Organic Reactions

Kinds of Reactions
Mechanisms (polar, non-polar)
Bond Dissociation Energy
Reaction Profiles
 Types of Reactions
Addition Reactions
H H Br
H
C=C + HBr C C
H H
H H
H H
Elimination Reactions
H Br
H H
C C H + NaOH C=C + H2O
H
H H H H + NaBr
 Types of Reactions
Substitution:
Polar
H H
H + KCN H + KBr
Br NC
H H
Non-polar
light (h)
CH4 + Cl2 CH3Cl + HCl
Rearrangement
 Substitusi polar

Substitusi polar

adisi

Substitusi nonpolar
 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 (menentukan
produk yang terbentuk paling cepat). One can predict
how the rate will change with changing conditions.
(dapat memprediksi bagaimana tingkat laju reaksi
akan berubah dengan adanya perubahan kondisi)
Reaction Profile (Exothermic)
a b
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

+ 435 - 431

= - 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 CH2 CH3
CH3 C H + Cl . CH3 C H + CH3 C.

CH3 CH3 CH3

.
CH2 CH2Cl
CH3 C H + Cl2 CH3 C H 65% + Cl .

CH3 CH3
CH3 CH3
CH3 C. + Cl2 CH3 C Cl 35% + Cl .

CH3 CH3
Monoklorinasi dari C5H12 yang
menghasilkan 1 jenis klorinasi

2,2-dimetil propana

2-klor-,2-dimetil propana
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
h
F C Cl F C. + Cl .
ultraviolet
Cl Cl

i) Cl . + O3 ClO. + O2

ii) ClO . + O
. Cl . + O2

net reaction O3 + O. 2 O2
 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 Two-
Step Mechanism
 How Many Mechanistic Steps?
How Many Intermediates?
How Many Transition States?
Which Step is Rate-Determining?