Organic Reactions

Kinds of Reactions
Mechanisms (polar, non-polar)
Bond Dissociation Energy
Reaction Profiles

Types of Reactions
Addition Reactions
H
C=C
H

H
+ HBr
H

Br
C

H
H

Elimination Reactions
H
H

Br
C

H + NaOH
H

H
C=C
H

H
+ H2O

H + NaBr

Types of Reactions
Substitution:
Polar
H
H
H

H
Br

+ KCN

NC

H
H

Non-polar
CH4 + Cl2

light (h)

CH3Cl + HCl

+ KBr

Rearrangement

Definitions
Mechanism: Complete step-by-step of exactly which
bonds break and which bonds form and in what
order.
Thermodynamics: The study of the energy changes
that occur in chemical transformations. This allows
for comparison of stability of reactants and products.
Kinetics: The study of reaction rates, determining
which products are formed most rapidly. One can
predict how the rate will change with changing
conditions.

Reaction Profile (Exothermic)

a

rate = kr[A] [B]

2nd Order Reaction

CH3Br + OH

CH3OH + Br

Rate = k[CH3Br][OH ]
second order rate kinetics

1st Order Reaction

(CH3)3CBr + H2O

(CH3)3OH + HBr

Rate = k[(CH3)3CBr]
First order rate kinetics

Bond Breaking:
Non-polar and Polar

Bond Forming:
Non-polar and Polar

Non-polar Reaction Involves

Free Radicals

Free Radicals are Neutral, but

Electron-Deficient

Free Radical Chlorination

Experimental Evidence Helps

to Determine Mechanism
Chlorination does not occur at room
temperature in the dark.
The most effective wavelength of light is
blue that is strongly absorbed by Cl2 gas.
The light-initiated reaction has a high
quantum yield (many molecules of product
are formed from each photon of light).

Free Radical Species are Constantly

Generated Throughout the Reaction
Propagation

Termination: Reaction of any 2 Radicals

Enthalpy of Reaction (Ho)

Measures Difference in Strength of
Bonds Broken and Bonds Formed
Bond Dissociation Energy

Ho = bonds broken-bonds formed

Hrxn = -105 kJ/mol

= + 4 KJ/mol

- 431

+ 435

= - 109 KJ/mol

+ 242

- 351

Why Not This Mechanism?

Chlorination of Propane

40%
60%

Hs are not abstracted at the same rate.

Reactivity of Primary (1o) H abstraction
40%
= 6.7
6H
Reactivity of Secondary (2o) H abstraction
60% =
30
2H
Rate of 2o H abstraction : 1o H abstraction
= 4.5:1

Chlorination of Methylpropane
CH3
CH3

H + Cl .

CH3

CH3

CH3

CH2Cl
H

+ Cl2

CH3

CH3

CH3

CH3

CH3

C.
CH3

C.
CH3

CH3

CH2
C

H + CH3

CH3

CH3

CH2

+ Cl2

CH3

C
CH3

H 65% + Cl .

Cl 35% + Cl .

Tertiary Hs removed 5.5 times more

readily than primary Hs in
chlorination reactions

3 Radicals are Easiest to Form

o

Stability of Free Radicals

Bromination is Very Selective

RDS in Bromination is highly

endothermic

Consider the free radical monochlorination of

2,2,5-trimethylhexane. Draw all of the
unique products (ignore stereoisomers; use
zig-zag structures please) and predict the ratio
or percent composition of the products.
The relative reactivity of H abstraction in a
chlorination reaction: 1o: 2o: 3o = 1: 4.5: 5.5

Chlorofluorocarbons and the

Depletion of Ozone
h

O3

O2 + O .

a CFC
F
F

F
h
ultraviolet

Cl

Cl

Cl
i)

Cl .

ii)

ClO . + O

net reaction

C.

+ O3

O3 + O.

ClO.

+ O2

Cl . + O2
2 O2

Cl .

Polar Reactions:
Nucleophiles & Electrophiles

Nucleophiles are Bases

Electrophiles are Acids

Addition of HBr to Ethylene

Reactions Often Go Through

Intermediates

Transition State

Addition Reaction is a TwoStep Mechanism

How Many Mechanistic Steps?

How Many Intermediates?
How Many Transition States?
Which Step is Rate-Determining?