Organic Chemistry (I)
Lecture 1
Chapter 1: Alkyl Halides
What are Alky Halides?
Alkyl halides are organic molecules containing a halogen atom X bonded to an
sp3 hybridized carbon atom.
Alkyl halides are classified as primary (1°), secondary (2°), or tertiary (3°)
Dipole–dipole interactions:
They exhibit dipole–dipole interactions because of their
polar C – X bond.
Dipole-Dipole Interaction
+ – + – + – + –
– +
Dipole-Dipole Attractive Forces
+ – + – + – + –
– +
Nomenclature of Alkyl Halides
1) Find and name the longest carbon chain and
name it as the parent.
2) The prefixes are fluoro- for fluorine, chloro- for
chlorine, bromo- from bromine, an d iodo- for
iodine.
3) The name of a halogen is preceded by a number
indicating the substituent’s location on the
parent chain.
Reactions of Alkyl halides
Alkyl halides can undergo:
1- Substitution reactions
2- Elimination reactions
Important Terminology
1- Nucleophile: is the electron-rich species
donating a pair of electrons to carbon
Example: – –
Br , I , –
OH , –
RO , CN–
2- Electrophile: the electron-deficient species
accepting a pair of electrons
Examples of electrophiles are H3O+, NO2+
3- Leaving group: the group that leaves the
compound.
4- Rate of Reaction:
It is the rate at which reactants are
converted into products.
A first-order reaction: the reaction rate is dependent on
the concentration of only one reactant.
A second -order reaction: reaction rate that depends on
the concentrations of two reactants.
5- The rate determining step:
It is the slowest step of a chemical reaction that
determines the speed (rate) at which the overall
reaction proceeds
Reactions of Alkyl halides
Alkyl halides can undergo:
1- Substitution reactions
2- Elimination reactions
What is a Substitution Reaction?
A substitution reaction is chemical reaction during which
a functional group replaces an atom or another functional
group attached to a compound.
Components of substitution reaction
[1] R—An alkyl group
[2] X—An atom X (or a group of atoms) called a leaving group,
[3] Nu– A nucleophile. Nucleophiles contain a lone pair or a π
bond but not necessarily a negative charge.
The conjugate bases of strong acids (e.g. I-, Br-, Cl-, TsO-) is a good leaving group.
The conjugate base of weak acids are not good leaving groups.
Negatively charged nucleophiles like –OH and –SH are used as salts with Li+, Na+,
or K+
When the substitution product bears a positive charge and also contains a proton
bonded to O or N, the initial substitution product readily loses a proton forming a
neutral product .
There are 2 types of Nucleophilic Substitution :
The SN2 substitution reaction.
The SN1 substitution reaction.
Nucleophilic Substitution Mechanism
SN2 Mechanism
The SN2 substitution reaction
Two species are involved: Nu + R-x
The reaction involves a transition state in which both reactants
are together
• For SN2, reaction second order kinetics is observed
rate = k x [nucleophile] x [alkyl halide]
Where k is the rate constant, concentrations of nucleophile and
alkyl halide presented in square brackets.
Example of SN2 Reaction
• rate = k[CH3Br][CH3COO–]
Example of SN2 Reaction
- -
CH3Cl + OH CH3OH + Cl
Effect of Alky group on SN2 Reaction
As the number of R groups on the carbon with the leaving group increases, the rate
of an SN2 reaction decreases.
• Methyl and 1ry alkyl halides undergo SN2 reactions with ease.
• 2ry Alkyl halides react more slowly.
• 3ry Alkyl halides do not undergo SN2 reactions.
Stereochemistry of SN2 reaction
The nucleophile approaches from the opposite side to the leaving group, forming B.
This is called backside attack.
In this example, the leaving group was drawn on the right, so the nucleophile attacks
from the left. results in inversion of configuration around the stereogenic center.
Stereochemistry of SN2 reaction
SN2 displacement reactions occur with inversion of configuration. For
example, if we treat (R)-2-bromobutane with sodium hydroxide, we obtain
(S)-2-butanol.
The SN1 Mechanism
It occurs in two steps and depends on the concentration of
alky halides.
The SN1 reaction exhibits first-order
kinetics.
rate = k[(CH3)3CBr]
The SN1 Mechanism
Example
The key features of the SN1 mechanism are:
Stereochemistry of SN1
SN1 give a racemic mixture of R and S configuration
Racemic mixture, also called racemate, a
mixture of equal quantities of two
enantiomers,
Predicting the Likely Mechanism of a Substitution Reaction.
1) The identity of the alkyl halide.
Methyl and 1° halides (CH3X and RCH2X) undergo SN2 reactions only.
3° Alkyl halides (R3CX) undergo SN1 reactions only.
2° Alkyl halides (R2CHX) undergo both SN1 and SN2 reactions. Other factors determine
the mechanism.
2) The identity of Nucleophile
Strong nucleophiles present in high concentration favor SN2 reactions (-OH, -OCH3,-SH).
Weak nucleophiles favor SN1 reactions (i.e. water, ROH)
3) The nature of the solvent
Polar protic solvents like H2O and ROH favor SN1 reactions.
Polar aprotic solvents favor SN2 reactions.