ASSIGNMENT: ALKYL HALIDE

INTRODUCTION:
Alkyl Halide also known as Haloalkanes. They are compounds in which
one or more hydrogen atoms in an alkane have been replaced by halogen
atoms (fluorine, chlorine, bromine or iodine).
EXAMPLES:

CLASSIFICATION OF ALKYL HALIDES:

Alkyl halides fall into different classes depending on how the halogen
atom is positioned on the chain of carbon atoms. Alkyl halides can be
classified as primary, secondary, or tertiary.
1. PRIMARY ALKYL HALIDE:
In a primary (1°) haloalkane, the carbon bonded to the
halogen atom is only attached to one other alkyl group.
 2. SECONDARY ALKYL HALIDE:
In a secondary (2°) haloalkane, the carbon bonded with the halogen
atom is joined directly to two other alkyl groups that can be the same or
different.

3. TERTIARY ALKYL HALIDE:

In a tertiary (3°) halogenoalkane, the carbon atom holding the
halogen is attached directly to three alkyl groups, which may be
any combination of same or different.

PHYSICAL PROPERTIES:
1. With respect to electronegativity, halogens are more
electronegative than carbons. This results in a carbon-halogen
bond that is polarized. As shown in the image below, carbon atom
has a partial positive charge, while the halogen has a partial
 negative charge, because in the periodic table from iodine to
fluorine, electronegativity increases.

2. When comparing alkanes and haloalkanes, we will see that

haloalkanes have higher boiling points than alkanes containing
the same number of carbons. Dipole-dipole interaction is the
force contributes to a higher boiling point. this type of interaction is
a coulombic attraction between the partial positive and
partial negative charges that exist between carbon-halogen bonds
on separate haloalkane molecules.
3. Alkyl halides have little to no solubility in water in spite of
the polar carbon-halogen bond. The attraction between the
alkyl halide molecules are stronger than the attraction between the
alkyl halide and water.
4. Alkyl halides are soluble in most organic solvents. The London
Dispersion forces play a dominant role in solubility.
PREPARATION OF ALKYL HALIDE:
1. FREE RADICAL HALOGENATION:
Usually, this method gives mixtures of mono-, di-, tri- etc.
halogenated compounds, which is considered an inefficient
method for the synthesis of a desired compound.
 2. FROM ALKANES & ALKYNES:

3. FROM ALCOHOLS:

Alcohols can be converted to alkyl halides by reaction with thionyl

chloride, SOCl 2·, phosphorous trichloride, PCl 3·, phosphorous
pentachloride, PCl 5·, or phosphorous tribromide, PBr 3.
4. FROM ALLYLIC BROMINATION:
The bromination of cyclohexene produces a high yield of 3-
bromocyclohexene.

REACTION OF ALYL HALIDE:

 1. The halogen atom may leave with its bonding pair of electrons to
give a halide ion which is stable – a halide is called a good leaving
group.
2. If an atom replaces the halide the overall reaction is a substitution.
3. If the halide loss is accompanied by the loss of another atom, the
overall reaction is called an elimination.
4. Very often the other atom lost is a hydrogen (as H+). The
elimination of H-X is common, and is called a
dehydrohalogenation.
NUCLEOPHILIC REACTION:
The nucleophile Nuc:¯ displaces the leaving group (producing X¯) from
the carbon atom by using its lone pair to form a new bond to the carbon
atom.
 There are two types of nucleophilic substitution reaction:
 Sn1 reaction.
 Sn2 reaction.

 Sn2 REACTION (BIMOLECUAR):

The term SN2stands for Substitution reaction, Nucleophilic, 2nd
order (also called bimolecular). According to the SN2 mechanism, there
is a single transition state because bond-breaking and bond-making
occur simultaneously. Notice that there is not intermediate in an SN2
reaction, just a transition state. A transition state has no real lifetime, it
is the highest energy point on the reaction coordinate as starting
materials transition into products.
  Sn1 REACTION (UNIMOLECULAR):
The SN1 reaction is a nucleophilic substitution reaction where the
rate determining step is unimolecular. It is a type of organic substitution
reaction. SN1 stands for substitution nucleophilic unimolecular. Thus, the
rate equation (which states that the SN1 reaction is dependent on the
electrophile but not on the nucleophile) holds in situations where the
amount of the nucleophile is far greater than the amount of the
carbocation intermediate.
The Sn1 reaction takes place in 3 steps:
 Formation of a tert-butyl carbocation by separation of a leaving
group (a bromide anion) from the carbon atom: this step is slow.

 Nucleophilic attack: the carbocation reacts with the nucleophile. If

the nucleophile is a neutral molecule (i.e., a solvent) a third step is
required to complete the reaction. When the solvent is water, the
intermediate is an oxonium ion. This reaction step is fast.
  Deprotonation: Removal of a proton on the protonated nucleophile
by water acting as a base forming the alcohol and a hydronium ion.
This reaction step is fast.

ELIMINATION REACTION:
When a haloalkane having – hydrogen atom is heated with alcoholic
solution of potassium hydroxide, it will lead to the elimination of
hydrogen atom from β – carbon atom and a halogen atom from the α –
carbon atom. As a result, an alkene is formed as one of the products.
Since β – hydrogen atom is involved in elimination, it is often called β –
elimination reaction.
 Also, there are two types of elimination reaction:
 E1 reaction.
 E2 reaction.
GRIGNARD REAGENT:
Alkyl halide react with magnesium metal in anhydrous ether to give
alkyl magnesium halides or Grignard's reagents.

 HYDROLYSIS OF GRIGNARD REAGENT:

Methyl magnesium bromide (CH3MgBr) reacts with water and produce
methane as the organic product. As another product, MgBr(OH).

 REACTION WITH ALCOHOL: