John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 3
An Overview of
Organic Reactions

Credits to Paul D. Adams • University of Arkansas

 General Chemistry 2

Organization of Organic
Reactions
Organic reactions can be organized in 2 ways:
 By what kind of reactions that occur (Section 3.1)

 By how reactions occur, or in other words, reaction

mechanism (Section 3.2)

Thus, organic chemistry is a beautifully logical

subject that is unified by a few broad themes or a
few fundamental ideas. Then learning organic
chemistry will be easier with lesser memorization
to do!
 General Chemistry 2

3.1 Kinds of Organic Reactions

1. Addition reactions
 two molecules combine or add together to form a
single new product with no atoms “left over”, i.e.,

A + B → C
E.g.
 General Chemistry 2

3.1 Kinds of Organic Reactions

(Continued)
2. Elimination reactions
 The opposite of addition reactions
 A single reactant splits into two products

A → B + C
E.g.
 General Chemistry 2

3.1 Kinds of Organic Reactions

(Continued)
3. Substitution reactions
 Two reactants exchange parts to give two new
products

A—B + C—D → A—C + B—D

E.g.
 General Chemistry 2

3.1 Kinds of Organic Reactions

(Continued)
4. Rearrangement reactions
 A single reactant undergoes reorganization of bonds
and atoms to get an isomeric product

A → B (an isomer of A)
E.g.
 General Chemistry 2

3.2 How Organic Reactions Occur:

Mechanisms

 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
 General Chemistry 2

About Reaction Mechanisms

1 All chemical reactions involve bond breaking and bond
making.
2. The bond breaking and bond making may either be:
 Symmetrical

- i.e., one electron remains with each product fragment in

bond breaking (homolytic) AND one electron is donated to
a new bond by each reactant in bond making
(homogenic)
- associated with radical reactions
 General Chemistry 2

Types of Steps in Reaction

Mechanisms
 Unsymmetrical
– i.e., an electron bonding pair remains with one product fragment
thus leaving the other fragment with vacant orbital (heterolytic)
AND the bonding electron pair is donated to the new bond by one
reactant (heterogenic).
- associated with polar reactions
 General Chemistry 2

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’)
 Arrowheads with a complete head indicate
heterolytic and heterogenic steps (called ‘polar
processes’)

Reminder!!!
• Half-headed arrow refers to 1 electron.
• Full headed arrow refers to 2 electrons.
 General Chemistry 2

3.3 Radical Reactions

 Not as common as polar reactions
 Radicals react to complete electron octet of valence
shell
 A radical can break a bond in another molecule and
abstract a partner with an electron, giving substitution
in the original molecule

A radical can add to an alkene to give a new radical, causing

an addition reaction
 General Chemistry 2

Steps in Radical Substitution

Reactions
 Three types of steps:
 Initiation – homolytic formation of two reactive species with
unpaired electrons

 Propagation – reaction with molecule to generate radical

 Example - reaction of chlorine radical with methane to
give HCl and CH3●
 General Chemistry 2

Steps in Radical Substitution

 Termination – combination of two radicals to

form a stable product:
 General Chemistry 2

3.4 Polar Reactions

 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
 Elements such as O, F, N, Cl are more electronegative
than carbon
 General Chemistry 2

Polarity Patterns in Some Common

Functional Groups
 General Chemistry 2

Polarizability
 Polarization is a change in electron distribution
as a response to change in electronic nature of
the surroundings
 Polarizability is the tendency to undergo
polarization
 Polar reactions occur between regions of high
electron density and regions of low electron
density
 General Chemistry 2

Generalized Polar Reactions

 An electrophile, an electron-poor species
(often positively charged), combines with a
nucleophile, an electron-rich species (often
negatively charged)
 The combination is indicated with a curved
arrow from nucleophile to electrophile
 General Chemistry 2

Some Nucleophiles and

Electrophiles
 General Chemistry 2

3.5 An Example of a Polar Reaction:

Addition of HBr to Ethylene
 HBr adds to the  part of a 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
 General Chemistry 2

Mechanism of Addition of HBr to

Ethylene
 HBr electrophile is attacked
by  electrons of ethylene
(nucleophile) to form a
carbocation intermediate and
bromide ion
 Bromide adds to the positive
center of the carbocation,
which is an electrophile,
forming a C-Br  bond
 The result is that ethylene and
HBr combine to form
bromoethane
 All polar reactions occur by
combination of an electron-
rich site of a nucleophile and
an electron-deficient site of an
electrophile
 General Chemistry 2

3.6 Using Curved Arrows in Polar

Reaction Mechanisms
 Curved arrows are a way to keep track of changes in
bonding in a polar reaction
 The arrows represent the “electron movement”
 Electrons always move in pairs
 Charges change during the reaction
 One curved arrow corresponds to one step in a reaction
mechanism
 General Chemistry 2

Rules for Using Curved Arrows

 The arrow goes from the nucleophilic reaction site to the electrophilic
reaction site

 The nucleophilic site can be neutral or negatively charged

 General Chemistry 2

Rules for Using Curved Arrows

(Continued)
 The electrophilic site can be neutral or positively
charged

 The octet rule should be followed

 General Chemistry 2

Self-test Problems
1. Classify these reactions as additions, eliminations,
substitutions or rearrangements:
(a) CH3Br + KOH → CH3OH + KBr
(b) CH3CH2OH →H2C=CH2 + H2O
(c) H2C=CH2 + H2 → CH3CH3

2. Identify these species as to whether they behave as

electrophiles or nucleophiles:
(a) H+ (b) OH− (c) NH3 (d) Mg2+

3. What product would you expect from reaction of HBr with

cyclohexene? (You can draw the product instead of
naming them).