Types of Organic Reactions

1. Addition Reactions: A + B C
O

O
OH

HO

+ H 2O

OH
OH

HO

fumarate

malate

2. Elimination Reactions: D E + F
O

O
OH

HO

OH

HO

+ H2

O
fumarate

succinate

3. Substitution Reactions: G-H + I G-I + H

O

HO

O
OH

O
a-ketoglutarate

SCoA

HO

SCoA

OH

O
succinyl CoA

Types of Organic Reactions

4. Rearrangements: J K
O
HO

OH

CO2H

O
OH

citrate
i

CO2H
O

HO

OH
OH
i i
isocitrate

How do these reactions occur?

Why do these reactions occur?
We must explain how electrons are exchanged during the formation of
new bonds and breaking of old bonds.
bonds

How Reactions Occur

Symmetrical Bond Making/Breaking (homolytic process)
vs
Unsymmetrical Bond Making/Breaking (heterolytic process) - POLAR Reactions

Indicating Electron Movement in

Reaction
i Mechanisms
h i
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)

Polar Reactions
Opposite charges attract
Nucleophiles (electron rich sites, seek nucleus) - have lone pair of

electrons or C=C bond

H

O H

Cl

NH2

Electrophiles (electron poor sites, seek electrons) - have formal

positive charge or partial positive charge via bond dipole

Nucleophiles are synonymous with Lewis Bases,

Bases Electrophiles
are synonymous with Lewis Acids, Polar reactions are Lewis AcidBase reactions.
5

Nucleophiles and Electrophiles

Note that compounds can be nucleophilic and electrophilic. You
must look at specific atoms and what the compound is reacting with
to determine how it will react:
O OH

O H

O H

Judging relative 'strengths' of Nuc and E+

Strong Nuc
less stable anion
more stable anion
lone pair less EN atom
lone pair more EN atom
C=C
Weak Nuc

Strong E+
less stable cation
more stable cation
neutral atom incomplete octet
large partial positive atom
small partial positive atom
Weak E+
7

Drawing Reaction Mechanisms

Use of curved arrows to show electron movement in bond making
and bond breaking process. For polar reactions, electrons move as a
pair. Note that charges must also balance.
The
Th arrow goes from
f
the
th nucleophilic
l hili reaction
ti site
it tto th
the electrophilic
l t hili

reaction site

The nucleophilic site can be neutral or negatively charged

Drawing Reaction Mechanisms

The electrophilic site can be neutral or positively charged

The
h octet rule
l must be
b followed
f ll
d

(never have +2 or -2 charge on a single atom)

9

Drawing Reaction Mechanisms

+

O
+

O
+

Br

10

Drawing Reaction Mechanisms

O
+

O
+

Br

+ Br

11

An Example of a Polar Reaction:

Addition
ddi i off HBr to Ethylene
h l
HBr adds to the p
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

12

Mechanism of Addition of HBr to

Ethylene
h l

13

Why Reactions Occur

All organic
g
reactions we will studyy will reach equilibrium
q
that favors the
more stable side. In most cases, these will be reaction products as written
from left to right (note, however, sometimes you must predict which side is
favored as in acid-base reactions).

G = - RT ln Keq = H - TS
If Keq > 1, energy is released to the surroundings
(exergonic reaction, negative value of G, reaction favored)
If Keq
eq < 1,, energy
e e gy iss absorbed
abso bed from
o thee su
surroundings
ou d gs
(endergonic reaction, positive value of G, reaction not favored)
Energy changes in a reaction are illustrated by Energy Diagrams

14

Reaction Energy Diagrams

One Stepp Reactions:

Exergonic (- G)
(th
(thermo
favored)
f
d)

Endergonic (+ G)
(th
(thermo
nott favored)
f
d)
15

Reaction Energy Diagrams

Multiple
p Stepp Reactions:

16

Reaction Energy Diagrams

The highest
g
energy
gy point
p

in a reaction step is called

the transition state
The
Th energy needed
d d to
t go
from reactant to transition
state is the activation
energy (G)

Br
H
H

17

Reaction Energy Diagrams

If a reaction occurs in more

than
h one step, it
i must involve
i
l
species that are neither the
reactant nor the final product
These
Th
are called
ll d reaction
ti
intermediates or simply
intermediates
Each
E h step has
h its
i own free
f
energy of activation
The complete diagram for the
reaction
ti shows
h
the
th free
f energy
changes associated with an
intermediate

18

Estimating G from H
H = (energy needed to break bonds) - (energy released when bonds form)

Bonds Breaking
C=C = 611 kJ/mol
H B = 366 kJ/
H-Br
kJ/moll

Bonds Forming
C-C = 355 kJ/mol
C B = 285 kJ/
C-Br
kJ/moll
C-H = 420 kJ/mol

H = (977 kJ/
kJ/mol)
l) - (1060 kJ/mol)
kJ/ l) = - 83 kJ/
kJ/moll (exothermic)
( th
i )

19

20

21

22

Are the following reactions

thermodynamically
h
d
i ll favored?
f
d
+

O
+

O
+

Br

+ Br

23