.
Test tube D Test tube E Test tube F Test tube G
68
(d) Discussion
The halogen-compounds used in the experiment are of

different classes:
The rate of formation of the white precipitate of silver

chloride decreases in the order:
2-chloro-2-methylpropane > 2-chlorobutane

1-chlorobutane >> chlorobenzene
69
The rate of hydrolysis of halogeno-compounds is related to

the structure of the substrate around the carbon which is
being attacked
The experimental condition favours SN1 reactions
tertiary haloalkane reacts at the fastest rate

while primary haloalkane proceeds at a slower rate
Chlorobenzene can be hydrolyzed to phenol under severe

conditions (cannot be carried out in school laboratory)
70
Unreactivity of Halobenzene
Halobenzenes are comparatively unreactive to

nucleophilic substitution reactions
the p orbital on the carbon atom of the benzene ring

and that on the halogen atom overlap side-by-side to
form a delocalized bonding system
71
Delocalization of electrons throughout the ring and
halogen atom
The C X bond has partial double bond character

stronger than that of haloalkane
larger amount of energy is required to break the

bond
substitution reactions become more difficult to

occur
Delocalization of electrons makes the polarity of
C X bond
electropositive carbon center is less
susceptible to nucleophilic attack
72
Delocalized electrons repel any approaching

nucleophiles
unreactive towards SN2 reactions
Benzene cations are highly unstable because of loss

of aromaticity
unreactive towards SN1 reactions
73
Example 32-2
The reactions between three bromine-containing
compounds and aqueous silver nitrate at room conditions
are summarized in the following table:
Compound Reaction with aqueous silver nitrate
A pale yellow precipitate appears
Sodium bromide
immediately
No reaction at first; a pale yellow
1-Bromobutane precipitate appears after several
minutes
Bromobenzene No reaction even after several hours
Solution:
(a) What is the pale yellow precipitate produced in the
(a) Silver bromide Answer
reaction between silver nitrate and sodium bromide?
74
Example 32-2
(b) Write an ionic equation for the reaction.
Answer
Solution:
(b) Ag+(aq) + Br(aq) AgBr(s)
75
Example 32-2
(c) Why does silver nitrate produce no immediate
precipitate with 1-bromobutane, even though it
contains bromine? Why is there the formation of the
pale yellow precipitate after several minutes?
Answer
Solution:
(c) The hydrolysis of 1-bromobutane takes time.
Precipitation of AgBr occurs only after OH from
water has replaced Br from 1-bromobutane.
76
Example 32-2
(d) Briefly explain why bromobenzene does not give any
precipitate with aqueous silver nitrate. Answer
Solution:
(d) The C Br bond of bromobenzene is strengthened
due to the delocalization of electrons throughout the
benzene ring and the halogen atom. As the breaking of
the C Br bond of bromobenzene requires a larger
amount of energy than 1-bromobutane, the substitution
reaction becomes more difficult to occur. Thus,
bromobenzene does not give any precipitate with
aqueous silver nitrate.
77
Example 32-3
Which is the stronger nucleophile in each of the following
pairs? Explain your choice briefly.
(a) OH and H2O
(b) OH and CH3CH2O Answer
Solution:
(a) OH is a stronger nucleophile than H2O because it
carries a negative charge while H2O is electrically neutral.
(b) CH3CH2O is a stronger nucleophile than OH. It is
because the ethyl group (CH3CH2) is an electron-
releasing group, this increases the electron density on
the oxygen atom. This makes CH3CH2O to be a stronger
nucleophile than OH.
78
Check Point 32-3

Predict whether the following substitution reaction follows
mainly SN1 or SN2 pathway. Briefly explain your answer.
(a) CH3I + OH CH3OH + I
Answer
(a) The reaction follows mainly the SN2 mechanism because
of the following reasons. The haloalkane (CH 3I) is a methyl
halide. There is little steric hindrance for the nucleophile to
attack the carbon atom of the molecule. On the other hand, if
the reaction follows the SN1 mechanism, the carbocation
(CH3+) formed is not stabilized by the inductive effects of
alkyl groups. Thus the SN1 mechanism for this reaction is
unfavourable.
79
Check Point 32-3

Predict whether the following substitution reaction follow
mainly SN(b)
1 orThe
SN2reaction
pathway. Briefly
follows mainly explain your answer.
the S 1 mechanism. It is
N
(b) because the haloalkane is a secondary haloalkane with a

bulky phenyl group attached directly to the carbon atom
bearing the halogen atom. The bulky phenyl group exerts a
dramatic steric hindrance to the approaching nucleophile.
Therefore, the SN2 mechanism for this reaction is not
favoured. On the other hand, the carbocation formed in Answer
the
SN1 reaction is stabilized by both the inductive effect of the
electron-releasing ethyl group and the resonance
effect of the phenyl group.
80
Reactionwith
Reaction withPotassium
PotassiumCyanide
Cyanide
A nitrile is formed when a haloalkane is heated under reflux

with an aqueous alcoholic solution of potassium cyanide
e.g.
81
Cyanide ion (CN) acts as a nucleophile

Halobenzenes do not react with potassium cyanide
The reaction is very useful because the nitrile can be

hydrolyzed to carboxylic acids which can be reduced
to alcohols
A useful way of introducing a carbon atom into an

organic molecule, so that the length of the carbon
chain can be increased
82
Reactionwith
Reaction withAmmonia
Ammonia
When a haloalkane is heated with an aqueous alcoholic solution

of ammonia under a high pressure, an amine is formed
e.g.
83
Ammonia is a nucleophile because the presence of a

lone pair of electrons on the nitrogen atom
As the lone pair electrons on nitrogen atom in ethylamine

are still available, the ethylamine will compete with
ammonia as the nucleophile.
A series of further substitutions take place
A mixture of products is formed
84
The reaction stops at the formation of a quaternary

ammonium salt
The competing reactions can be minimized by using an

excess of ammonia
85
Example 32-4
Give the reagents and reaction conditions needed for each
of the following conversions:
(a) (CH3)3CBr (CH3)3COH
(b) CH3I CH3OC2H5
Answer
(c) CH3I (CH3)4N I+
Solution:
(a) Dilute NaOH
(b) C2H5ONa+ or Na in C2H5OH
(c) NH3 in excess CH3I
86
Check Point 32-4

Give the name(s) and structural formula(e) of the major
organic product(s) formed in each of the following reactions.
(a)
(a)
(b)
(b) CH3NH2 Methylamine
(c) (c)
Answer
87
Elimination Reactions
Formationof
Formation ofAlkenes
Alkenes
The elimination of HX from adjacent atoms of a haloalkane

is widely used for synthesizing alkenes
e.g.
88
The elements of a hydrogen halide are eliminated from a

haloalkane in this way, the reaction is called
dehydrohalogenation
89
Dehydrohalogenation of most haloalkanes yields more than

one product
e.g.
90
The major product will be the more stable alkene
The more stable alkene has the more highly substituted
double bond
Elimination follows the Saytzeffs rule when the elimination

occurs to give the more highly substituted alkene as the
major product
The stabilities of alkenes:
91
Elimination Versus Substitution
Nucleophiles are potential bases
Bases are potential nucleophiles
In SN2 pathway, elimination & nucleophilic subst.

compete each other
92
The products of reactions between haloalkanes and OH are
influenced by the solvent
SOLVENT ROLE OF OH MECHANISM PRODUCT
WATER NUCLEOPHILE SUBSTITUTION ALCOHOL
ALCOHOL BASE ELIMINATION ALKENE
Modes of attack
Aqueous soln OH attacks the slightly positive carbon bonded to the
halogen.
OH acts as a nucleophile
Alcoholic soln OH attacks one of the hydrogen atoms on a carbon atom

adjacent the carbon bonded to the halogen.
OH acts as a base (A BASE IS A PROTON ACCEPTOR)
Both reactions take place at the same time but by varying the solvent you can
influence which mechanism dominates.
93
Substitution is favoured when the substrate is primary
alcohol and the base is hydroxide ion
Elimination is favoured when the substrate is secondary

alcohol
94
Complication
OH removes a proton from a carbon atom adjacent the C bearing the

halogen. If there had been another carbon atom on the other side of the C-
Halogen bond, its hydrogen(s) would also be open to attack. If the
haloalkane is unsymmetrical (e.g. 2-bromobutane) a mixture of isomeric
alkene products is obtained.
but-1-ene
but-2-ene
can exist as cis and trans isomers
95
With tertiary haloalkanes, SN2 reactions cannot take place
Elimination is highly favoured especially at high

temperatures
Substitution occurs through SN1 mechanism only
96
Eliminations will be favoured when using:
1. higher temperatures
2. strong sterically hindered bases (e.g. (CH3)3CO)
97
CH3X RCH2X R2CHX R3CX

Methyl 1 2 3
Gives SN2 Gives mainly SN2 Gives mainly No SN2 reaction.
reactions only and gives mainly SN2 with a weak In hydrolysis,
E with a strong base (e.g. I, gives SN1 or E.
sterically hindered CN, RCO2) and At low
base (e.g. gives mainly E temperatures,
(CH3)3CO) with a strong SN1 is favoured.
base (e.g. RO) When a strong
base (e.g. RO)
is used or at
high
temperatures, E
predominates.
Summary of the reaction pathways for the substitution and
elimination reactions of simple haloalkanes
98
Formationof
Formation ofAlkynes
Alkynes
Alkynes can be produced by dehydrohalogenation of

dihaloalkanes
Two molecules of hydrogen halides are eliminated
e.g.
99
Example 32-5
(a) Hot and concentrated alcoholic potassium hydroxide
can eliminate hydrogen iodide from the compound
CH3CH2CHICH3. Suggest and name two possible
products. Answer
Solution:
(a)
100
Example 32-5
Solution:
(b) Draw the structural formulae and give the names of all
possible
(b) products formed by elimination of hydrogen
bromide from the dibromoalkane, CH3CHBrCHBrCH3.
Answer
101
Check Point 32-5

(a) Notice how the hydrogen and halogen atoms come off
from adjacent carbon atoms in an elimination reaction.
Could (iodomethyl)benzene undergo an elimination to
give a HI molecule? Why?
(a) No, because there is no hydrogen available

on the carbon atom adjacent to the carbon Answer
atom that is directly bonded to the iodine
atom.
102
Check Point 32-5

(b) 2-Iodo-2-methylbutane gives two elimination products:
one is 2-methylbut-2-ene, what is the other one?
Answer
(b) 2-Methylbut-1-ene
103
Check(c)Point 32-5
(c) Arrange the following compounds in order of increasing
tendency towards elimination reactions:
2-bromo-2-methylbutane, 1-bromopentane and
2-bromopentane
Answer
The rate of elimination depends on the stability of the

alkene formed. A more highly substituted alkene is more
stable and is formed more readily.
104
Reaction with Metals
Most organic chlorides, bromides and iodides react with certain metals to
give compounds containing carbon-metal bonds. Such compounds are
organo-metallic compounds e.g. alkyl magnesium halide, RMgX,
referred as Grignard Reagents.
These reagents are obtained by the reaction of haloalkanes with

magnesium metal in dry ether.
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.
105
Reaction with Metals
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. 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.
Wurtz reaction
Alkyl halides react with sodium in dry ether to give hydrocarbons containing
double the number of carbon atoms present in the halide. This reaction is known as
Wurtz reaction.
106
Reaction of Haloarenes
NucleophilicSubstitution
Nucleophilic Substitution
extremely less reactive towards nucleophilic substitution reactions due to:
(i) Resonance effect: electron pairs on halogen in conjugation with -

electrons of the ring resulting in following resonating structures.
CCl bond acquires a partial double bond, so, bond cleavage is difficult
than haloalkane and therefore, less reactive towards nucleophilic
substitution reaction.
halide substituents are ortho-para directing & deactivating

Br Br Br Br
BrOH
(hypobromous Br Br
acid)
Bromobenzene
107 Br
35.7% 1.0% 64.3%
(ii) Difference in hybridisation of carbon in CX bond:
In haloalkane, C-atom is sp3 hybridised but in haloarene, it is sp2-
hybridised (more electronegative) and can hold the electron pair of C
X bond more tightly than sp3-hybridised carbon. Thus, CCl bond
length in haloarene shorter and more difficult to break than in
haloalkane. Therefore, less reactive than haloalkanes.
(iii) Instability of phenyl cation: In haloarenes, phenyl cation formed as a

result of self-ionisation not stabilized by resonance and therefore, SN1
mechanism is ruled out.
108
empty
sp2 orbital
Cl
SN 1
C
Cl
SN1 not reasonable because:
1) CCl bond is strong; therefore, ionization

to a carbocation is a high-energy process
2) aryl cations are highly unstable
109
(iv) SN2 is not reasonable because the

aromatic ring blocks back-side approach of the
nucleophile. Inversion is not possible.
110
Replacementby
Replacement byhydroxyl
hydroxylgroup
group
Converted into phenol by heating in aqueous sodium hydroxide solution at a
temperature of 623K and a pressure of 300 atm.
Electron withdrawing group (-NO2) at ortho- and para-positions increases the

reactivity of haloarenes.
111
Replacementby
hydroxylgroup
group
The effect is pronounced when (-NO2) is at ortho and para-
positions but no effect by presence of electron withdrawing
group at meta-position.
112
Replacementby
hydroxylgroup
group
Presence of nitro group at ortho- and para-positions withdraws e-
density from benzene ring and thus facilitates the attack of the
nucleophile on haloarene. Carbanion thus formed is stabilised
through resonance. -ve charge appeared at ortho- and para-
positions w.r.t. halogen substituent is stabilised by NO2 group
In meta-nitrobenzene, no resonating structures bear -ve charge on

carbon atom bearing the NO2 group. Therefore, presence of nitro
group at meta- position does not stabilise the -ve charge & have no
effect on reactivity.
113
ElectrophilicSubstitution
Electrophilic SubstitutionReactions
Reactions
Haloarenes undergo usual electrophilic reactions of the benzene ring such as
halogenation, nitration, sulphonation and Friedel-Crafts reactions.
Halogen atom (slightly deactivating) is o, p directing; therefore, further substitution
occurs at ortho- and para positions w.r.t. halogen atom.
e- density increases more at ortho- and para-positions than at meta-.
But X-atom withdraw e- from benzene ring (I effect). So, ring gets deactivated as
compared to benzene & hence electrophilic subst. in haloarenes occur slowly & require
drastic conditions as compared to those in benzene.
114
Reactions
(i) Halogenation
(ii) Nitration
(iii) Sulphonation
115
Reactions
(iv) Friedel-Crafts reaction
116
Reactionswith
Reactions withMetals
Metals
Wurtz-Fittig reaction
A mixture of an alkyl halide and aryl halide gives an
alkylarene when treated with sodium in dry ether and is called
Wurtz-Fittig reaction.
Fittig reaction
Aryl halides also give analogous compounds when treated
with sodium in dry ether, in which two aryl groups are joined
together. It is called Fittig reaction.
117
Polyhalogen Compounds
Dichloromethaneor
Dichloromethane ormethylene
methylenedichloride
dichloride
widely used as a solvent as a paint remover, as a propellant in aerosols, and
as a process solvent in the manufacture of drugs.
used as a metal cleaning and finishing solvent.
It harms the human CNS. Exposure to lower levels of MDC in air can lead
to slightly impaired hearing and vision whereas higher levels cause
dizziness, nausea, tingling and numbness in the fingers and toes.
In humans, direct skin contact with MDC causes intense burning and mild
redness of the skin. Direct contact with the eyes can burn the cornea.
118
Trichloromethaneor
Trichloromethane orChloroform
Chloroform
Chloroform is employed as solvent for fats, alkaloids, iodine and other substances.
Major use of chloroform today is in the production of freon refrigerant R-22.
It was once used as a general anaesthetic in surgery but has been replaced by less toxic,
safer anaesthetics, such as ether.
Inhaling chloroform vapours depresses the central nervous system.
Breathing about 900 ppm for a short time can cause dizziness, fatigue, & headache.
Chronic exposure cause damage to liver (where CHCl3 is metabolised to phosgene) & to
kidneys, and some people develop sores when the skin is immersed in CHCl3.
CHCl3 slowly oxidised by air in presence of light to extremely poisonous gas, carbonyl
chloride, therefore stored in closed dark coloured bottles completely filled so that air is
kept out.
119
Triiodomethaneor
Triiodomethane orIodoform
Iodoform
earlier used as an antiseptic but antiseptic properties are due to

liberation of free iodine and not due to iodoform itself.
Due to its objectionable smell, it has been replaced by other
formulations containing iodine.
120
Tetrachloromethaneor
Tetrachloromethane orCarbon
CarbonTetrachloride
Tetrachloride
in manufacture of refrigerants and propellants for aerosol cans.
used as feedstock in the synthesis of chlorofluorocarbons and other chemicals,
pharmaceutical manufacturing, and general solvent use.
it was also widely used as a cleaning fluid, both in industry, as a degreasing agent, and in
the home, as a spot remover and as fire extinguisher.
Exposure to CCl4 causes liver cancer. Most common effects are dizziness, light headedness,
nausea and vomiting, which can cause damage to nerve cells.
In severe cases, these effects lead to stupor, coma, unconsciousness or death.
Exposure to CCl4 make the heart beat irregularly or stop.
may irritate the eyes on contact. When it is released into air, it rises to the atmosphere and
depletes the ozone layer leading to increased skin cancer, eye diseases and disorders, and
possible disruption of the immune system.
121
FREONS
FREONS
Chlorofluorocarbon compounds of methane and ethane known as freons.
extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable

gases.
Freon 12 (CCl2F2) one of the most common freons in industrial use.
It is manufactured from CCl4 by Swarts reaction.
These are usually produced for aerosol propellants, refrigeration and air
conditioning purposes.
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.
122
p,p-Dichlorodiphenyltrichloroethane
p,p-Dichlorodiphenyltrichloroethane
prepared in 1873 and discovered by Paul Muller (awarded Nobel Prize).
use of DDT increased after World War II, because of its effectiveness against
the mosquito that spreads malaria and lice that carry typhus.
Problems: Many species of insects developed resistance to DDT, and have a
high toxicity towards fish.
chemical stability of DDT and its fat solubility compounded the problem. DDT
not metabolised rapidly by animals; instead, deposited and stored in the fatty
tissues.
If ingestion continues at a steady rate, DDT builds up within the animal over
time. Use of DDT was banned in the United States in 1973, although it is still in
use in some other parts of the world.
123
Uses of Halogeno-compounds
AsSolvents
As Solventsin
inDry-cleaning
Dry-cleaning
Chlorinated hydrocarbons are good solvents for oil and

greases
widely used in the dry-cleaning industry
e.g. trichloroethene, CCl2 = CHCl

tetrachloroethene, CCl2 = CCl2
Properties that favour the use:

1. Relatively non-flammable
2. Volatile
3. Little or no structural effect on fabrics

124
AsRaw
As RawMaterials
Materialsfor
forMaking
MakingAddition
AdditionPolymers
Polymers
Poly(chloroethene) (also known as PVC):
Produced by means of the addition polymerization of

the chloroethene monomers in the presence of a
peroxide catalyst
125
Polar C Cl bond results in dipole-dipole interactions

between polymer chains, making PVC hard and brittle
and used to make pipes and bottles
Products made of PVC without

plasticizers
126
PVC becomes flexible when plasticizer is added
Used to make shower curtains, raincoats, artificial

leather, insulating coating of electrical wires
Products made of PVC with

plasticizers
127
Poly(tetrafluoroethene) (PTFE, Teflon):
Produced through addition polymerization of the

tetrafluoroethene monomers under high pressure and
in the presence of catalyst
128
Teflon has a high melting point and is chemically inert
Used to make non-stick frying pans
129
Chlorofluorocarbons - CFCs
dichlorofluoromethane CHFCl2 refrigerant, aerosol propellant,
blowing agent
trichlorofluoromethane CF3Cl refrigerant, aerosol propellant,
blowing agent
bromochlorodifluoromethane CBrClF2 fire extinguishers
CCl2FCClF2 dry cleaning solvent, degreasing

agent
130
PROBLEMS WITH CFCs AND THE OZONE LAYER
CFCs blamed for damage to the environment by thinning ozone layer
Ozone absorbs a lot of harmful UV radiation
However it breaks down more easily in the presence of CFC's
CFCs break up in the atmosphere to form radicals CF2Cl2 > CF2Cl
+ Cl
Free radicals catalyse the breaking up of ozone 2O3 > 3O2
CFCs were designed by chemists to help people
Chemists are now having to synthesise alternatives to CFCs to

protect the environment
This will allow the reversal of the ozone layer problem
131
PROBLEMS WITH CFCs AND THE OZONE LAYER
There is a series of complex reactions but the basic process is :-
ozone in the atmosphere breaks down naturally O3 > O + O2
CFC's break down in UV light to form radicals CCl2F2 > Cl +

CClF2
chlorine radicals then react with ozone O3 + Cl > ClO +
O2
chlorine radicals are regenerated ClO + O > O2 + Cl
Overall, chlorine radicals are not used up so a small amount of

CFC's can destroy
thousands of ozone molecules before they take part in a termination
132
stage.
133
The END
134

Unit 10

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Unit 10

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Chapter 10

Haloalkanes & Haloarenes

Haloalkanes are organic compounds having one or more

On the Basis of Number of Halogen Atoms:

Monohalocompounds further be classified according to the hybridisation of

(b) Allylic halides

(c) Benzylic halides

(b) Aryl halides

Halobenzenes are organic compounds in which the halogen

not a halobenzene, because the

Naming haloalkanes are similar to those for naming

The halogens are written as prefixes: fluoro- (F), chloro-

When the parent chain has both a halogen and an alkyl

gem-dihalides are named as alkylidene halides and vic-dihalides are named

In case of halobenzenes, the benzene ring is numbered so as

Different structures are possible due to...

Check Point 32-1

Melting Boiling Density at

Haloalkanes have higher b.p. and m.p. than alkanes

No. of carbon m.p. and b.p.

Relative molecular mass

closer packing of the smaller molecules in the

Bromo and iodoalkanes are all denser than water at

Although C X bond is polar, it is not polar enough to

Immiscible with water

Soluble in organic solvents

For a haloalkane to dissolve in water, energy is required to overcome the

Carbon-Halogen (CX) Bond Lengths, Bond Enthalpies and Dipole Moments

Prepared by substituting OH group of alcohols

Common reagents used: HCl, HBr, HI, PCl3 or PBr3

The ease of substitution of alcohols:

This is related to the stability of the reaction

Dry HCl is bubbled through alcohols in the presence

For the preparation of bromo- and iodoalkanes, no

The reactivity of hydrogen halides: HI > HBr > HCl

Addition of halogen or HX to Alkenes & Alkynes

Addition of halogens or hydrogen halides to an alkene or

Addition of Br2 in CCl4 resulting in discharge of reddish brown colour of

Propene yields two products, however only one predominates

Alkyl fluorides best synthesized by heating alkyl

Benzene reacts readily with chlorine and bromine

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 HI

formed during iodination.

Fluoro compounds are not prepared by this method due to high

Check Point 32-2

Halogens have a greater electronegativity than

Carbon atom bears a partial positive charge

Halogen atom bears a partial negative charge

The carbon is thus open to attack by nucleophiles

Nucleophilic substitution reaction

the result is substitution following attack by a nucleophile

Mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION

Alcohols, ethers, esters, nitriles & amines formed by

C-I 238 kJmol-1 weakest - easiest to break

C-Br 276 kJmol-1

C-Cl 338 kJmol-1

C-F 484 kJmol-1 strongest - hardest to break

C2H5Br(l) + H2O(l) > C2H5OH(l) + H+ (aq) + Br(aq)

Another characteristic reaction:

Haloalkane Base Alkene

Bases and nucleophiles are the same kind of reagents

Nucleophilic substitution and elimination reactions