Ionic Reactions

Nucleophilic Substitution
Reactions of Alkyl Halides
 INTRODUCTION
Mechanism of the reaction
The description of the step-by-step process by which
reactants are changed into products

Curved arrows
To help us understand a mechanism
Show which bonds are formed and which are broken.
 INTRODUCTION

An arrowhead with two barbs An arrowhead with one barb

the simultaneous The movement of one
movement of two electrons electron
(an electron pair)

The curved arrows show how the electrons flow, they are
drawn from an electron-rich center (at the tail of the
arrow) to an electron-deficient center (at the point of
the arrow) intramolecular and intermolecular
Using Curved Arrows in Polar
Reaction Mechanisms
Using Curved Arrows in Polar
Reaction Mechanisms
Using Curved Arrows in Polar
Reaction Mechanisms
 EXERCISE 1

Supply the curved arrows necessary for the

following reactions:
 Organic Halides
The halogen atom of an alkyl halide is attached
to an sp3-hybridized carbon
Organic Halides
 Organic Halides
Naming Alkyl Halides
EXERCISE 2
Nucleophilic Substitution Reactions
 NUCLEOPHILE
A nucleophile : a substance that is nucleus-loving.
(nucleus : positively charged.)
has a negatively polarized, electron-rich atom
Can form a bond by donating a pair of electrons to a
positively polarized, electron poor atom.
Can be either neutral or negatively charged
Ex : ammonia, water, hydroxide ion, and chloride ion
Nucleophilic Substitution Reactions

A good leaving group is a substituent that can leave as a

relatively stable, weakly basic molecule or ion
 Kinetics of a Nucleophilic Substitution
Reaction: An SN2 Reaction

The reaction is bimolecular: two species are involved in the

step whose rate is being measured
SN2 reaction, meaning substitution, nucleophilic,
bimolecular
The nucleophile approaches the carbon bearing the leaving
group from the back side, that is, from the side directly
opposite the leaving group
The substrate carbon atom undergoes inversion
Single step (without any intermediates) through an unstable
arrangement of atoms called the transition state
 Kinetics of a Nucleophilic Substitution
Reaction: An SN2 Reaction

Concerted reaction: bond forming and bond breaking

occur in concert (simultaneously) through a single
transition state
Kinetics of a Nucleophilic Substitution
Reaction: An SN2 Reaction
Transition State Theory: Free-Energy Diagrams

Exergonic : A reaction that proceeds with a negative free-energy

change (releases energy to its surroundings)
The Stereochemistry of SN2 Reactions
The Stereochemistry of SN2 Reactions
The Effect of the Structure of the Substrate
The Effect of the Structure of the Substrate
 SN1 Reaction

This reaction is said to be unimolecular (first order) in

the rate-determining step
SN1 reaction : substitution, nucleophilic, unimolecular
SN1 Reaction
SN1 Reaction
 Carbocations

Carbocations are trigonal planar

The p orbital of a carbocation contains no electrons, but
it can accept an electron pair when the carbocation
undergoes further reaction
 Carbocations

Hyperconjugation involves electron delocalization (via partial orbital

overlap) from a filled bonding orbital to an adjacent unfilled orbital
The Stereochemistry of an SN1 Reaction
The Stereochemistry of an SN1 Reaction
The Stereochemistry of an SN1 Reaction
 Solvolysis
The SN1 reaction of an alkyl halide with water is an example of
solvolysis.
A solvolysis reaction : a nucleophilic substitution in which the
nucleophile is a molecule of the solvent (solvent lysis: cleavage
by the solvent).
The solvent is water the reaction a hydrolysis
The solvent is methanol a methanolysis.
Summary
Summary
Summary
 EXERCISE 3

Show how you might use a nucleophilic substitution

reaction of 1-bromopropane to synthesize each of the
following compounds.
THANK YOU