Types of Organic Reactions

1. Addition Reactions: A + B → C

O O OH
OH + H 2O OH
HO HO
O O
fumarate malate

2. Elimination Reactions: D → E + F

O O
OH OH + H2
HO HO
O O
succinate fumarate

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

O O O O
+ SCoA + OH
HO OH HO SCoA
O O
a-ketoglutarate succinyl CoA

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 Types of Organic Reactions

4. Rearrangements: J → K
CO2H
O OH O O O

HO OH HO OH
CO2H
OH
citrate
i 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

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 How Reactions Occur

Symmetrical Bond Making/Breaking (homolytic process)

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

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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’)

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Polar Reactions
Opposite charges attract

 Nucleophiles (electron rich sites, seek nucleus) - have lone pair of

electrons or C=C bond
O
O O H Cl NH2
H H

 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 Acid-
Base reactions.
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 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 O H

Judging relative 'strengths' of Nuc and E+

Strong Nuc Strong E+
less stable anion less stable cation
more stable anion more stable cation
lone pair less EN atom neutral atom incomplete octet
lone pair more EN atom large partial positive atom
C=C small partial positive atom
Weak Nuc Weak E+

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 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

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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)

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Drawing Reaction Mechanisms

O
+
Br

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 Drawing Reaction Mechanisms

O O

O O
+ + Br
Br

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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

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Mechanism of Addition of HBr to
Ethylene
h l

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 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).

Gº = - RT ln Keq = H - TS

If Keq > 1, energy is released to the surroundings
(exergonic reaction, negative value of Gº, 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 Gº, reaction not favored)

Energy changes in a reaction are illustrated by Energy Diagrams

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 Reaction Energy Diagrams

One Stepp Reactions:

Exergonic (- G) Endergonic (+ G)

(th
(thermo favored)
f d) (th
(thermo nott favored)
f d)

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 Reaction Energy Diagrams

Multiple
p Stepp Reactions:

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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 C C H

H H

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 Reaction Energy Diagrams
 If a reaction occurs in more
than
h one step, iti 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

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 Estimating G from H

H = (energy needed to break bonds) - (energy released when bonds form)

Bonds Breaking Bonds Forming

C=C = 611 kJ/mol C-C = 355 kJ/mol
H B = 366 kJ/
H-Br kJ/moll 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 )

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 Are the following reactions
thermodynamically
h d i ll favored?
f d

O O

O O
+ + Br
Br

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