CHAPTER 16 ALKYL HALIDES

Definition: Monohaloalkanes are usually called “Alkyl halides”.

Alkyl halides are the compounds of carbon, hydrogen and halogen. The functional group of
these compounds is __X (halogen). These are the derivatives of alkanes in which one
hydrogen atom has been replaced by a halogen atom.
Formula R___X R= alkyl group, X= F, Cl, Br, I
General formula CnH2n+1

Classification of alkyl halides

Primary alkyl halides

When halogen atom is directly bonded to the primary carbon, this is called primary alkyl
halide.
Secondary alkyl halides
When the halogen atom is directly bonded to the secondary carbon, this is called secondary
alkyl halides
Tertiary alkyl halides
When the halogen atom is directly bonded to the tertiary carbon, this is called tertiary alkyl
halides. For example,
H R R

R C X R C X R C X

H H R halide
primary alkyl halide secondary alkyl halide tertiary alkyl

H CH3 CH3

H3C C X H3C C X H3C C X

H H CH3 halide
primary alkyl halide secondary alkyl halide tertiary alkyl

Nomenclature of alkyl halides

Common system: Alkyl halides are named by giving first alkyl name and then halogen
atom. For example,
 H 3C F CH3 CH2 F
Methylflouride Ethylflouride

H3C Cl CH3 CH2 Cl

Methylchloride Ethylchloride

H 3C Br CH3 CH2 Br
Methylbromide Ethylbromide

H 3C I CH3 CH2 I
Methyliodide Ethyliodide

IUPAC System:

1. Select the longest continuous carbon chain having halogen atom.

2. Number the longest continuous carbon chain. Start 1 from that end nearer to the halogen
atom.
3. Alkyl halides are named as “haloalkanes” according to IUPAC.
4. When there are more than one substituent, they are named alphabetically.
Some IUPAC names of alkyl halides have been written as;
H3C F CH3 CH2 F
1 2 1
Flouromethane Flouroethane

H3C Cl CH3 CH2 Cl

1 2 1
Chloromethane Chloroethane

H3C Br CH3 CH2 Br

1 2 1
Bromomethane Bromoethane

H3C I CH3 CH2 I

1 2 1
Iodomethane Iodoethane

CH3 CH3 C2H5 CH3

CH3 CH2 CH CH2 CH Cl CH3 CH2 CH2 C C Cl

5 4 3 2 1 5 4 3 2 1
1,3-Dimethylchloropentane
NO2 NH2
1-Amino-2-ethyl-1-methyl-2-nitrochloropentane
Physical properties of alkyl halides

1. Lower alkyl halides like methyl fluoride, methyl chloride, methyl bromide and ethyl
chloride etc are gases at room temperature. Alkyl halides up to C18 are colourless liquids
while higher alkyl halides are solids.
2. They are insoluble in water and having no hydrogen bond.
3. They are soluble in organic solvents like benzene, ether etc.
4. They have higher melting points and boiling points than alkanes.
5. Melting points, boiling points and densities increase with increasing molecular mass.
Structure of alkyl halides

All alkyl halides having carbon-carbon single covalent bond. All carbon atoms have sp3
hybridization having bond angle 109.50. Let us consider the structure of methyl chloride
(CH3Cl). In methyl chloride, carbon atom forms four sigma bonds having sp3 hybridization
and bond angle 109.50. For example,
109.50 H
sp3

H C Cl

H
Fig: Structure of methyl chloride
structure: Tetrahedral
bond angle: 109.50
hybridization: sp3
sigma bonds: 4

Preparation of alkyl halides

1. Reaction of halogen acids with alcohols

Alcohols react with halogen acids like HCl and HBr to form alkyl chloride and alkyl
bromide. For example,
 ZnCl2
CH3 CH2 OH + H Cl CH3 CH2 Cl + H2O
Ethyl alcohol Ethyl chloride

CH3 CH2 OH + H Br CH3 CH2 Br + H2O

Ethyl alcohol Ethyl bromode

CH3 CH2 OH + H I CH3 CH2 I + H2O

Ethyl alcohol Ethyl iodide

2. Reaction of phosphorous halides with alcohols

Alcohols react with phosphorous trihalides like PCl3, PBr3 and PI3 to form the corresponding
alkyl halides. For example,

3 CH3 CH2 OH + PCl3 3 CH3 CH2 Cl + H3PO3

Ethyl alcohol Ethyl chloride

3 CH3 CH2 OH + PBr3 3 CH3 CH2 Br + H3PO3

Ethyl alcohol Ethyl bromide

3 CH3 CH2 OH + PI3 3 CH3 CH2 I + H3PO3

Ethyl alcohol Ethyl iodide

3. Reaction of alcohols with thionyl chlorides (SOCl2)

Alcohols react with thionyl chlorides (SOCl2) in the presence of a catalyst pyridine to form
alkyl halides. For example,
O
Pyridine
CH3 OH + Cl S Cl CH3 Cl + HCl + SO2
Methyl alcohol O Methyl chloride
Pyridine
CH3 CH2 OH+ Cl S Cl CH3 CH2 Cl + HCl + SO2
Ethyl alcohol Ethyl chloride
 4. Free radical halogenation of alkanes
Alkanes react with halogens in the presence of ultraviolet light (UV) or at high temperature
400 C0 to form alkyl halides. This reaction occurs through free radical mechanism. This
method of preparation is not important. For example,
UV
R H + Cl Cl R Cl + HCl
400 °C

Chemical properties of alkyl halides

Alkyl halides are polar organic molecules having partial negative charge on halogen atom
and partial positive charge on carbon atom. Halogen atoms have high E.N. than carbon atom.
Alkyl halides are reactive molecules having good leaving groups of halogen atoms.
Nucleophile will attack at partial positive carbon atom and electrophile will attack at partial
negative charge due to which the halogen-carbon bond (C__X) is broken down.
The reactivity order of alkyl halides are:
R___I > R___Br > R___Cl > R___F

Carbocations and their stability

Carbon atoms having positive charge (C+) and forming three covalent bonds are called
“carbocations”. Carbocations are also called “carbonium ion”.
There are three carbocations. Primary carbocations, secondary carbocations and tertiary
carbocations.
Tertiary carbocations are more stable than secondary carbocations which in turn are more
stable than primary carbocations.
Greater the number of alkyl groups, higher will be the stability. Therefore, tertiary
carbocation has three alkyl groups while secondary carbocation has two alkyl groups and
primary carbocation has one alkyl group. This is the reason. For example,
R R H
+ + +
R C R C R C

R H H
tertiary carbocation secondary carbocation primary carbocation
 R R

+ -
R C Br R C + Br H = 149 kcal/mol

R R

R R

+ -
R C Br R C + Br H = 163 kcal/mol

H H

H H

+ -
R C Br R C + Br H = 182 kcal/mol

H H

Nucleophile and base

Nucleophile: The species which can donate a pair of electrons in a chemical reaction are
called “nucleophiles” which are denoted by “Nu-). Nucleophiles have negative charge or
neutral molecules having lone pair of electrons.
Base: The species which can donate a pair of electrons to the protons (H+) is called “base”.
Bases have also negative charge or neutral molecules having lone pair of electrons.
Nucleophile can attack any electrophile like carbon atom while base can attack hydrogen
atoms (protons H+).

Aliphatic Nucleophilic Substitution Reactions

Definition: Those reactions in which one nucleophile is replaced by another nucleophile in

an aliphatic molecules are called “aliphatic nucleophilic substitution reactions”.

Substrate:

Species which undergo aliphatic nucleophilic substitution reactions or which are attacked by
attacking reagents are called “substrate”. For example, alkyl halides are substrates.

Attacking nucleophile:

Species which can attack on the substrate molecule is called “attacking nucleophile”.

Product:

The yield which is formed as a result of aliphatic nucleophilic substitution reactions is called
“product”.
Leaving group:

Species or group which leaves the substrate molecule or which is replaced by the attacking
nucleophile is called “leaving group”. For example, halogen atoms (Cl, Br, I) are good
leaving groups.

- -
H3C Cl + HO H3C OH + Cl
substrate attacking nucleophile product leaving group

Mechanism of aliphatic nucleophilic substitution reactions (SN1)

S stands for substitution and N1 stands for unimolecular. Thus there is one molecule which is
taking part in SN1 reactions. It is a first order reaction.
There are two steps of this mechanism.

MECHANISM SN1

Step-I:

In the first step, substrate (ter-butyl chloride) is ionized into carbocation and chloride ion (Cl-
)

Step-II:

In the second step, the attacking nucleophile (OH-) attacks at carbocation to form the product
(ter-butyl alcohol).
CH3 CH3
slow -
Step-I: CH3 C Cl +
CH3 C + Cl

CH3 CH3
substrate carbocation leaving group

CH3 CH3
- fast
Step-II: CH3 C +
+
HO CH3 C OH
nucleophile
CH3 CH3
carbocation product (ter-butyl alcohol)

MECHANISM SN2
S stands for substitution and N2 for bimolecular. Thus, there are two molecules which are
taking part in SN2 reactions. It is a second order reaction. There is one step of this
mechanism.

Step-I:

The attacking nucleophile (OH-) attacks the electrophilic carbon atom of the substrate
molecule (methyl chloride) before the leaving group (Cl-) departs. The attacking nucleophile
can attack only from the back side because the front side is blocked by the halogen atom. As
the reaction proceeds, the bond between the substrate and the attacking nucleophile starts to
form and the bond between the substrate and the leaving group weakens. Thus a transition
state is formed in which both the attacking nucleophile and the leaving group are partially
bonded to the carbon atom of the substrate. Finally, the bond between the substrate and the
leaving group is completely broken down and the new bond between the substrate and the
attacking nucleophile is formed completely.
H H H

- - - - -
Step-I: HO + H C Cl HO C Cl HO C H + Cl

H H H H
attacking substrate transition state product leaving
nucleophile group

Note: Primary alkyl halides undergo SN2 mechanism while tertiary alkyl halides
undergo SN mechanism. Secondary alkyl halides undergo both SN1 and SN2 mechanisms.
1

ELIMINATION REACTIONS

Definition: Those reactions which involve the removal of atoms or group of atoms from two
adjacent carbon atom atoms in the substrate molecule to form a multiple bond are called
“Elimination reactions”.
Elimination reactions are the reverse of addition reactions. In these reactions two sigma
bonds are lost and a new pi bond is formed and saturated compound become unsaturated. For
example,
H H H H

H C C H + Zn H C C H + ZnBr2

Br Br
1,2-Dibromoethane ethene zinc bromide

Elimination reactions are divided into two classes.

1. Unimolecular elimination reactions (E1)
2. Bimolecular elimination reactions (E2)
1. E1 MECHANISM
E1 stands for unimolecular elimination reaction. In E1 elimination reactions, there is only one
molecule which is taking part in a reaction. It is a first order reaction. There are two steps of
this mechanism. It is like SN1 mechanism.

Step-I:

In the first step, alkyl halide is ionized into carbocation and halide ion.

Step-II:

In the second step, a proton (H+) is eliminated (lost) by a base from the adjacent carbon atom
to form unsaturated compound. For example,
CH3 CH3
slow/E1 Mechanissm
+ -
Step-I: CH3 C Br CH3 C + Br
ter-butylbromide ter-carbocation
CH3 CH3
H H

Step-II: H C H H C

- fast
+
CH3 C + HO CH3 C + H2O
E1 Mechanism

CH3 CH3
2-Methylpropene

2. E2 MECHANISM
E2 stands for bimolecular elimination reactions. In E2 elimination reactions, there are two
molecules which are taking part in a reaction. It is a second order reaction. There is one step
of this mechanism. It is like SN2 mechanism.

Step-I:

Base (OH-) attacks on the substrate. Hydrogen atom is attacked by a base and at the same
time, a leaving group (Br-) is departed, resulting in the formation of unsaturated compound.
Hydrogen is eliminated (lost) by a base and bromide ion (Br-) is departed from the carbon
atom. For example,
 -
HO H H H
E2 Mechanism
-
H C C Br H C C + H2O + Br

H H H H
Ethyl bromide Ethene

Substitution versus Elimination

As all the bases are also nucleophiles, the competition between elimination and substitution
reactions is determined by the fact that whether it is a better base or a better nucleophile.
A stronger base will favour elimination while a stronger nucleophile will favour substitution
in the substrate. For example, 2-bromopropane on reaction with ethoxide undergoes
elimination and produces alkene as the major product because ethoxide is a strong base. On
the other hand, the same 2-bromopropane on reaction with an anion thiolalcohol (C2H5S-)
undergoes substitution because C2H5S- is more nucleophilic and less basic than C2H5O-.

ORGANOMETALLIC COMPOUNDS (GRIGNARD’s REAGENT)

Definition: Those organic compounds which contain at least one carbon-metal bond (C__M)
in their structures are called “Organometallic compounds”.
Organometallic compounds were studied, discovered and prepared by Victor Grignard,
therefore they were named as “Grignard’s reagent”.
Organometallic compounds are highly reactive. They are used in the synthesis of a large
number of organic compounds like alkanes, alkynes, alcohols, aldehydes, ketones and
carboxylic acids.
Formula R___MgX : R= alkyl group X=halogen atom (Cl, Br, I)

Nomenclature

Organometallic compounds are named by simply adding the name of the metal to the organic
group (alkyl group) directly bonded to the metal atom. For example,
Preparation of Grignard’s Reagents

Grignard’s reagents are prepared in the laboratory by the action of alkyl or aryl halides on
freshly prepared magnesium metal in the presence of dry ether. There are two steps of this
reaction. In the first step, alkyl halides react with magnesium metal (Mg) to produce alkyl
radical (R.) and Mg.X. In the second step, R. combines with Mg.X to form Grignard’s
reagents.

Reactivity of Grignard’s Reagents

The bond between carbon and magnesium (R___MgX) is polar. Carbon has high
electronegativity and magnesium has low electronegativity, therefore carbon has partial
negative charge and magnesium has partial positive charge. The alkyl group is considered as
electron rich center, thus it can acts as carbanion or nucleophile. It would attack polarized
molecules at the point of low electron density. Therefore the reactions of Grignard’s reagents
are nucleophilic substitution and nucleophilic addition reactions.

Chemical reactions of Grignard’s reagents

Reaction with aldehydes and ketones

Grignard’s reagents react with aldehydes and ketones to produce addition products. These
addition products on hydrolysis forming alcohols.
Formaldehydes form primary alcohols, higher aldehydes form secondary alcohols while
ketones form tertiary alcohols. There are two steps of these reactions. For example,

Reaction with Esters (Ethyl formate)

Ethyl formate reacts with Grignard’s reagent to produce addition product. This addition
product undergoes elimination and forms aldehyde. This aldehyde further reacts with another
molecule of Grignard’s reagent to form secondary alcohol. For example,

Reaction with Ethyl acetate

Ethyl acetate reacts with Grignard’s reagent in the same manner as with ethyl formate but the
end product is tert-alcohol (30alcohol). For example,
Reaction with carbon dioxide (CO2)

Grignard’s reagent reacts with CO2 to produce addition product. This addition product further
undergoes hydrolysis to form carboxylic acids. For example,

AMINES

Definition: Derivatives of ammonia in which one or more hydrogen atoms have been
replaced by one or more similar or different alkyl or aryl groups are called “Amines”.
The functional group of amines is ____NH2. Its general formula is R___NH2. Its example is
methyl amine CH3____NH2.
Primary amines
When nitrogen atom is directly bonded to the primary carbon, this is called primary amines.
Secondary amines
When nitrogen atom is directly bonded to the secondary carbon, this is called secondary
amines
Tertiary amines
When nitrogen atom is directly bonded to the tertiary carbon, this is called tertiary amines.

Nomenclature of Amines

Common system

Common names of amines are given as “alkylamines”.

Write first the name of alkyl group and then amine. Typical examples of amines having
common names have been written as;

IUPAC system

Select the longest continuous carbon chain having amino group (___NH2).
Number this longest continuous carbon chain starting 1 from that end nearer to the amino
group
Indicate the positions of different groups. If two or more same groups are present, they are
named as “di” for two, “tri” for three and so on.
IUPAC names of amines are written as “Aminoalkanes”.
Physical properties of Amines

1. Low molecular mass amines are gases or low boiling liquids.

2. They possess a characteristic ammonia like smell.
3. They have higher boiling points and melting points than alkanes.
4. They have hydrogen bonding.
5. They are polar and are soluble in polar solvents.
Structure of Amines

Ammines are the derivatives of ammonia (NH3). All amines have a single sigma bond
between nitrogen atom and carbon atom.
Let us consider the structure of methyl amine (CH3___NH2). In methyl amine, nitrogen and
alkyl group (carbon) have sp3 hybridization having bond angle 107.50 and trigonal pyramidal
structure. For example,

Basicity of Amines

Amines have lone pair of electrons due to which all amines are considered as bases. Amines
can donate a pair of electrons to the protons (H+). Amines react with acids to from salts. e.g.,
Aliphatic amines are stronger bases than ammonia and aromatic amines. The reason is that
aliphatic amines can donate lone pair of electrons very easily to the protons (H+) in the first
chance while aromatic amines can donate lone pair of electrons to the ring in the first chance
and after delocalization in the ring, they can donate lone pair to the protons. Thus aliphatic
amines are stronger bases than aromatic amines.
Electron donating groups increase the basicity and electron withdrawing groups decrease the
basicity of amines. Greater the number of electron donating groups (like alkyl), stronger will
be the basicity of amines. For example,

Preparation of Amines

Alkylation of ammonia by alkyl halides

Alkyl halides react with ammonia to form primary, secondary, tertiary and quaternary amines
salt. For example,

Reduction of nitroalkanes

Primary amines are prepared by the reduction of nitroalkanes with hydrogen (H2) in the
presence of a catalyst Ni/Pd/Pt. They can also be reduced by lithium aluminium hydride
(LiAlH4) in ether. For example,
Reduction of nitriles

Alkyl cyanides are reduced by hydrogen in the presence of a catalyst Ni/Pd/Pt or by lithium
aluminium hydride (LiAlH4). For example,

Reduction of amides

Amides are reduced by lithium aluminium hydride (LiAlH4) in ether to form primary amines.
For example,

Chemical properties of Amines

Amines have lone pair of electrons and considered as nucleophiles. An electrophile will
attack at this nucleophile (nitrogen).
Alkylation of amines by alkyl halides

When amines react with alkyl halides, forming a mixture of primary, secondary, tertiary and
quaternary ammonium salts. For example,

Reaction of amines with aldehydes and ketones

Primary amines react with aldehydes and ketones forming condensation products called
“imines”. These imines are called “Schiff’s base”. For example,

Reaction with acetyl chloride (preparation of amides)

Amines react with acetyl chloride to form amides. For example,

Reaction with sodium nitrite (preparation of diazonium salts)

Primary amines react with sodium nitrite (NaNO2) to form diazonium salts. For example,

The End

Written by: Saeed Anwar Marwat

Lecturer in Chemistry

Government College Peshawar Pakistan

E-mail: saeedchemistry28@gmail.com

Class-XII Notes…Organic Chemistry

Contact: +923025126034