HALOGEN COMPOUNDS

II B.Sc.
SEMESTER – III

Dr. Narayana Rao Vykunthapu

Lecturer in Chemistry
P.R. Govt. College (A), Kakinada
 Outline
 Introduction
 Nomenclature
 Classification of alkyl halides
 Nucleophilic aliphatic substitution reactions
 Summary
 Introduction
 Fluorine, Chlorine, Bromine and Iodine are called as Halogens.

 These derivatives are obtained by replacing of one or more

hydrogen atoms in Hydrocarbons.

 General symbol for alkyl halides is R-X, where X is halogen

 Reactivity of Halogen compounds is high, so these compounds used

as starting material in the preparation of many organic compounds.
Alkyl Halides in day to day life

 Due to stable, non-toxic, non-inflammable and non-corrosive

nature these are used as Solvents, Coolants in fridges and
Propellants
 Fire Extinguishers
 Anaesthetic and Medicine
 Pesticides, Fungicides
 Feedstock's for PVC, PTFE and Teflon
Examples:
 Nomenclature
 IUPAC system:
Ex:1 Give the IUPAC name of the following alkyl halide

Step-1: Find the parent carbon chain containing the halogen

Step-2 Apply all other rules of IUPAC: Name and position of Substituents
Chloro at 3rd position, hence name is 3 – Chloro pentane
Ex: 2. Give the IUPAC name of the following alkyl halide

Step-1: Find the parent carbon chain containing the halogen

Step-2 Apply all other rules of IUPAC: Name and position of Substituents

Hence the name of the compound is 3- Fluoro, 6- methyl heptane

 Common Names
 Common names are often used for simple alkyl halides
Rules to assign:
• Name all the carbon atoms of the given molecule as a single alkyl
group.
• Name the halogen bonded to the alkyl group
• Combine the names of alkyl group and halide
EX:
 Classification of alkyl halides
 Generally Halides of Alkanes, Alkenes and Alkynes are called as
Alkyl halides, Alkenyl halides and Alkynyl halides.
 Based on number of hydrogen atoms replaced by halogen,
these compounds are classified as mono, di, tri and tetra
halogen compounds.
 Mono alkyl halides further classified as Primary (10), Secondary
(20) and Tertiary (30) based on the alkyl group linked to the
halogen atom.
 Classification of Mono halogen derivatives:
 Primary alkyl halides: Halogen atom is linked to primary carbon atom.
Examples:

 Secondary alkyl halides: Halogen atom is linked to secondary carbon atom.

Examples:
 Tertiary alkyl halides: In this type halogen atom is linked to tertiary carbon
atom.
Ex:

 Halo alkenes or alkenyl halides: In this type halogen atom is directly linked
to alkenyl carbon atom or C-C double bond
Ex:

 Allylic Halides: in this type halogen atom is bonded to carbon atom

adjacent to the C-C double bond
Ex:
 Aromatic Halogen compounds: These are obtained by replacement of hydrogen
atoms of an aromatic hydrocarbon with an equal number of halogen atoms, i.e.
halogen atom is directly attached to aromatic ring.

Ex:

 Aralkyl halides (side chain halogen derivatives): In these compounds halogen

atom is directly linked to one of the carbon atoms of the side chain carrying the
aryl group.
Ex:
Nucleophilic Substitution reactions
 The substitution reactions in which one nucleophile is replaced by another
incoming strong nucleophile is called as Nucleophilic Substitution reactions.
 Generally alkyl halides participated in Nucleophilic Substitution reactions
Since halogen atoms electro negativity is higher than carbon, so bond pair
electrons of C-X bond are attracted towards halogen atom as a result
halogen atom gets partial negative charge and carbon will get same
magnitude of positive charge.
 General representation of reaction is
 Nucleophilic substitution reactions

Unimolecular Bimolecular Intra moleclar

Nucleophilic Nucleophilic Nucleophilic
substitution substitution Substitution
reactions (SN1) reactions (SN2) (SNi)
Unimolecular Nucleophilic substitution reactions (SN1):

 In these reactions rate determining step of the reaction involves only alkyl
halide not nucleophile, i.e. rate of the reaction depends on only
concentration of alkyl halide, so these are called as Unimolecular reactions.
Rate of reaction α [Alkyl Halide][ Nucleophile]
 It is a two – step process, in the first step ionization of R - X takes place,
resulting in the formation of carbocation intermediate. It is the slow step
hence is the rate determining step.
 In the second step Nucleophile vigorously combining with Carbocation
intermediate and forms product.
 Generally tertiary alkyl halide participates in SN1 reaction and relative
reactivity of alkyl halides in SN1 reactions is:
Benzyl halide > Allyl > Tertiary halide > Secondary > Primary >
Methyl.
 Polar protic solvents (ROH, H2O etc.) favors SN1 reaction mechanism.
 In SN1 reaction racemic mixture is formed if substrate is asymmetric
molecule.
Ex: Base hydrolysis of tertiary butyl bromide with aqueous alkali such as
NaOH or KOH to form tertiary alcohol as a product.

Mechanism:
Step-1: Heterolysis of the C – Br bond Forms a Carbocation Intermediate
Step-2: Nucleophile attack on Carbocation Intermediate
Nucleophile attack on carbocation forms the new C-O bond in
the product. This is a Lewis acid – base reaction the nucleophile
is the Lewis base and carbocation is the Lewis acid
 Stereochemistry in SN1 reactions:
 if the reaction takes place at a stereo center in asymmetric molecule, racemic
mixture of enantiomers is formed.

 Since the Carbocation intermediate is formed in the SN1 reaction is

a sp2 hybridized carbon with Trigonal Planar molecular geometry. This allows
two different possibilities for the Nucleophile attack on either side of the
planar molecule to afford two products which are a pair of enantiomers.

 Because there is no preference for nucleophilic attack from either direction, an

equal amount of the two enantiomers is formed a racemic mixture. We say
that racemization has occurred
Ex: Base hydrolysis of 2-Bromo butane with aqueous alkali such as NaOH or
KOH to form racemic 2- butyl alcohol as a product.
Energy profile diagram for SN1:
The SN1 Reaction: Carbocation Rearrangements:
• In SN1 reaction Carbocation rearrangement takes place, i.e.
involve 1,2-hydride shift or 1,2-alkyl shifts
 Bimolecular Nucleophilic substitution reactions (SN2):

 In these reactions rate determining step of the reaction involves both alkyl halide
and nucleophile, i.e. rate of the reaction depends on both the concentrations of
alkyl halide and Nucleophile, so these are called as Bimolecular reactions.
Rate of reaction α [Alkyl Halide][ Nucleophile]
 This is a single step reaction process, in these reactions Nucleophile attacks on
alkyl halide from the side opposite to the leaving group (X).

 In this the bond between Nucleophile and carbon formation and C-X bond
breakage happens simultaneously, this state is called as transition state. this is
highly energized and unstable state, so it can easily breaks and forms products.
 The SN2 reaction is a concerted reaction because bond formation and
breaking occur simultaneously in a single transition state.

 Generally primary alkyl halides participates in SN2 reactions and relative

reactivity of alkyl halides is

Methyl halide > Primary > Secondary > Tertiary

 Polar aprotic solvents (Like: DMSO, DMF etc.) favors SN2 reaction
mechanism

 In this reaction Walden inversion takes place if substrate is asymmetric

molecule.
Ex: Base hydrolysis of Ethyl bromide with aqueous alkali such as NaOH or
KOH to form Ethyl alcohol as a product.

Mechanism:
 Stereochemistry in SN2 reactions:

 All SN2 reactions proceed with backside attack of the nucleophile,

resulting in inversion of configuration takes place.
 if the reaction takes place at a stereo center in asymmetric molecule,
spatial orientation of groups around the central carbon atom is inverted
like reverted umbrella in a very strong wind, i.e. 100% inversion of
product formation taking place in SN2 Reactions. It is called as Walden
inversion
 Ex: Base hydrolysis of (R)-2-Bromo butane with aqueous alkali such as
NaOH or KOH to form inverted (S)-2- butyl alcohol as a product.

Mechanism:
Energy profile diagram for SN2:
Factors affecting the rate of Nucleophilic Substitution reactions of
Alkyl Halides:

Nature of alkyl group:

 In SN1 reactions, a carbocation intermediate is formed, hence as the stability
of carbocation increases rate of reaction increases. Therefore order of
reactivity of alkyl halides in SN1 reaction is Benzyl > Allyl > Tertiary >
Secondary > Primary > Methyl halide
 In SN2 reaction back side attack of the Nucleophile on carbon atom occurs,
so as the crowding increases on carbon atom in alkyl halides backside attack
of the Nucleophile becomes more difficult. Therefore the reactivity of alkyl
halides in SN2 reaction is Methyl > Primary > Secondary > Tertiary halide.
 Nature of Leaving group (Halogen):
 A better leaving group increases the rate of both SN1 and SN2 reactions. Usually
leaving group carries negative charge hence groups which best stabilize a negative
charge are the best leaving groups, i.e., the weakest bases are stable as anions and
are the best leaving groups.
Increasing basicity

pKb values 23 22 21 11 - 1.7 -2 -21

Ions I- Br - Cl - F- OH - OR - NH2 -

Leaving ability 30,000 10,000 200 1 0 0 0

Increasing leaving ability

therefore the reactivity of alkyl halides in both SN1 and SN2 reactions is
R – F < R – Cl < R – Br < R – I
 Nature of Solvent:
 Polar protic solvents like H2O and ROH favors SN1 reactions, this is due to
polar solvents stabilizes the ionic intermediates (carbocation and anion) by
solvation.
 Polar aprotic solvents like acetonitrile (CH3CN), Acetone (CH3COCH3),
Dimethyl sulfoxide (DMSO) and Dimethyl Formamide (DMF) favor SN2
reaction since these are well solvates the metal cations but not the
nucleophiles hence they are more nucleophilic.
 Nature and Concentration of Nucleophile:
 In SN1, Rate of reaction does not depend on concentration of Nucleophile,
so weak (like H2O and ROH) and low concentrated Nucleophiles
accelerate the rate of SN1 reaction.
 In SN2, Rate of reaction is depending on concentration of Nucleophile, so
strong and high concentrated Nucleophiles accelerate the rate of SN2
reaction.
 Differences between SN1 and SN2 Reactions:
SN1 Reaction SN2 Reaction
Unimolecular Reactions Bimolecular Reactions
It is two step reaction process It is a single step reaction process
Carbocation intermediate is formed No Carbocation intermediate is formed

Racemic mixture is formed Walden inversion takes place

Reactivity of alkyl halides is Tertiary Reactivity of alkyl halides is Methyl
Halide >Secondary > Primary > halide > Primary > Secondary >
Methyl halide Tertiary halide

Weak and low concentrated Strong and high concentrated

Nucleophiles favors Nucleophiles favors
Polar protic solvents Favors this Polar aprotic solvents Favors this
reaction reaction
Intra moleclar Nucleophilic Substitution (SNi)

• In these reactions alcohols with SOCl2 to give corresponding

halide
• Retention of configuration takes place
• First alcohol reacts with SOCl2 to form an alkyl chloro sulphite
• Next step is loss of a SO2 molecule and its replacement by the
chloride, which was attached to the sulfite group and it is
concerted.
EX: Conversion of (R)-butan-2-ol to (R)-2-chlorobutane
 Summary
 Applications of Alkyl halides in day to day life.
 Classification of Alkyl halides into aliphatic (primary, secondary, tertiary)
aromatic and aralkyl.
 Nomenclature of Alkyl halides; IUPAC and Common names.
 Nucleophilic aliphatic substitution reactions.
Unimolecular (SN1) and Bimolecular (SN1) reactions and their mechanisms.
 Stereochemistry and Energy profile diagrams of Unimolecular (SN1) and
Bimolecular (SN1) reactions.
 Factors influencing on Unimolecular (SN1) and Bimolecular (SN1) reactions
and their mechanisms.
 Differences between SN1 and SN2 reactions.
Thank you