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TOPIC 14.

0 : HALOALKANES (ALKYL HALIDES)


OVERVIEW
TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)

INTRODUCTION

 Haloalkanes also known as alkyl halides


 Alkyl halides are organic molecules containing a halogen atom bonded to an sp3 hybridized carbon
atom.

where X : halogen atom (F, Cl, Br or I)


 General Formula : CnH2n+1X (acyclic)
CnH2n-1X (cyclic)
 Compounds, which contain a halogen (F, Cl, Br or I) covalently bonded to an sp 3 hybridized carbon are
called- haloalkanes/alkyl halides. If the carbon is part of an aromatic ring, then the compound is
a haloarene (aryl halide)

CLASSIFICATION OF ALKYL HALIDES

 Alkyl halides are classified as primary (1°), secondary (2°), or tertiary (3°), depending on the
number of carbons atom/alkyl group bonded to the carbon with the halogen atom.
 The halogen atom in halides is often denoted by the symbol “X”.

EXAMPLE :
TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)

EXERCISES: Classify the following haloalkanes:

IUPAC NOMENCLATURE OF HALOALKANES

Step 1: Haloalkanes are named as alkanes with halogen as substituents.

Step 2: Locate and number the parent chain from the direction that gives the substituent encountered
first the lower number.

Step 3: Show halogen substituents by the prefixes flouro-, chloro-, bromo- and iodo-, and list them in
alphabetical order along with other substituents.

EXERCISES:
TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)
1. 2. 3.
Cl
Br Br
H3C C CH2CH3
H2C CH2 CH CH2CH3 H3C CH C CH CH3
CH2CH3 H3C CH CH3 CH3

4. 5. 6.
CH2Cl I Br
CH2CH3
H3C C CH2CH2CH3 H3C
CH
H3C CH3

7. 8. 9.
CH2I
H3C Cl H2C CH C CH2CH 3

C CH3
H3CH2C
H

 Common names are often used for simple alkyl halides. To assign a common name:
i. Name all the carbon atoms of the molecule as a single alkyl group.
ii. Name the halogen bonded to the alkyl group.
iii. Combine the names of the alkyl group and halide, separating the words with a space
*Useful only for small alkyl groups.

STRUCTURE OF HALOALKANE
TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)
The Polar Carbon-Halogen Bond

Reaction Types for Alkyl Halides

Nucleophiles and Bases


TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)

Trends in Nucleophilicity

 A negatively charged nucleophile is stronger than its neutral counterpart:

 Nucleophilicity decreases across a period from left to right

 Nucleophilicity increases down periodic table, as size and polarizability increase:


TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)
Chemical Properties

Nucleophilic Substitution Reaction

 Haloalkanes undergo nucleophilic substitution reactions in which the halogen atom is


replaced by a nucleophile.

 Haloalkanes undergo nucleophilic substitution reactions in which the halogen atom is


replaced by a nucleophile.

 Negatively charged nucleophiles like HO¯ and HS¯ are used as salts with Li+, Na+, or K+
counterions to balance the charge.

 When a neutral nucleophile is used, the substitution product bears a positive charge. The
substitution product’s positive charge is usually caused by a proton bonded to O or N.

 That proton is readily lost from this in a BrØnsted-Lowry acid-base reaction, forming a
neutral product..
TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)
Nucleophilic Substitution Reaction Chemical Equation

General Equation :
1. Hydrolysis with strong base
/strong Nu- (NaOH/KOH) H2O
R X + NaOH R OH + Na X
Starting Material : Haloalkane
Example :
Reagent : Strong Base (KOH /
NaOH)
H 2O
Condition : presence of H2O as a
solvent
H3CH2C Br + NaOH
Product : Alcohol
CH2Cl
H2O
+ KOH

General Equation :
2. Hydrolysis with H2O (weak Nu-)
Starting Material : Haloalkane R X + H2O R OH + H X

Product : Alcohol Example :

CH3
H3C C Br + H 2O
CH3

CH3
Cl

+ H2 O

3. Alcoholysis with ROH (weak General Equation :


Nu- )
When R-X reacts with alcohol, the halogen atom is
Starting Material : Haloalkane substituted by the RO- (alkoxide ion) to produce ether and
Reagent : Alcohol HX.
Product : ether
R X + R'-OH R OR' + H X

Example :

CH3
H3C C Br + CH3OH
H3C

H3C
CH Br
+ CH3CH2OH

General Equation :
TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)
4. Reaction with Sodium alkoxide
or Potassium alkoxide
(strong Nu-) When R-X reacts with sodium alkoxide or potassium
alkoxide, the halogen atom is substituted by the RO-
Starting Material : Haloalkane (alkoxide ion) to produce ether and HX.
Reagent : Sodium alkoxide or
Potassium alkoxide R X + Na-OR' R OR' + Na X
Product : ether
Example :

H3CH2C Br + CH3OK

CH2Cl
+ CH3CH2ONa

General Equation :
-
5. Reaction with CN /cyanide ion
(strong Nu-) When R-X is refluxed with KCN/ NaCN in alcohol, the
halogen atom is substituted by the CN- to produce a nitrile
Starting Material : Haloalkane compound.
Reagent : KCN or NaCN
Condition: Reflux in ethanol *Important in this reaction, number of C atom in the product
Product : nitrile compoun is increase by one (lengthening the chain)

CH3CH2OH
R X + KCN R CN + K X
reflux

Example :

CH3CH2OH
H3C CH2 Cl + KCN
reflux

H2C CH2 Br

CH3CH2OH
+ NaCN
reflux
TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)
6. Reaction with excess Ammonia General Equation :
(weak Nu-)
When R-X is reflux with excess concentrated NH3 in ethanol,
Starting Material : Haloalkane the halogen atom is replaced by the amino group, NH2-
Reagent : excess NH3
Condition: Reflux in ethanol CH3CH2OH
Product : Amine compound R X + NH3 R NH2 + H X
. reflux

Example :

CH3
H3C C Br + NH3 CH3CH2OH
reflux
H3C

CH3
Cl
CH3CH2OH
+ NH3
reflux

7. Reaction with RCOO- General Equation :


/carboxylate ion (Strong Nu- )
When R-X reacts with carboxylate ion, the halogen atom is
substituted by the RCOO- to produce an ester compound.

Starting Material : Haloalkane O O


Reagent : RCOO- / salt from R X + H3C C ONa H3C C O R + NaX
carboxylate ion
Product : Ester
Example :

CH3CH2Br + CH3COONa

CH2Cl

CH3CH2COONa

Mechanisms of Nucleophilic Substitution Reaction


TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)

They are 2 important mechanisms for the Nucleophilic Substitution reaction:

I. Unimolecular Nucleophilic Substitution Reaction (SN1)

II. Bimolecular Nucleophilic Substitution Reaction (SN2)

Bond Breaking and Making in Nucleophilic Substitution Mechanisms

But what is the order of bond making and bond breaking? In theory, there are two possibilities:

I. Bond making and breaking occur at the same time.

II. Bond breaking occurs before bond making.

There are two possibilities for which direction the nucleophile will approach the carbon that bonded
to the halogen atom( α-carbon)

I. Frontside Attack: The nucleophile approaches from the same side as the leaving group.

II. Backside Attack: The nucleophile approaches from the side opposite the leaving group.

Nucleophilic Substitution Mechanisms


TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)
I. Bond making and bond breaking occur at the same time.

 From the above reaction, show that rate of reaction depends on the concentration of both
reactants (RX and Nu-), which suggests a bimolecular reaction with a one-step mechanism.
So, The rate equation is second order.

 This is an example of an SN2 reaction ( Bimoleular Nucleophili Substitution reaction)


and all SN2 reactions proceed with backside attack of the nucleophile

II. Bond breaking occurs before bond making.

 From the above reaction, show that the rate of reaction 2 depends on the concentration of
only the RX. This suggests a two-step mechanism and a carbocation is formed as an
intermediate

 The first step is rate-determining step, in which the rate-determining step involves the alkyl
halide only. The rate equation is first order.

 This is an example of an SN1 ( Unimolecular Nucleophilic Substitution) reaction and all


SN1 reactions proceed with frontside attack of the nucleophile.

 SN2 is Bimolecular Nucleophilic Substitution.

 Bimolecular because the rate-determining step involves two species; RX and nucleophile

 Thus, rate of reaction depends on [RX] and [Nu-]

Rate = k [RX] [Nu-]


S 2 reactions
N Mechanism involves one step.

 Involved formation of transition state as a intermediate species

 Methyl alkyl halides and 1° alkyl halides undergo SN2 reactions with ease.
TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)

Example 1: Reaction of Iodomethane with aqueous sodium hydroxide.

H 2O
H3C I + NaOH H3C OH + NaI

SN2 Mechanism :

SN2 mechanism

 All SN2 reactions proceed with backside attack of the nucleophile, resulting in inversion of
configuration at a stereogenic .

 Back-side attack causes the product formed has inverse configuration from the original
configuration.
Example 2: Reaction of ethyl bromide with sodium cyanide.
* turns the tetrahedron of the carbon atom inside out, like umbrella caught by the wind.

CH3H2Br + NaCN CH3CH2CN + NaBr

SN2 Mechanism :

-
CH3 CH3
CH3
- slow fast H -
CN C Br NC C + Br
NC ----- C Br
H slow fast
H H H
H
transition state

Reactivity in SN2 Reactions

 Reactivity of haloalkanes for SN2 reaction is determined by the steric effect (size of atoms or
groups attached to carbon that bonded to halogen atom.) The presence of bulky alkyl groups
will prevent the nucleophilic attack and slow the reaction rate.
 The transition state always has partial bonds forming between carbon-nucleophile and partial
bond effect
 Steric breaking- between carbon-leaving
is an effect group.
on relative rates caused by the space-filling properties of those
parts of a molecule attached at or near to the reacting site.

 Relative reactivities of haloalkanes in an SN2 reaction :


SN2 Mechanism
R3-C-X , R2-CH-X , R-CH2-X , CH3-X
3o 2o 1o , methyl halide

increasing reactivity toward SN2 rxn


TOPIC 14.0 : HALOALKANES (ALKYL HALIDES)

slow fast

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