CHAPTER 2: INTRODUCTION TO ORGANIC REACTION

OPPOSITE CHARGES ATTRACT

Electrostatic potential maps for BF3, NH3, and the product that results from reaction between them.
Attraction between the strongly positive region of BF3 and the negative region of NH3 causes them
to react. The electrostatic potential map for the product for the product shows that the fluorine
atoms draw in the electron density of the formal negative charge, and the nitrogen atom, with its
hydrogens, carries the formal positive charge
 CHAPTER 2: AN INTRODUCTION TO ORGANIC
REACTIONS:

 In a clock the hands move but the mechanism behind the face is what
causes the movement
 In an organic reaction, we see the transformation that has occurred.
The mechanism describes the steps behind the changes that we can
observe
 Reactions occur in defined steps that lead from reactant to product
CHAPTER 2: INTRODUCTION TO ORGANIC REACTION

REACTIONS AND THEIR MECHANISMS

 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-BOND BREAKING
BOND FORMATION

Heterolytic bond dissociation (heterolysis): electronically

unsymmetrical bond breaking produces ions

 Both electrons from the bond that is broken become associated with one
resulting fragment
 A common pattern in reaction mechanisms
CHAPTER 2: INTRODUCTION TO ORGANIC REACTION
CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-BOND BREAKING
BOND FORMATION

Homolytic bond dissociation (homolysis): electronically

symmetrical bondbreaking produces radicals

Radical species

 One electron comes from each fragment

 No electronic charges are involved
 Not common in organic chemistry
 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-BOND BREAKING
BOND FORMATION

 One fragment supplies two electrons

 One fragment supplies no electrons
 Combination can involve electronic charges
 Common in organic chemistry
CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-BOND BREAKING
BOND FORMATION

 One electron comes from each fragment

 No electronic charges are involved
 Not common in organic chemistry
 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION- Indicating
Steps in Mechanisms

 Curved arrows indicate breaking and forming

of bonds
 Arrowheads with a complete head indicate
heterolytic and heterogenic steps (called
‘polar processes’)
 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION- Indicating
Steps in Mechanisms

 Curved arrows indicate breaking and forming

of bonds
 Arrowheads with a “half” head (“fish-hook”)
indicate homolytic and homogenic steps
(called ‘radical processes’)
 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-
Polar Reactions and How They Occur

 Molecules can contain local unsymmetrical electron distributions due to

differences in electronegativities
 This causes a partial negative charge on an atom and a compensating partial
positive charge on an adjacent atom
 The more electronegative atom has the greater electron density
 Example: Nucleophilic addition of a carbonyl group
 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-
Generalized Polar Reactions

 An electrophile (+), an electron-poor species, combines with a nucleophile

(-), an electron-rich species
 An electrophile is a Lewis acid
 A nucleophile is a Lewis base
 The combination is indicated by a curved arrow from a nucleophile to an
electrophile
 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-
Generalized Polar Reactions

 HBr adds to the  part of C-C double bond

 The  bond is electron-rich, allowing it to function as a nucleophile
 H-Br is electron deficient at the H since Br is much more electronegative,
making HBr an electrophile


Br
H
Example of an
electrophilic addition
 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-
Using Curved Arrows in Polar Reaction Mechanisms

 Curved arrows are a way to keep track of changes in bonding in polar

reaction
 The arrows track “electron movement”
 Electrons always move in pairs
 Charges change during the reaction
 One curved arrow corresponds to one step in a reaction mechanism
 The arrow goes from the nucleophilic reaction site to the electrophilic
reaction site
 The nucleophilic site can be neutral or negatively charged
 The electrophilic site can be neutral or positively charged
 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-
Acid Base reaction

THE BRØNSTED-LOWRY DEFINITION OF ACIDS AND BASES

Acid is a substance that can donate (or lose) a proton; Base is a

substance that can accept (or remove) a proton

Hydrogen chloride, a very strong acid, transfer its proton to water

Water acts as a base and accepts the proton

 CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-
Acid Base reaction

THE LEWIS DEFINITION OF ACIDS AND BASES

Lewis acid-base theory: in 1923 proposed by G. N. Lewis

1) Acid: electron-pair acceptor

2) Base: electron-pair donor
CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-
THE STRENGTH OF ACIDS AND BASES: Ka AND pKa

In a 0.1 M solution of acetic acid at 25 °C only 1% of the acetic acid

molecules ionize by transferring their protons to water

An aqueous solution of acetic acid is an equilibrium:

General expression for any acid

CHAPTER 2: INTRODUCTION TO ORGANIC REACTION-
THE STRENGTH OF ACIDS AND BASES: Ka AND pKa

The larger the value of the pKa, the weaker is the acid

The larger the pKa of the conjugate acid, the stronger is the base