BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

Lecture 40
Electrophilic Addition Reaction
1 BITS Pilani, Pilani Campus
Electrophilic addition

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MECHANISM: STEP-BY-STEP ACCOUNT OF WHAT HAPPENS

:X-
X
step 1 step 2
C C C C C C
Slow + Fast
E E

E+
TS1 intermediates are formed during
Intermediate a reaction but are not products
intermediate
TS2
E TS1 TS2
EA2
X -
N
E
R
G
EA1
+
Y C C C C
+
Substrate DH E + E
product
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Carbocation Stability
R
R
C+ R +
CH R R +
CH2

R C R
R + R

Most > R CH R
+

> R +
CH 2 Least
stable stable
tertiary secondary primary
Empty p-orbital
electrons in an adjacent C-H s bond
help to stabilize the positive charge of
the carbocation by proximity (overlap)
-HYPERCONJUGATION
Alkenes Addition of water

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Addition of Hydrogen Halides: Markovnikovs rule

Addition is regioselective
Markovnikovs Rule
In the ionic addition of an acid to the carbon-carbon double
bond of an alkene, the hydrogen of the acid attaches itself to
the carbon atom which already holds the greater number of
hydrogens.
Them that has, gets!
The richer get richer!
(V. W. Markovnikov)
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Regioselectivity of HBr addition

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Stereochemistry of HX Addition
Rearrangement: Intermediate carbocation rearranges to more stable
carbocation

Stereochemistry

Carbocations are planar -> attack from both sides possible!! 7

Anti-Markovnikovs addition of HBr

When alkenes are having trace amounts of

peroxides then, reaction of HBr follows anti -
Markovnikov addition.
peroxides Rad (radical)
rad + H : Br rad : H + Br

Essence of the mechanism is that hydrogen and bromine add to

the double bond homolytically rather than heterolytically.
The intermediate is a free radical rather than a carbocation.
Like halogenation of alkanes, this is a chain reaction, this time
involving addition rather than substitution. 8
Addition of ICl and H2SO4
Addition of ICl

Addition of H2SO4 H
H H
O H
O O
H S O S O
O O
O O

very reactive
not favorable

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Addition of H2SO4

A Better Picture This is an alcohol synthesis

H
catalyst H
H O
O
+ S
H S O O
O O
O H2O H H
O
O
H H
H O
H H
O O
H H

Oxonium ion
O
H H

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Hydration of alkenes
Predict the product and draw a mechanism.

H2SO4
H2O HO
OH
H
H O
H H
O H
O
H CH3
H

CH3 O
the CH3 moves! CH3 H 11
H
Consequence of carbocation rearragement
The occurrence of carbocation rearrangements
limits the utility of alkene hydrations as a
laboratory method for preparing alcohols.

Modern statement of Markovnikov rule

In the ionic addition of an unsymmetrical
reagent to a double bond, the positive portion
of the adding reagent attaches itself to a
carbon atom of the double bond so as to yield
the more stable carbocation as an intermediate.
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Oxymercuration-demercuration

H2SO4
H2O
HO
OH
Hg(OAc)2
H2O
O
O
CH3
O
CH3
O Oxymercuration Hg
+ OAc
Hg

H
O O
H
H H
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 .
Oxymercuration-demercuration
The Hg+2 is reduced to
Hg(0) by BH4-.

H
+ Hg(0)
O
H

Oxymercuration and simple acid catalysis

have the same regiochemistry

OH

But what if you want the primary alcohol? OH

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Hydroboration
BH3 addition to an alkene
HH
+ BH3 BH2
H B

H
H B
H H H 3C
H B
H hydride shift
Preferred Path
or H
H
B H
H3C H3C

First approach,
not very stable
H 3C

hydride shift
Sterics is also very important, helping to direct the regiochemistry
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Hydroboration-Oxidation
+ BH3 BH2

tripropylborane

H
O

O
B

Hydroboration gives anti Markovnikovs alcohol

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Stereochemistry of Hydroboration
Hydroboration regiochemistry is opposite to Markovnikov
orientation
OH is added to carbon with most Hs
H and OH add with syn stereochemistry, to the same face of the
alkene.
STEREOSPECIFIC

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Summary of Alkene Hydration Methods
1,2-hydride
H shift
H

OH OH
H+ + H
H
H2O major
rearrangement
1. Hg(OAc)2, THF-H2O OH

2. NaBH4, OH- H
Markovnikov addition
H
1. BH3-THF anti-Markovnikov,
OH
syn addition of H2O
2. H2O2, OH-

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